IOGCA 2019 Conference Proceedings PDF

Conference Proceedings (IOGCA 2019), Ahmadabad
Content (List of Full Papers Submitted)
Paper No. Title Page No.
IOGCA(2019)/1 Title: “Importance of Controlling Fluid Loss & Settling Behavior 4

of Weighted Spacers in HPHT conditions”
-Abhinav Hazra, R.K. Raigar, Dr. Kishori Lal, H.S Negi & Pradeep
Kumar, Institute of Drilling Technology, Oil and Natural Gas
Corporation Limited Dehradun.
IOGCA(2019)/2 Title: “Robust design for Cement degradation in CO2under HPHT 14
Environment.”
-Abhinav Hazra, Dr Kishori Lal, R. K Raigar, Parvinder Singh, H.S
Negi & Pradeep Kumar, Institute of Drilling Technology, ONGC
IOGCA(2019)/3 Title: “Experimental investigation of Zwitterionic Surfactant for 25
Chemical Enhanced Oil Recovery in Sandstone and Carbonate
Reservoirs”
-Amit Kumar, Ajay Mandal, Petroleum Engineering Department,
IIT(ISM) Dhanbad
IOGCA(2019)/4 Title: “Study the Effect of Naturally Derived Products on 33
Asphaltene Solubilisation in Petroleum Reservoir Rock”
-Arnab Mandal, Barasha Deka, Rohit Sharma, Vikas Mahto,
Department of Petroleum Engineering, Indian Institute of Technology
(Indian School of Mines)
IOGCA(2019)/5 Title: “Application of Nanotechnology in Cementing High Pressure 39
High Temperature Oil & Gas wells.”
-Dr KishoriLal and Pradeep Kumar, Institute of Drilling Technology,
Oil and Natural Gas Corporation Limited,
IOGCA(2019)/6 Title: “Application of Thermally Activated Polymer for various 49
Drilling Complications”
-Dr KishoriLal, Dr Deepak Painuly and Pradeep Kumar, Institute of
Drilling Technology, Oil and Natural Gas Corporation Limited,
Dehradun.
IOGCA(2019)/7 Title: “Thermic Fluid Applications & Potential in Gujarat Market” 56
-Dr Rajiv Srivastava, Indian Oil Corporation
IOGCA(2019)/8 Title:“Efficient Breaking of Crude Oil Emulsions: A Proper Mix of 63
Engineering Science and Art”
-Dr A.K. Saxena, ONGC, Vadodara
IOGCA(2019)/9 Title: “Monitoring of Marine Environment by ABC (Abundance- 70
Biomass Curve) analysis - A Case Study on Eastern Offshore area
of Bay of Bengal”
-G.L.Das, Nikita Chiripal, Atul Garg, IPSHEM, ONGC
IOGCA(2019)/10 Title: - “Some Challenges and Experiences in Upstream Chemical 75
Treatment”
- Dr. Sanjay Misra, ADNOC
IOGCA(2019)/11 Title: “Effect of Reservoir Minerals and Fluids on Alkali 80
Transport”
-Himanshu Sharma, Department of Chemical Engineering, Indian
Institute of Technology Kanpur
Organized By MatCorr Page 1

IOGCA(2019)/12 Title: “Linear and Poly Alpha Olefins: Precursors to Synthetic 89

Lubricants”
-Gopal Tembe, Consultant, Reliance Technology Group, Reliance
Industries Limited
IOGCA(2019)/13 Title: "Silane Coated Silica Nanop Articles As An Additive for 95
Water Based Drilling Fluid"
-Himanshu Kesarwani1, Viswakanth Kandala2, Shivanjali Sharma*1,
1. Rajiv Gandhi Institute of Petroleum Technology,,2. Indian Institute
of Petroleum and Energy, Visakhapatnam
IOGCA(2019)/14 Title: “Kinetic Study of Exothermic Reaction Mixture for Paraffin 103
Removal”
-M. Q. Zaman, J. Joseph, Tej Pal, M. Mandal, T. K. Banerjee, B. Deuri,
Institute of Oil and Gas Production Technology
IOGCA(2019)/15 Title: “Green Corrosion Inhibitor for Biofuels Blended Gasoline 121
and Diesel: A Quality Control Viewpoint”
-P. K. Mondal, Dr. Sourav Bhunya, Haldia Installation, Indian Oil
Corporation Limited & Retired Prof. B.S. Saraswat, Department of
Chemistry, School of Sciences, Indira Gandhi National Open
University
IOGCA(2019)/16 Title: “Series of Failure and Success Trails of Offshore Well 132
Cement Plugs Leads to challenge of effective NDDF removal,
Optimization of WOC & Reduction in NPT-Case History.”
-R.K. Raigar, Dr.Kishori Lal, AbhinavHazra, Parvinder Singh &
Pradeep Kumar, Institute of Drilling Technology, Oil and Natural Gas
Corporation Limited Dehradun.
IOGCA (2019)/17 Title: “Application of Solvents for use in different way” 141
-Tilak Singh, Dileep Kumar, JM Karnik and R M Patil, Oil and Natural
gas Corporation
IOGCA(2019)/18 Title: “Inhibition effect of salts CaCO3 and MgCO3 on the kinetics 148
of Methane Hydrates”
-Ekta Chaturvedi, Ajay Mandal, Petroleum Engineering Department,
IIT (ISM), Dhanbad
IOGCA(2019)/19 Title: “Delaying the Onset of Asphaltene Flocculation Using 155
Asphaltene Inhibitors”
-Min Wang, Helen Sarginson, Bethan Warren, Craig Davies, Croda
IOGCA(2019)/20 Title: “Influence Of Guar Gum And BN Nanoparticles On 163
Rheology Of Drilling Fluid For Hydrate Bearing Sediments”
-Moumita Maiti, Ajoy Kumar Bhaumik, Ajay Mandal, Indian Institute
of Technology (ISM)
IOGCA (2019)/21 Title: “Sustainable Model for The Future Oil And Gas Industry” 171
-Rathnabai B, Sivashankari S, Department Of Petroleum Engineering,
Dhaanish Ahmed College of Engineering
IOGCA (2019)/22 Title: “Enhanced Oil Recovery (EOR): From Lab Screening to 176
Field Implementation – Connecting the Dots”
-Neeraj Rohilla, Christopher W. Nelson, Pete Rozowski, the Dow
Chemical Company

IOGCA(2019)/23 Title: “Drilling Fluid Design As A Relacement Of Kcl” 185

-Bishwjeet Binwal, Noida Institute of Engineering and Technology
IOGCA (2019)/24 Title: “Solutions to the carryover issues in the LPG Treating units: 191
A case study”
-S. K. Ganguly1,*, S. Kumar1, C. B. Mazumdar2 & A. Ray1, 1CSIR-
Indian Institute of Petroleum, & 2Department of Chemical Engineering,
Indian Institute of Technology
IOGCA (2019)/25 Title: “Future of the Oil and Gas Industry (Apply Data Science to 198
Analyze the Reservoir’s Hydrocarbon Content)”
-Syed Inayathulla, Khaja Abdul Rahman, Dhaanish Ahmed College of
Engineering,
IOGCA (2019)/26 Title: “Rheology and Microstructure Behaviors of Zwitterionic- 206
Anionic Surfactant for Fracturing”
-Silvia John Mushi, Wanli Kang, Hongbin Yang, Pengxiang Wang,
Xiaoyu Hou, China University of Petroleum
IOGCA (2019)/27 Tilte: “Synthesis of Newly Developed Re-Assembling, Self-Healing 223
Nanocomposite PPG (R-PPG) For Permeability Modification in
Heterogeneous Reservoirs”
-Seth Oppong Agrippa, Milan Mandal, and Keka Ojha,Indian Institute
of Technology (ISM), Dhanbad
IOGCA(2019)/28 Title: "Speciality Chemicals usage in the Crude Oil Refinery and 231
Oil fields and its related R&D and application tests in Laboratory"
-Sanjayendu Bikash Gope, TCG Life Sciences
IOGCA(2019)/29 Title: “Application of Low Salinity Water Flooding: Effect of 244
Dilution on Sea Water in Carbonate reservoirs”
-Rohit Kumar Saw, Ajay Mandal, IIT(ISM) Dhanbad
IOGCA (2019)/30 Title: “Trend Analysis of Heavy Metals, Ni and Pb, in Marine 252
Sediments – A Case Study around ONGC’s Western Offshore
Installations inMumbai High Region, Arabian Sea”
-Nikita Chiripal, G. L. Das, Atul Garg, IPSHEM- ONGC
IOGCA (2019)/31 Title: “Role of low dosage hydrate inhibitors for the control of 260
hydrate formation in oil and gas field operations: an overview”
-Vikas Mahto, Barasha Deka, Bineet K. Tripathi, A. K. Misra, M. V.
Lall, Gaurav Dixit, Mohinish Deepak, IIT (ISM), Dhanbad,
IOGCA (2019)/32 Title: “Effect OfImidazolium Based Ionic Liquid On Interfacial 268
And Wettability Alteration Behavior For Application In Enhanced
Oil Recovery”
-Prathibha Pillai, Ajay Mandal, IIT(ISM) Dhanbad
IOGCA (2019)/33 Title: “Rheological Study of Slick water Fluid Systems Consisting 276
of High-Vis Friction Reducers Additives for Hydraulic Fracturing
Applications”
-Navneeth Kumar Korlepara, Sandeep D. Kulkarni, Sumanth Ruttala,
Ashok Deva Kumar, Sree Karthik Dangeti, IIPE Vizag, Avinash Kumar
Singh, IIT Kharagpur
IOGCA (2019)/34 Title: “Crude Oil Flow Assurance Water Base Surfactant – A Case 285
Study Conducted On A Heavy Waxy Crude Oil At Various
Temperature Range.”
-Mr Noor Hisham Bin Ab Hamid, Euro-Circuit Technology Sdn Bhd

Paper No. IOGCA (2019)/1
Title: “Importance of Controlling Fluid Loss & Settling Behavior of Weighted Spacers in
HPHT conditions”
-Abhinav Hazra, R.K. Raigar, Dr. Kishori Lal, H.S Negi & Pradeep Kumar, Institute of Drilling
Technology, Oil and Natural Gas Corporation Limited Dehradun.
Abstract
The study discusses the role of fluid loss additives (FLA) and of anti-settling agents (ASA) in
weighted spacers for oil cement wells in details. Thermal thinning of spacers at elevated
temperatures leads to increase of fluid loss at higher temperatures, for that requires FLA is required.
Besides this, thermal stability of spacers is of serious concern at HPHT well conditions and hence
the role of anti-settling agents has also been studied.
This study elaborates the role of both FLA &ASA of spacers by performing series of experiments.
Studies of fluid loss tests of spacers were carried out in medium temperature &HPHT conditions
with & without FLA. Similarly the role of anti-settling agents & its effectiveness was tested in a
HPHT consist meter by measuring the specific gravity of spacer sample after an interval in
pressurized mud balance. Attempt has also been done to carry out fluid loss test of spacer: cement
admixtures at varying well conditions.
Spacers are responsible for eroding the mud cake & make the formation and casing water wet. At
the same time spacer filtration rate should not be so high at wellbore temperature that it deposits a
thick filter cake during its dynamic displacement against the formation which will ultimately defeats
its primary purpose. Results have shown that spurt loss of spacer should not be neglected, but rather
it is substantial when filtration takes place against porous rocks & permeable zones, hence the role
of FLA. A minimum 10 minutes contact time has been mentioned in literature for effective removal
of drilling fluid. It is of paramount importance that before any spacer is designed one should check
fluid loss of spacer and also check fluid loss of cement slurry & spacer admixture too specially if
drilling takes place in a high temperature and high pressure gas bearing zone.
Results have shown spacer filtration rates do contribute to increased filtration rates of cement slurry
in admixtures especially if the former has no FLA in it. Anti-settling agents are very much needed
as found in experiments as they give thermal stability of spacers at elevated temperatures.
The study further suggests to check fluid loss of spacer which can be extremely beneficial to oil
well industry and help us beware of potential problems. As per API RP 10B-2 thickening time
&UCA test is recommended for spacer: cement ratio of 10:90, this study recommends that fluid loss
test of spacer: cement 10:90 should also be carried out prior to cementing in very porous, permeable
zones and in HPHT well conditions as an extra precaution.
Introduction
The primary objective of cementation is that of zonal isolation & spacers play a very critical role for
that. Today with the increase in number of HPHT wells being drilled, design of robust and thermally
stable spacers is the need of the hour. However, many spacers are not suitable for HPHT wells as
the performance of spacer depends on the rheological properties of spacer at elevated temperatures.
The efficiency of spacers at the BHCT and their corresponding Fluid loss & rheological properties
is very imp.In a series of experiments conducted with fluid loss additives (FLA) and without fluid
loss additive (FLA) in spacers at high temperaturesit was found out that that FLA plays a crucial
role in preventing fluid loss of spacerespecially against a high porous &permeable zone. Controlling
fluid loss of spacer is also important as that of cement slurry for proper cementation job.
A standard spacer can occupy an annulus height around 500-900ft.Spacers are responsible for
eroding the mud cake but their individual fluid loss should not be so high at BHCT that it deposits a

thick filter cake during its dynamic displacement which will ultimately defeats its original purpose.
It is also possible that cement slurry may be mixed with spacer in little proportion during
displacement especially if cementation job doesn’t take place according to plan. It is of paramount
importance that before any spacer is designed one should check fluid loss of spacer and also the
fluid loss of cement slurry & spacer admixture too specially if drilling takes place in a high
temperature and highly porous and permeable formations.
Various literatures shown that dynamic filtration rates are much higher than static rates, and most of
the filtrate invades sub surface formations do so under dynamic conditions. Under equilibrium
dynamic conditions, rate of filtration depends on the thickness & permeability of the cake, which is
governed by Darcy’s law. Changes in temperature may also effect filtrate volume through changes
in electrochemical equilibria which govern the degree of flocculation and aggregation, thus
increasing the permeability of filter cakes significantly. Chemical degradation of one or more
components of the mud is also a mechanism by which high temperatures can affect filtration
properties (Darley& Gray).
Thermal stability of spacers is very important, without proper thermal stability there will be settling
of weighting agents in spacers and ultimately failing the desired objective. Therefore, anti-settling
agents are often added to broaden the concentration range within which low yield values can be
obtained. Anti settling agents are materials that restore some of the yield value but at a level
compatible with the pumping conditions and friction pressure the exposed formation can bear.
Nelson et.al. Bentonite may be used to reduce slurry settling (Morgan and Dumbauld, 1954).
Bentonite has the ability to absorb large quantities of water; as a result, slurry homogeneity is
reserved. Various hydrosoluble polymers reduce sedimentation by increasing the interstitial-water
viscosity. The most commonly used materials are cellulosic derivatives such as
hydroxyethylcellulose (HEC) and wel an gum (Allen etal., 1991; Skaggs et al., 2001). The same
arguments can be applied for spacers that its rheology (specially the Yield point) should remain
constant over a wide range of temperatures. The YP of the spacer plays a crucial role in the
displacement of mobile & dehydrated mud.
Spacers are designed to remove maximum amount of mud from the formation face and also to
create a filter cake. The filter cake minimizes the spacer filtration and eventually helps control
cement-slurry fluid loss (crinklemeyer et al., 1976). Jones et al. (1991) considered spacer fluid loss
to be of secondary importance, because the contact time with formation is short. But as chemical
washes and spacers are pumped after mud, one can expect the mud- filter cake properties and the
filtration rate to change.
The challenge for industry has always been is to achieve a long term annular cement seal and
prevent formation gas entry; a proper spacer design is of paramount importance for that. Successful
handling of gas migration is of every operator’s interest.
When dealing with high temperature (and high pressure) environments, it is critical to find and test a
proper spacer technology that will provide the required performance. Numerous spacer technologies
are currently on the market that will provide enough viscosity to be effective at temperatures lower
than 325°F. Those typically consist of biopolymers (e.g. welan gum, cellulose-ethers, etc.)
effectively providing suspension properties for the weighting agents and a sufficiently high overall
viscosity of the spacer system. But at temperatures beyond 325°F conventional spacers will start to
decrease—or even completely lose— their rheological performance and so typically their
suspending properties. The consequences of failure of spacer rheological properties are:
• Loss/ of carrying capacity results on barite settling

• Reduced rheologies cause reduced displacement efficiency

• Fluids intermixing and potential cement slurry contamination

• Insufficient cement slurry placement and incomplete zonal isolation results
Experiments
Instruments & Procedures
Cement slurry preparation- Cement slurries was prepared with the API recommended practices for
testing well cements(API 10B2 RP-2013).Cement slurries were prepared using standard waring
blender. Standard cement slurry already used & tested in field was prepared for Cement slurry
design at 90⁰C, 150⁰C & 200⁰C BHCT. Corresponding spacer design was too formulated prior to
cementation jobs.
Spacer preparation- Spacers were prepared using a suitable viscosifier from service provider and the
role of FLA& AS was investigated by optimizing their doses. The spacers were prepared in a heavy
duty mixer. First added a suitable viscosifier, mixed it thoroughly followed by 30 mins hydration
time, followed by fluid loss additive hydrated for 5mins, then added anti-settling agent wherever
required in tests, observed 5 mins hydration time, followed by barytes with a hydration time of
30mins. Proper mixing of the above chemicals is imperative.
API fluid loss test

Static fluid loss experiments were performed at 90C using a standard 175ml filtration cell fitted with
a 45um (325) mesh screen supplied by OFI Testing equipment (Houston, USA). The operating
procedure and test conditions are detailed in API10-B norm (API 2013). Conditioned slurry was
placed in the preheated fluid loss cell (the fluid loss cell was heated in the heating jacket prior to
conditioning). Nitrogen was used to apply 1000psi (69 bars) on top of the cell. The test was resumed
when the bottom outlet was opened to normal atmospheric pressure. The filtrate was collected.
Filtration lasted for 30mins in all the experiments without nitrogen break through. The fluid loss of
spacer was tested with the same equipment as that is being tested for cement slurry fluid loss test as
per API RP10B-2, to form a common standard for comparison purposes. It has to be noted that fluid
loss values may not be accurate if the spacer is unstable & settling occurs.
Stability tests of spacer

Besides the fluid loss test of spacer it’s also essential to do anti-settling tests of spacer, Also should
ensure whether spacer is thermally stable or not. An unstable spacer at BHCT can lead to barytes
sagging, and lead to a poor execution of cementation job.
The spacer fluid was prepared according to API RP 10B-2 standard and then poured into a slurry
cup with a dynamic settling paddle(Brandl et.al 2017). This is a bladeless paddle that has a base for
collecting the solid particles as they settle at low rotation speed or in complete irrotation. The slurry
cup is placed in a HPHT consistometer and brought to circulating temperature and downhole
pressure at a rotation speed of 150 rpm then it is given 30 minutes to reach equilibrium
temperature.After that the motor is switched off and the consistometer is then cooled as quickly as
possible until reaching a safe temperature to remove the cup from the consistometer. Then the cup is
removed carefully without inverting it and the top of the cup is disassembled. The differential
density from top to bottom of the slurry cup is measured with the help of syringe and mud balance.
The desired density difference or differential density between top & bottom(ppg) of spacer should
be less than 1.0 ppg & the height of settled solids should be as low as possible. The condition of
settled solids is also important & it is preferred that it should be non-compacted.

Fig 1. Dynamic Settling paddle compared with HPHT consistometer paddle
After the paddle is removed from the cup, the presence of settled solids on the plate is observed, and
the height and condition of the solids are recorded. The height of settled solids is observed and the
condition of potentially settled solids whether it is compacted or non-compacted is inferred.
The spacer designs for 3 different sets of temperatures were carried out with & without FLA. With
FLA, anti-settling agents were also added in variable doses and optimized the same.
This way it can be checked whether there is any significant change in sp.gravity and monitor the
settling tendency of spacer and role of anti-settling additives. The specific gravity of spacer that was
initially prepared and difference of the specific gravity of top sampleand bottom sample of spacer
after conditioning to BHCT & BHP was noted for stability studies.The top spacer sample specific
gravity is recorded at first very carefully, after that the required bottom sample is collected from the
slurry container using the same syringe. The difference of top & bottom sample of spacer gives us a
fair idea of the settling tendencies in spacer. This fact is deduced from the knowledge that a
cementation job will be completed in few hours and cement sets within few hours, so initial spacer
stability around that duration is very important.
Along with the general measurement of sp. Gravity of spacer using the mud balance the settling
tendency of spacer is recorded visually too by observing the bottom of the container& observing
any settling of solids. By varying the dose of anti-settling agents, the difference in specific gravity
of top & bottom samples was noted. The density difference in top vs. bottom (ppg) should be less
than 1ppg or 0.12 gm/cc approximately.
Compatibility tests of spacer

Preparation of cement slurry/spacer and spacer/mud admixtures: The volumetric proportions of the
cement slurry/spacer and spacer/mud admixtures were 95/5, 75/25, 50/50, 25/75, and 5/95. The
various-ratio mixtures shall be prepared as follows (Table 4), based on section 13 of API RP 10 B-2,
2013: Rheological compatibility of fluids (cement & spacer and mud & spacer) shall also be
assessed by calculating the R-Index Value (R). The calculation is as follows: R = [Highest 100-
RPM reading from a mixture - Highest 100- RPM reading from an individual fluid]. The
compatibility assessment is given as

Definition of R-Index Value

If R < 0 Fluids are compatible.
0 < R< 40 Fluids are compatible, BUT friction pressures should be verified to avoid
fracturing the formation.
41< R < 70 Fluids are slightly incompatible. Additional testing is required.
R >71 Definitely Incompatible. An alternative formulation must be found.
RESULTS & DISCUSSIONS

The Cement slurry was designed at bottom hole circulating temperature (BHCT)-900C, and bottom
hole pressure-5000psi using various chemicals such as silica flour, fluid loss additives, dispersant,
retarders and defoamer. The data presented in Table No-1.
Table 1 Cement slurry design, BHCT-900C, pressure-5000psi (Sp.gr -1.94)
Cement Water S.Flour FLA Dispersant Retarder Defoamer

100 48.32 35 0.75 0.5 0.35 0.1
The spacer designed for the above cement slurry at BHCT-900C, pressure-5000psi was done by a
suitable spacer from a service provider, similarly FLA & AS were used at required doses and results
placed at Table -2
Table 2 Fluid loss and thermal stability data of spacer (Sp. gr 1.70)
Water Defo Spac FL ASA Barytes Fluid Thermal Remarks

amer er A (%) loss stability(densit < 1ppg
(%) (%) (%) in ml y difference in
gm/cc)
100 0.1 2.5 Nil Nil As Reqd 260 0.04 Pass
100 0.1 2.5 0.1 Nil As Reqd 160 0.02 Pass
100 0.1 2.5 0.15 Nil As Reqd 55 - Pass
An innovative study was carried out to check the fluid loss of cement and spacer admixtures in
varying proportions to check any drastic effects in change in fluid loss, if there is contamination at
the interface. Studies were carried out to check fluid loss with 90 cement: 10 spacer to see if there is
significant change in fluid loss as minute contaminations of spacer at interface during displacement
is possible. Besides during displacement if something goes wrong specially if not maintaining the
critical parameters like density & rheological hierarchy, cement & spacer do gets mixed the end
effect shouldn’t be catastrophic, i.e., the fluid loss should be (< 50 ml /30 min) and ultimately
contributing to annular gas migration& other job execution problems.
Table 3 Fluid loss of cement & slurry admixtures without FLA in spacer
Cement Spacer Fluid loss(ml) At 880C after

proportions Proportions conditioning in HPHT consistometer
100 - 60
90 10 105

Table 4 Fluid loss of cement & slurry (90:10) admixtures with optimized FLA in spacer
Cement proportions Spacer Fluid loss(ml) At 880C after conditioning in
Proportions HPHT consistometer
90 10 65
In case of spacer designed at 900C, a slight dose of fluid loss additive is sufficient to control its fluid
loss properties. At this moderate temperature there is no need of using anti settling agents as the
spacer showed no settling behaviour.
The Cement slurry was designed at BHCT-1500C, and BHP-5000psi using various chemicals such
as silica flour, FLA, dispersant, retarders & defoamer. The data presented in
Table5 Cement slurry design, BHCT-1500C, pressure-10000psi,Sp.gr - 2.20
Cement Wat S.Flour FLA Micro Dispers Retarder Co Defoamer

er (fine) max ant Retarder
100 41.3 40 0.5 30 1.5 0.5 1.96 0.1
The spacer designed for the above cement at BHCT-1500C, pressure-12000psi was done by a
suitable HPHTspacer from a service, and results are placed at Table 6
Table 6 Fluid loss and thermal stability data of spacer (2.00 SG)
Wat Defoa Spacer FL AS Baryte Fluid Thermal Remarks

er mer (%) A A s loss stability(density
(%) (%) (%) (ml) difference)
100 0.1 2.5(normal Nil Nil As - Observed settling Fail
spacer) Reqd of barytes
100 0.1 2.5(HPHT Nil Nil As 275 Observed Fail
spacer) Reqd settling(0.45)
100 0.1 2.5 0.2 Nil As 120 0.22 Fail
Reqd
100 0.1 2.25 0.2 0.1 As 85 0.09 Pass
Reqd
100 0.1 2.0 0.2 0.2 As 80 0.02 Pass
Reqd

(a) (b) (c)
Fig 2-
a) Observed Heavy Settling when normal spacer was used at HPHT conditions (Image on
the left)
b) Observed No settling when optimized FLA & ASA for designing ofspacer at 1500C
(Image on the middle)
c) Observed No settling when optimized FLA & ASA for designing of spacer at 2000C
(Image on the right)
The above figure 2a(Image on the left) corresponds to dynamic settling test for a conventional
spacer at 1500C, which fails & shows clearly the settling of barytes. While the images on the middle
& right of the figure shows no settling with optimized FLA & AS in HPHT spacers for 1500C &
2000C spacer respectively.
Table 7 Fluid loss of neat cement slurry, cement slurry& spacer(90:10) admixtures without
FLA in spacer
Cement Spacer Fluid loss(ml) at 880C after conditioning in HPHT

proportions Proportions consistometer
100 - 90
90 10 210
Table 8 Fluid loss of cement slurry & spacer admixtures with optimized FLA & ASA in
spacer
Cement Spacer Fluid loss(ml) at 880C after conditioning in

proportions Proportions HPHT consistometer
90 10 85
In this spacer the importance of fluid loss is seen but along with it the role of anti-settling agents
was inferred when spacer stability test was carried out. Without anti-settling agents marginal settling
of barytes was at the bottom of the plate. Optimization of spacer rheology is very important, as the

concentration of spacer is increased, the dose of FLA & ASA also needs to be optimized along with
it.The height of settled solids was also noted to determine the index of thermal stability of spacers.
Table 9 Cement slurry design, BHCT-2000C, pressure-16500 psi, sp.gr -2.35
Cemen Wate S.Flou FLA Dispe Micro High Temp Co- Defoamer
t r r(fine) rsant max Retarder Retarder
100 51 40 0.5 2.0 110 6.5 1.96 0.1
0
The spacer designed for the above cement slurry at BHCT-200 C, pressure-15000psi by a suitable
high temperature viscosifier from a service provider, similarly FLA & AS were used at required
doses.
Table 10 Fluid loss and thermal stability data of spacer (2.10 SG)
Water Defoamer HPHT FLA ASA Barytes Fluid Thermal Remarks

(%) Spacer (%) (%) loss stability(density
(%) (ml) difference)
100 0.1 3 Nil Nil As 238 Observed Fail
Reqd Settling (0.43)
100 0.1 2.75 0.3 Nil As 122 0.25 Fail
Reqd
100 0.1 2.5 0.3 0.15 As 78 0.12 Pass
Reqd
100 0.1 2.5 0.3 0.25 As 65 0.04 Pass
Reqd
Table 11 Fluid loss of cement & slurry admixtures without FLA in spacer
Cement proportions Spacer Fluid loss(ml) at 880C after conditioning

Proportions in HPHT consistometer
100 - 40
90 10 110
Table 12 Fluid loss of cement & slurry admixtures(90:10) with optimized FLA & ASA in
spacer
Cement proportions Spacer Fluid loss(ml) at 880C after conditioning

Proportions in HPHT consistometer
90 10 80
Since spacer usually erodes the deposited mud filter cake, the importance of spacer fluid loss is also
looked into it & its contamination effect with cement slurry.
The Composition of spacer needs to be optimized to decrease their rheology without compromising
thermal stability, allowing turbulent flow displacement; hence the role of anti-settling agents
becomes critical.
Compatibility tests were carried out in HPHT consistometer to check their compatibility with HPHT
cement slurries & HPHT drilling fluid at BHCT & also at ambient temperature, satisfactory results
were achieved with the use of fluid loss additives &anti-settling agents. Detailed experiments &
analysis have been carried out.
Anti-settlingagent’s role was critical here, it restored some of the yield value but at a level
compatible with the pumping conditions and friction pressure the exposed formation can bear for
HPHT conditions.
CONCLUSIONS
After an extensive study was carried out in laboratory following conclusions can be drawn
• The spacers were successfully designed for WBM at various temperatures& Pressure ranges
(BHCT varying from 90 to 2000C& BHP varying from 5000to 16500PSI).
• Designing of spacer was done with optimized fluid loss additives and anti-settling chemicals
especially for HPHT conditions.
• It has been observed that role of fluid loss additives and anti-settling chemical in designing
Spacers for HPHT condition showedexcellent results.
• For Dynamic settling test an innovative modified paddle was fabricated and it was used for
determining the thermal stability of spacer at HPHT conditions.
• Compatibility Tests of Spacer carried out at desired BHCT & BHP to ascertain any
incompatibility problems of spacer with mud & spacer with cement.
• Density & Frictional hierarchy should be maintained for proper mud removal & efficient
cementation jobs.
Acknowledgements
The authors are highly thankful to management of Oil and Natural Gas Corporation, Ltd for
permission to publish this paper. Authors are also thankful to HOI-IDT, for his constant
encouragement& support. Special thanks are due to many colleagues for their advice and assistance
provided during the study in the laboratory.
References
a) API RP 10B-2, Petroleum and natural gas industries - Cements and materials for well
cementing - Part 2: Testing of well cements. 1st Edition, July 2005. Washington, DC: API.
b) Erik B. Nelson and Dominique Guillot.: Well Cementing, second edition, Schlumberger,
Texas (2006).
c) Composition and properties of Drilling & Completion Fluids, Sixth Edition Darley & Gray
d) Brandl, A., Acorda, E., Ellis, T., Bray, W., 2013, Improving Mud Removal and Simplifying
Challenging Cement Design: A Deepwater Case History in the South China Sea, IPTC-
16761.
e) Doan, A.A., Holley, A.C., Li, L., Kellum, M.G., 2017, A Novel Cement System to Ensure
Slurry Stability in Horizontal Well, SPE-185123-MS.

f) Higgins, M. C., Nolan, T. J., Brandl, A., Bottiglieri, A., Jha, L. K., 2015 Numerical
Computer Modelling and an Innovative Spacer-Cement Train Results in Successful Zonal
Isolation in Critical Well Offshore Australia with Minimal Casing Centralisation, 176214-
MS.
g) Shadravan, A., Narvaez, G., Alegria, A., Carman, P., Perez, C., Erger, R. 2015 Engineering
the Mud-Spacer-Cement Rheological Hierarchy Improves Wellbore Integrity. SPE-173534-
MS.
h) Shadravan, A., Alegria, A., & Castanedo, R. 2015a. Rheological Hierarchy Optimization
Improves Fluid Displacement and Well Integrity, 3 Worldwide Case Studies. SPE Paper
174773 presented at the SPE Annual Technical Conference and Exhibition held in Houston,
Texas, USA, 28–30 September 2015.
i) Brandl, Angela, & Adriana 2017. Advances in Spacer Technologies for Improved Zonal
Isolation Results in Challenging Deep Deviated HPHT Wells Containing Heavy Oil Based
Muds.

Paper No. IOGCA(2019)/2
Title: “Robust design for Cement degradation in CO 2 under HPHT Environment.”

-Abhinav Hazra, Dr Kishori Lal, R. K Raigar, Parvinder Singh, H.S Negi & Pradeep Kumar,
Institute of Drilling Technology, ONGC
Abstract:
The effects of temperature on the cement properties strongly depend on the calcium to silica ratio.
At high temperature (greater than 110°C) and high calcium to silica ratio, the C-S-H phase will
transform into more stable α-C2SH phase that leads to increased permeability and loss of
compressive strength of the cement sheath. This can be prevented by adding more silica to the
cement to stabilize the tobermoritephase. At temperature greater than 150°C, the tobermorite
converts into xonotlite and/or gyrolite. This improves the cement properties.
The cement exposed to CO2 environment may shrink, which creates a pathway between the cement
and casing resulting in fluid leakage. Effects of CO2 on Cement Degradation Carbon dioxide
dissolves in water forming acidic solution (water + carbonic acid). This reaction reduces the local
pH. Temperature, partial pressure of CO2 and other ions present in water, such as salts, determine
the pH of the solution. The produced carbonic acid penetrates into the cement matrix and attacks the
main hydration products or binding materials. These reactions cause densification, which increases
the cement hardness and decreases its permeability, resulting in reduced CO2 diffusion and
expansion up to 6% in volume that can create the leaching or dissolution of CaCO3 occurs when the
cement is surrounded by liquid water containing dissolved CO2. The dissolution tends to increase
porosity and permeability, and degrade mechanical properties of the cement.
To mitigate this problems, an extensive laboratory work were carried out with different cement
designs, one conventional HPHT & another innovative cement design have been used to determine
the effects of CO2 in HPHT conditions. Cement slurries were cured in HPHT curing chamber & and
then exposed to CO2 in a specially arranged HPHT cell at 170 0 C and a differential pressure of 700
psi for duration of one month. The porosity & permeability measured by helium gas injection
method, phenolphthalein dye testing along with compressive strength were measured before and
after exposure to CO2 to understand the leaching mechanism and effects of carbonic acid on cement
sheath in HPHT environment. Further XRD analysis was also done to determine the mineralogical
changes in the structure of cement sheath before and after exposure to CO2.
Based on the innovative designed slurries which were prepared by using indigenously available
cement additives (such as fly ashes, latex, silica flour fine & Nano silica fume). The Results indicate
that innovative cement system shown excellent properties i.e. lesser permeability & porosity and
cement moulds were found to be much stronger than compared to conventional HPHT cement
design. Another significant change also observed in XRD analysis which confirms the change in
mineralogical composition of cement sheath after exposure to CO2.
The present study also suggests that the cement degradation under HPHT environment can be
reduced, by lowering the amount of Ca(OH)2 and/or increasing the amount of filler material i.e.
silica fume or fly ash. Since there is less amount of the substance which reacts with CO2, there will
be less carbonation.These novel cement formulations can further provide considerable benefit in
terms of maintaining long term integrity of cement sheath under this harsh environment in a cost
effective & efficient way.

Introduction
Carbonate reservoirs are often characterized by high pressure and high content of H2S and CO2. For
these reasons, drilling the reservoir is the most challenging activity of such fields and long-term
zonal isolation across the reservoir section is one of the primary requirements. Theseboth
gasescarbon dioxide (CO2) is a common element in downhole fluids, whether naturally occurring in
ground waters or the result of CO2 injection processes. When CO2 comes into contact with the
Portland cement that is used to cement well casings, it produces a deterioration phenomenon in the
cement called carbonation can cause serious damage to downhole tubular and destroy zonal
isolation integrity, resulting in costly remedial services or even abandonment of a well.
The origin of cement degradation can be due to physical, chemical or mechanical processes or
combination of these. Physical degradation occurs after the exposure of cement to reactive fluids,
which leads to physical discoloration. This mode of degradation also takes place when cement
shrinks during hydration, which may result in loss of hydraulic and shear bonding. Chemical
degradation occurs when cement reacts with aggressive fluids to form minerals that are easily
leachable or susceptible to further reaction. Mechanical degradation occurs when cement is
subjected to expansion and thermally induced pressurization, which leads to the formation of cracks
thereby increasing permeability. This mode of degradation arises when cement is exposed to
extreme loading conditions resulting from drilling, reservoir depletion and geological processes.
CO2 downhole generally falls within two categories— dry CO2, which is a result of carbon capture
and sequestration (CCS) activities, and wet CO2, which accounts for naturally formed CO2.This
CO2in the wellbore is exposed to residual moisture and free water in the wellbore and forms
carbonic acid, as illustrated in Eq. 1. The portlandite and C-S-H phases of cement subsequently
react with carbonic acid to precipitate calcium carbonate, shown in Eq. 2 & 3. The reactions of C-S-
H phase with carbonic acid and bicarbonate ion are not thermodynamically favoured compared to
the reaction of the acids with portlandite. This is the first stage of the process of carbonation where
portlandite phase of cement reacts with carbonic acid to form calcium carbonate. The formation of
calcium carbonate causes densification of the cement matrix because of the increase in mass in the
same volume of solid set cement. This increases strength and hardness, and decreases permeability,
thereby limiting the rate of diffusion.
(1)
(2)
(3)
(4)
(5)
Depending on the prevailing temperature and pressure, calcium carbonate (CaCO3) exists in
different forms. These include calcite, aragonite, vaterite and ikaite. However, calcite is the most
thermodynamically stable form at low temperature and is the most expected polymorph of
CaCO3.The carbonation is of significant concern if the CO2 enters the cemented annulus. The
surface area of the cement sheath that contacts CO2 should be minimized to help prevent
carbonation. This can be achieved by reducing the permeability of cement, preventing the formation
of cracks and micro-annulus, and reducing the components in the cement sheath prone to attack
from CO2.

The second step of carbonation of cement is a long term process. In case of long term exposure to
carbonic acid, or if the carbonic acid is refreshed, the calcium carbonate formed in the first step
further reacts with the acid to produce a more soluble product, calcium bicarbonate. This reaction
results in increased porosity, permeability, and loss of overall mechanical integrity. This can lead to
inefficient or even potential loss of zonal isolation in extreme cases. Eq. 7 illustrates this
mechanism.
(6)
(7)
The rate of carbonation is controlled by several parameters such as temperature, pressure, cement
formulation, CO2 partial pressure. Moderate carbonation can be beneficial for cement porosity and
permeability, since it forms CaCO3 that plugs the pores of the cement and acts as a protective layer
that limits further ingress of dissolved CO2. However, extensive carbonation can result in the loss of
structural integrity.
Experimental Work & Procedure

The experimental methodology and procedure for evaluation of effects of static CO2 on cement
molds were carried out as follows
Preparation of Cement Slurry & molds

a) Preparation & conditioning of cement slurry: Cement slurry was prepared according to
section 5 or Annex A of API RP 10 B-2, 2013.
b) Molds were cured at the same temperature at where the effects of carbon dioxide gas are to
be measured.
c) 2 sets of molds were used to compare the effects, one conventional cement sample (1) with a
normal permeability value and another cement sample (2) with lower permeability value
using the particle packing concept.
d) The initial 2” *2” molds were cut into cylindrical cores of 1” dia and their porosity &
permeability measurements were measured along with their weights
Modification of existing equipment

a) UCA cell was modified to carry out the effects of carbon dioxide gas in HPHT environment.
b) Carbon dioxide cylinder was rented from local agency in Dehradun for this purpose.
c) At a temperature of 170C & a pressure differential of 700psi was continuously applied to

both the cement molds.
d) The molds were submersed in water inside the uca cell for this purpose. CO2 gas was
injected continuously for 1 month. The amount of carbon dioxide dissolved in water depends
on the temperature, pressure & partial pressure of CO2.

Testing Procedure
a) Parameters like weight loss/gain, Initial & final pH change, Initial and final porosity &
permeability values of cement molds were carried out.
b) Porosity & permeability values were obtained from reservoir division of KDMIPE, Ongc
c) Compressive strength was determined in hydraulic press to observe the effects of carbon
dioxide before and after exposure.
d) Phenolphthalein dye testing was done in both the sample A & B, to check whether there has
been calcium carbonate deposition in the outer layers of core.
Results & Discussions

The effect of carbon dioxide was studied in details before and after exposure to carbon dioxide for
one month duration at 1700C & 700PSI.
Table 1 Composition of Cement Sample 1

Cement(Dalmia Wate S.Flour( FLA Dispersant Retarder ASA Defoamer
) Mumbai r Coarse)
100 48 35 0.6 0.2 0.28 0.21 0.1
Table 2 Composition of Cement Sample 2

Cement(Dalm Water S.Flour S.Fume FL Dispersan Retarder ASA Defoam
ia) Mumbai (Fine) A t er
100 48 35 5 0.4 0.6 0.3 0.1 0.1
Table 3: Before exposure to CO2

Sample. Length Breadth( Weight(gms) Porosity K(he) K C.S in PSI of
No (mm) mm) in % (md) ∞(md) 1”’dia core
1 47.31 25.26 39.716 34.358 0.15 0.112 2596
2 48.69 25.24 43.015 14.108 0.093 0.013 3770
Table 4: After exposure to CO2 for one month at 1700C & 700psi
Sample. Length Breadth( Weight(gms) Porosity K(he) K C.S in PSI of
No (mm) mm) in % (md) ∞(md) 1”’dia core
1 47.31 25.26 49.499 0.133 0.01 0.112 5497
2 48.69 25.24 48.946 1.021 0.071 0.008 7019
The results showed us that carbonation has taken place i.e. formation of calcium carbonate causes
densification of the cement matrix because of the increase in mass in the same volume of solid set
cement. Since the cement was exposed to one month only, the bicarbonation reaction could not take
place.
This result was substantiated by the weight of samples before & after exposure to carbon dioxide.
Both the sample showed an increase in weight while the relative weight gained by sample 2 was
lesser due to lower porosity of sample 2 initially. The lower initial porosity of sample 2 was because
of addition of cement additives which provided a better particle packing and a significant increase in

compressive strength. So less available pores resulted in lesser diffusion/ingress of carbon dioxide
gas into cement sheath & and resulted in lesser depth of penetration.
Similarly the permeability of set cement sample 1 showed a significant reduction in permeability i.e.
93.3% due to carbonation compared to sample 2 because of the aforesaid mentioned reason. So one
can infer that both sample showed reduction in porosity & permeability due to carbonation
reaction,albeit the degree of carbonation may be different for both of them. Further detailed inputs
have been provided by XRD analysis, which was carried out in KDIMPE.
Out of 2 cement samples, sample 2 initially exhibited higher compressive strength because of use of
common particle packing additives like S.flour (fine) & S.Fume. But after exposure to carbon
dioxide the gain in compressive strength was higher for the sample 1 which had lower initial
permeability & porosity compared to sample 2. Due to carbonation reaction the percentage increase
in compressive strength was more in Sample 1(45%) compared to sample 2 that of only (27.7%).So
one can say that lesser degree of penetration of carbon dioxide took place in sample 2 compared to
sample 1. The same has been depicted in figures below for both the samples before and after
exposure to CO2 gas.
Fig1- Sample 1 before exposure to static CO2 gas
Fig2- Sample 2 after exposure to static CO2 gas

Fig3- Sample 1 before exposure to static CO2 gas
Fig 4- Sample 2 after exposure to static CO2 gas
Phenolphthalein dye test experiment showed no colour change for both samples 1 & 2, after
exposure to CO 2 gas as most of the Ca (OH) 2 has reacted to form calcium carbonate in the outer
layers of the cement core.
While the cement samples that were not exposed to CO2 gas, turned pink in presence of
Phenolphthalein indicator due to presence of portlandite phase in outer layers.
Before exposure to
CO2
After exposure to CO2
Fig 5 Phenolphthalein Dye Experiment
The carbonated samples were tested for extent of carbonation using dye testing to help visualize a
clear demarcation of carbonated and noncarbonated zones. Dye testing was performed using
phenolphthalein indicator to determine the depth of penetration (DOP) of the carbonation reactions.
The samples were cut into two halves axially and phenolphthalein dye was applied to identify the
carbonated region. Phenolphthalein turns pink in colour in the presence of alkaline medium. Cement
is alkaline in nature & due to presence of calcium hydroxide; it turns into pink colour upon
application of phenolphthalein. Fig. below on the left side image shows a cement sample, which is
not subjected to CO2 corrosion environment. It can be observed that the entire surface is pink in
colour. But when the cement sample is exposed to CO2 corrosion environment (Fig below on right
side image), a non-pink band of surface is exhibited, which indicates the presence of carbonated
zone.

Figure 6 —Cement sheath after phenolphthalein test (a) Noncarbonated (left side) (b) After partial
carbonation (right side)
Analysis of mechanical and physical properties provides valuable input regarding the bulk
properties of the set cement. Because carbonation reactions change the cement chemistry, properties
such as permeability and porosity are expected to change within the cement sample. This change, in
turn, affects the rate of diffusion of reactants into the unreacted cement core; thus, in a way, it acts
as the rate defining step for the process. Understanding how these properties vary over time can help
in terms of the cement design to prevent carbonation
The second step of carbonation of cement is a long term process as already mentioned, which
ultimately results in deterioration of cement, and that requires experiment to be conducted for a
longer duration or in harsher experimental conditions.
XRD analysis is being carried out to confirm the presence of Calcium carbonate after reaction of
carbon dioxide with cement sheath. Relative formation of CaCO3 was compared to samples 1 & 2
after their exposure to carbon dioxide.
750
700
650
600 C
550
500
Q Bulk Mineralogy
450
400
350
300
250
Intensity (cps)
200
150
100
50
SAMPLE = 1-B
0
10 20 30 40 50 60
2-theta (deg)

700
650
600 Ca Bulk Mineralogy
550
500
450 Ar
400
350 Q
300
250
Intensity (cps)
200
150
100
50
SAMPLE= 1-A
0
10 20 30 40 50 60
2-theta (deg)
Ar. = Aragonite, Q = Quartz, Ca= Calcite
Sl.N SAMPLE ARGONITE QUARTZ (%) CALCITE (%)

O DETAILS (%)
1 SAMPLE 1- B - 71.57 28.43
2 SAMPLE 1-A 34.32 27.50 38.18

Sl.NO SAMPLE DETAILS QUARTZ (%) CALCITE MAGNESITE (%)

(%)
1 SAMPLE 2- B 60.9 21.56 17.54
2 SAMPLE 2-A 59.26 22.91 17.83
Sample 1B denotes the sample 1 before exposure & sample 1A denotes the sample 1 after exposure
to CO2 while, Sample 2B denotes the sample before exposure & sample 2A denotes the sample
after exposure.
Due to higher porosity of sample 1 initially more amount of carbon dioxide was able to penetrate
and react with cement, resulting in larger quantity of conversion of calcium hydroxide to calcium
carbonate. It is to be noted that presence of aragonite which is a polymorph of calcium carbonate
and with subsequent passage of time it will be transformed to calcium carbonate. For sample 1
which has a very low initial permeability & porosity has shown a change in formation of calcium
carbonate from 28.4 to 38.2% and an additional presence of mineral aragonite to 34.3%.
While in case of sample 2 & after its exposure to carbon dioxide the change in calcite was just a
little from 21.56% to 22.91%. This XRD analysis clearly shows that only a little calcite has formed
in sample 2 which is a relatively low permeable cement while sample 1 which has high porosity &
permeability reacted substantially with carbon dioxide.
Conclusion
Based on the study carried out following conclusions can be drawn,
• The rate of carbonation is controlled by several parameters such as temperature, pressure,
cement formulation.
• The study also suggests that moderate carbonation can be beneficial for cement porosity and
permeability, since it forms CaCO3 that plugs the pores of the cement and acts as a
protective layer that limits further ingress of dissolved CO2.
• However, extensive carbonation may result in the loss of structural integrity.

• It was also found that partial carbonation resulted in improvement in mechanical & transport
properties of cement cores.
Recommendations
• While designing well cements slurry for CO2 environments a holistic approach is required.
Firstly, it is necessary to carefully consider plan and then execute the task of effectively
displacing the drilling fluid from the annular space while avoiding losses and well control
issues and replacing this drilling fluid with cement in slurry form.
• Gas tight slurry need to be designed to restricts fluid or gas migration as it transitions from
slurry to solid form.
• Then, the set cement needs to be endowed with low permeability and mechanical properties
that would be expected to allow it to withstand predicted well events.
Acknowledgement
The authors thank the management of Institute of Drilling Technology, Dehradun for the
opportunity to publish this paper. They also thank and appreciate the strong support of the Head of
the Institute, IDT, Dehradun.
References
1. American Petroleum Institute Publication, API RP 10B-2, "RecommendedPractice for
Testing Well Cements." 2nd Edn. , April 2013.
2. American Petroleum Institute Publication, API Specification 10 A,"Specification for
Cements and Materials for Well Cementing." 24th Edn.,Dec. 2010
3. Erik B. Nelson and Dominique Guillot.: Well Cementing, second edition, Schlumberger,
Texas (2006).’
4. Barlet-Gouedard, V., Rimmele, G., Goffe B. etalet al. 2006. Mitigation strategies for the risk
of CO2 migration through wellbores. Presented at the IADC/SPE Drilling Conference,
Miami, Florida, 21–23 February. SPE-98924-MS. http://dx.doi.org/10.2118/98924-MS.
5. Brandl, A., Cutler, J., Seholm, A.J. etalet al. 2010. Cementing Solutions For Corrosive Well
Environments. Presented at the International Oil and Gas Conference and Exhibition in
China, Beijing, China, 8 –10 June. SPE-132228-MS. http://dx.doi.org/10.2118/132228-MS.
6. Campos, G., Alex Simao, C., Richard de Miranda, C. etalet al. 2014. Salt Tolerant Cement
Systems to Mitigate Gelling Effect. Presented at the IADC/SPE Asia Pacific Drilling
Technology Confer- ence, Bangkok, Thailand, 25–27 August. SPE-170477-MS.
http://dx.doi.org/10.2118/170477-MS. Carey, J.W., Wigand, M., Chipera S.J. etalet al. 2007.
Analysis and performance of oil well cement with 30 years of CO2 exposure from the
SACROC unit, West Texas, USA. International Journal of Greenhouse Gas Control 1 (1):
75–85.
7. Duguid, A., Radonjic, M., and Scherer, G. 2006. The effect of carbonated brine on the
interface between well cement and geologic formations under diffusion controlled
conditions, 8th Interna- tional Conference on Greenhouse Gas Control Technologies.
Trondheim, Norway.
8. Duguid, A. 2008. The Effect of Carbonic Acid on Well Cements as Identified Through Lab
and Field Studies. Presented at the SPE Eastern Regional/AAPG Eastern Section Joint
Meeting, Pittsburgh, Pennsylvania, 11–15 October. SPE-119504-MS.
http://dx.doi.org/10.2118/119504-MS.

9. Kutchko, B.G., Strazisar, B.R., Dzombak, D.A. etalet al. 2007. Degradation of well cement
by CO2 under geological sequestration conditions. Environmental science & technology 41
(13): 4787– 4792.
10. Le Guen, Y., Le Gouevec, J., Chammas, R. etalet al. 2008. CO2 Storage - Managing the
Risk Associated With Well Leakage Over Long Time Scales. Presented at the SPE Asia
Pacific Oil and Gas Conference and Exhibition, Perth, Australia, 20 –22 October. SPE-
116424-MS. http://dx.do-i.org/10.2118/116424-MS.
11. Moroni, N., Santra, A.K., Ravi, K. etalet al. 2009. Holistic Design of Cement Systems to
Survive CO2 Environment. Presented at the SPE Annual Technical Conference and
Exhibition, New Orleans, Louisiana, 4 –7 October. SPE-124733-MS.
http://dx.doi.org/10.2118/124733-MS. Cement and Concrete Research 22 (2): 259 –272.
12. Santra, A.K., Reddy, B.R., Liang, F. etalet al. 2009. Reaction of CO2 with Portland Cement
at Downhole Conditions and the Role of Pozzolanic Supplements. Presented at the SPE
International Symposium on Oilfield Chemistry, The Woodlands, Texas, 20 –22 April. SPE-
121103-MS. http://dx.doi.org/10.2118/121103-MS.

Title: “Experimental investigation of Zwitterionic Surfactant for Chemical Enhanced Oil

Recovery in Sandstone and Carbonate Reservoirs”
-Amit Kumar, Ajay Mandal, Petroleum Engineering Department, IIT(ISM) Dhanbad
Keywords: Zwitterionic surfactant, Enhanced oil recovery, Interfacial tension, Salt tolerance
Abstract
Conventional practices of pressure maintenance an only recover about 30-40% of oil from the
reservoir. Thus, most oil and gas companies have started venturing into the practices of enhanced oil
recovery to recover the trapped oil. Injection of chemicals such as surfactant, polymer and alkali has
been experimented at laboratory scale and these tests show promising results for applicability in
field scale. Polymer injection improves the macroscopic efficiency of the injected slug, whereas the
injected surfactant shows its effect at the microscopic level by reduction of IFT between oil and
surfactant slug.
Selection of surfactants for a reservoir requires exclusive compatibility of injected chemicals,

reservoir rock and fluids. The following criteria are needed to be fulfilled for selection of surfactant:
• Surfactant should have low CMC.
• Surfactant should reduce the IFT to ultralow value.
• Surfactant should have high salt tolerance.
• Loss of surfactant due to adsorption should be minimal.
Presently, anionic surfactants have shown excessive loss due to adsorption in carbonate reservoirs
and similarly cationic surfactants cannot be used in sandstone reservoirs. Thus, the aim of this paper
was to test a zwitterionic surfactant that is compatible with all types of reservoir and fulfils the
above stated criteria. The CMC of the surfactant was tested by the analysis of surface tension of
surfactant solution. IFT between oil and surfactant solution was measured using spinning drop
tensiometer and it was found that the surfactant was able to achieve ultralow IFT. The salt tolerance
of surfactant showed that it can be used in high saline reservoirs. The loss of surfactant due to
adsorption was tested with sandstone and carbonate rock samples and it was found resistant to
adsorption loss for both sandstone and carbonate samples. Thus, the zwitterionic surfactant can be
used to recover oil from all types of reservoirs.
Introduction
The conventional technique of oil recovery technique, also known as secondary oil recovery,
involves injection of water or gas for pressure maintenance, and water flooding leads to sweeping of
the trapped oil towards production wells [1]. However, the recovery factor of water flooding
technique is limited up to 30-40% of original oil in place, due to various reservoir rock and fluid
properties such as rock type, pore shape and size, reservoir heterogeneities, density, viscosity and
interfacial tension (IFT) of the reservoir fluids and the initial wetting state of the reservoir rock[2].
Thus, the recovery of the remaining crude oil trapped in the reservoir is targeted by changing these
reservoir rock and fluid properties by various enhanced oil recovery (EOR) techniques. Primarily,
the EOR techniques are categorised as thermal, gas and chemical injection, and the selection of a
particular technique depends on the reservoir properties and conditions. Among these categories,
chemical EOR, which includes the injection of chemicals such as alkali, surfactant and polymer, is a
proven method of improving oil recovery [3]. Polymer injection improves the macroscopic
efficiency of the injected slug by controlling the mobility ratio of the displacing fluid to the

displaced fluid. Polymer injection is extremely important in heterogenous reservoirs for prevention
of fingering, which leads to early breakthrough of injected fluid. The microscopic efficiency of the
injected slug is improved by the use of alkali and surfactant, which reduces the IFT between the
injected slug and the trapped crude oil and improves the water-wetting property of the reservoir
rock.
The selection of surfactant for application in a reservoir is based on various factors which include
the type of surfactant and type of reservoir, as well as, the pH, salinity and temperature conditions of
the reservoir. Surfactants are categorised as anionic, cationic, non-ionic and zwitterionic, depending
upon the charge of the hydrophilic head group of the surfactants. Anionic surfactants have
negatively charged hydrophilic head group such as carbonate, sulphate and sulfonate ions, whereas,
cationic surfactants have positively charged hydrophilic head groups such as ammonium and
imidazolium ions. Non-ionic surfactants have neutral charge and their surface behaviour is the result
of ethylene oxide or propylene oxide groups present in their molecular structure. Zwitterionic
surfactants are specific type of surfactants containing both positively and negatively charged groups
in their hydrophilic head. The type of surfactant is an important selection criterion for a particular
type of reservoir, as the anionic surfactants have been found unsuitable for carbonate rock and the
cationic surfactants are not compatible for usage in sandstone reservoirs. Non-ionic surfactants have
better applicability in high saline reservoirs but their dominating oil recovery mechanism is
wettability alteration [4]. The presence of amphoteric charges in zwitterionic surfactant makes it
uniquely suitable for application in sandstone as well as carbonate reservoirs, and its net neutral
charge leads to better compatibility for application in high saline reservoirs [5].
In this work, a zwitterionic surfactant was selected constituting the hydrophilic head of ammonium
and carboxylate ions as positively and negatively charged groups respectively, and the hydrophobic
tail had a chain length of 16 carbons. The surfactant was characterized by measuring its critical
micelle concentration (CMC), salt tolerance, reduction in IFTand resistance to loss due to adsorption
on rock surface, to test for its applicability for chemical EOR.
1. Experimental procedure
1.1Materials
A carboxybetaine based zwitterionic surfactant, N-Hexadecyl-N,N-dimethyl-2-ammonio-1-
ethanecarbonate (C16DmCB), was selected for testing its applicability in EOR. The synthesis of the
surfactant has been reported in our previous work [6].NaCl and CaCl 2 , procured from Rankem
Chemicals, were used to study the effect of salinity. All chemicals procured were used without any
further modification. Double distilled water was used for the preparation of solutions. Crude oil,
having 34º API gravity, was used as oleic phase for IFT measurement of surfactant solution.
1.2 Surface tension

Surface tension of aqueous solutions was measured using pendant drop methodology using Kruss
DSA25 Drop Shape Analyzer. The droplet of surfactant solutions, with varying surfactant
concentration, was suspended at the tip of needle with air as its surrounding phase. The images of
the suspended droplet were analysed to determine the surface tension of the surfactant solutions.
The plot of surface tension of solutions versus the variation in surfactant concentration was used to
determine the CMC of the surfactant. The instrument was calibrated with distilled water prior to
testing of surfactant solutions. All the readings were taken at 30 °C.

1.3 Salt tolerance

Salt tolerance of the surfactant is tested by determination of the highest salinity for which the
surfactant solution does not form any precipitate. To test the salt tolerance, the surfactant solution of
concentration of 4 × CMC and salt concentration varying from 0% to 20% of NaCl and CaCl 2 were
analysed at 30 °C and at higher temperature of 80 °C. The solution mixture of surfactant and salt
was prepared using Tarsons Rotospin to obtain a clear solution. The solution was centrifuged at
2500 rpm for 10 mins to check for the formation of precipitate. The salt concentration of the
solution for which precipitate was formed was termed as salt tolerance of the surfactant.
1.4 Interfacial tension

IFT between surfactant solution and crude oil was measured using Data Physics SVT20 tensiometer
by spinning drop methodology. A drop of crude oil was injected into the capillary tube filled with
surfactant solution of varying concentrations. The capillary tube was rotated at 5500 rpm at 30 °C
and the shape of crude oil drop was analysed to calculate the IFT between the crude oil and
surfactant solutions. Dynamic IFT of surfactant solutions was plotted with time and the equilibrium
IFT was taken as IFT between the crude oil and the surfactant solution. The effect of salinity was
tested by varying the concentration of NaCl in the surfactant solution at its CMC.
1.5 Adsorption test

The loss of surfactant due to adsorption on powdered samples was studied by mixing 4 gm of
powdered rock sample with 40 mL of the surfactant solutions. The solutions and powdered samples
were mixed using Tarsons Rotospin at 30 °C for 24 hrs. The supernatant liquid was collected after
centrifuging for 15 mins at 5000 rpm. The unknown concentration of surfactant in the supernatant
liquid was calculated using the calibration curve, plotted using the absorbance values of solutions of
known surfactant concentration. The absorbance of the surfactant solutions was determined at
wavelength of 265 nm using SHIMADZU UV-1800 UV-Visible spectrophotometer. The adsorption
density was calculated using the initial and final bulk concentrations of surfactant as[7]:
v
Γ = (Ci − Ce ) m
where, ℾ(mg/g) is the adsorption density, C i (ppm) is the initial concentration of the surfactant, C e
(ppm) is the final concentration of the surfactant, v (L) is the volume of the surfactant solution and
m (g) is the mass of the powdered sample.
2. Results and Discussions
2.2 Surface tension

The measurement of surface tension of surfactant solutions is used to determine the CMC of the
surfactant. The plot of surface tension of solutions with varying surfactant concentration has been
shown in Figure 1. It can be seen from the figure that the increase in surfactant concentration in the
solution, its surface tension decreases. This phenomenon can be seen for increase of surfactant
concentration up to 50 ppm, where, the surface tension of water has reduced from 71.5 mN/m to
30.71 mN/m. With increase in concentration of surfactant in the bulk of solution, greater amount of
surfactant molecules is adsorbed at the air-water interface, leading to decrease in surface tension.
However, further increase in surfactant concentration does not reduce the surface tension, as the air-
water interface is saturated with surfactant molecules and CMC of the surfactant was achieved.
After CMC is attained, the surfactant molecules are present in the bulk of the solution in the form of
micelles and the surface tension of the solution remains constant.

70
Surface Tension (mN/m)
60
50 CMC
40
30
0 20 40 60 80 100
Concentration (ppm)
Figure 1: Surface tension of surfactant solution at 30 °C
2.3 Salt tolerance

The testing of salt tolerance of surfactant is a key aspect in the selection of surfactant for application
in high saline reservoirs. Increase in salinity causes the reduction in solubility of surfactant micelles
and leads to formation of precipitate at higher salt concentration. The ions of salt disrupt the
electrostatic repulsion between the hydrophilic head group, leading to changes in micelle shape, size
and solubility [8].The precipitate formation can be extremely damaging to the reservoir, as it can
lead to scale formation in the pores, causing the blockage of the pores and subsequent reduction of
oil recovery. The salt tolerance of the zwitterionic surfactant was tested by varying the
concentration of NaCl and CaCl 2 and it was observed that the surfactant solution was clear up to the
salt concentration of 20% at 30 °C. This signifies that the zwitterionic surfactant has better salt
tolerance in comparison to the petroleum sulfonates which have the salt tolerance of 14% of
NaCl[9]. The zwitterionic surfactant was also found to be salt tolerant up to high salinity of 20% at
the higher temperature of 80 °C. This significantly higher salt tolerance was due to overall neutral
charge of the surfactant molecule, which leads to its lower interaction with both monovalent and
divalent ions. As most reservoirs have the presence of monovalent and divalent ions present in the
formation water and the surfactant was salt tolerant for more than 20 % salt concentration, it can be
used in high saline oil reservoirs.
2.4 Interfacial tension

The initial distribution of crude oil in a reservoir is dependent on the shape and size of the pores, the
IFT between the oil and aqueous phase and the wet ability of the reservoir rock surface [10]. IFT
between oleic phase and aqueous phase present in reservoir is generally more than 20 mN/m [10–
13]. Due to such high value of IFT, the oil drops remain trapped within narrow pores of reservoir
and the movement of oil through the pores is possible only when the capillary forces holding the
drop in its pores are overcome by either the reservoir pressure or the pressure of the injected flood.
Thus, the high IFT between the trapped crude oil and the brine injected during water flooding
process, leads to the lower recovery of crude oil from the reservoir [14]. The reduction of IFT of oil-
water interface by the use of surfactants in the injected flood causes the oil drops to easily deform
and get displaced through narrow capillaries [15].The reduction of IFT between the crude oil and

surfactant solutions with varying concentration have been shown in Figure 2.It can be seen from the
figure that the IFT between the crude oil and the aqueous solution was 17.55 mN/m. However, with
the addition of surfactant in aqueous solution, it was seen that the IFT of the oil-water interface
reduced significantly. This decrease in IFT is due to increase in surfactant adsorption at water-oil
interface. The adsorbed surfactant molecules align itself such that the hydrophobic carbon chain is
in oil phase and the hydrophilic head group is in aqueous phase. The carbon chain interacts with oil
components and reduces the IFT [16]. As surfactant concentration increases in aqueous phase,
diffusion of surfactant molecules increases from bulk of solution to oil-water interface. Minimum
IFT was measured for concentration of 50 ppm at which the adsorption rate is equal to the
desorption rate [17]. For the concentration of surfactant greater than its CMC, the surfactant
molecules are present in the form of micelles in the bulk of the solution and the oil-water interface is
saturated with the surfactant molecules. Thus, further reduction of IFT with increase in surfactant
concentration was not observed. So, the surfactant was found capable to reduce the IFT of oil and
surfactant solution by the order of 3 and reached the lowest IFT of 1.1×10-2 mN/m.
10
1
IFT (mN/m)
CMC
0.1
0.01
0 10 20 30 40 50 60 70 80 90 100
Surfactant concentration (ppm)
Figure 2: IFT between crude oil and surfactant solutions at 30 °C
Presences of salt in surfactant solution also have significant effect on the IFT properties of the
surfactant [31]. Figure 3 shows the effect of concentration of the salt to IFT reduction by C16DmCB
surfactant. As seen from the curve, IFT of the surfactant solutions decreases with increase in the salt
concentration in the bulk of the solution. This reduction is due to decreased solubility of surfactant
in presence of salt which increases the adsorption of the surfactant at the oil-water interface [32]. At
higher salt concentration the surfactant is more soluble in oleic phase leading to desorption of
surfactant from the oil-water interface into oleic phase [33]. Thus, the interface concentration of
surfactant decreases and IFT reduction by surfactant is reduced at higher salinity. This phenomenon
of increase in IFT was observed for salt concentration above 3%.

0.012
0.010
0.008
IFT (mN/m)
0.006
0.004
0.002
0.000
0 1 2 3 4 5
Salinity (%)
Figure 3: Effect of salinity on the IFT between surfactant solution and crude oil at 30 °C
2.5 Adsorption test

The adsorption of surfactant molecules on the rock surface can lead to significant loss of surfactant
during flooding of surfactant slug in a reservoir. The loss of surfactant can lead to the reduction in
the effectiveness of the surfactant, leading to huge economical loss [18]. The adsorption of
surfactant is mainly affected by the charge of the surface of rock. Thus, strong attractive forces exist
between anionic surfactant and carbonate rock, and cationic surfactant and sandstone rock [19].
However, the presence of both positive and negative charges in a zwitterionic surfactant suggests
that both sandstone and carbonate rock can have the existence of both attractive and repulsive forces
between the surfactant molecule and rock surface. Figure 4 shows the adsorption profile of the
zwitterionic surfactant on sandstone and carbonate samples. It can be seen from the curve that the
adsorption density is increasing with the increase in the concentration of the surfactant. However,
for bulk concentration of surfactant greater than its CMC, the surfactant molecules are present in the
form of micelles, leading to decrease in the interaction of surfactant molecules and rock surface.
Thus, a plateau in the curve of adsorption density was obtained for higher surfactant concentration.
The maximum adsorption density of 0.273 and 0.405 mg/g was obtained for initial surfactant
concentration at 2 × CMC with sandstone and carbonate rock samples respectively. This suggests
that the zwitterionic surfactant is a suitable and economical chemical EOR agent.
0.5
Sandstone
Carbonate
0.4
Adsorption density (mg/g)
0.3
0.2
0.1
0.0
0 10 20 30 40 50 60 70 80 90 100 110
Initial surfactant concentration (ppm)
Figure 4: Adsorption profile of surfactant on sandstone and carbonate samplesat 30 °C

3. Conclusions
A zwitterionic surfactant with 16 carbons in hydrophobic chain and the hydrophilic head consisting
of ammonium and carboxylate ions as positively and negatively charged groups respectively was
tested for its applicability in chemical EOR. The CMC of the surfactant was determined as 50 ppm
by surface tension measurement. The surfactant was found to have excellent salt tolerance to both
monovalent and divalent ions. Ultralow IFT between crude oil and surfactant solution at its CMC
was achieved, signifying its excellent effectiveness in recovering the trapped crude oil from the
reservoir. The IFT was found to initially decrease and then increase with increase in salinity. The
loss of surfactant due to adsorption was also within the recommended range for applicability in oil
reservoirs. These excellent results obtained for laboratory scale experiments suggest that the
zwitterionic surfactants have good prospective for use as a chemical EOR agent in oil fields.
Acknowledgement
The authors are thankful to Petroleum Engineering Department for providing the necessary facilities
for this study.
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Title: “Study the Effect of Naturally Derived Products on Asphaltene

Solubilisation in Petroleum Reservoir Rock”
-Arnab Mandal, Barasha Deka, Rohit Sharma, Vikas Mahto, Department of Petroleum Engineering,
Indian Institute of Technology (Indian School of Mines)
Keywords: Asphaltene inhibitor, Asphaltene deposition, Natural product, Reservoir rock
Abstract
Precipitation of organic solids particularly asphaltene is a serious threat to the productivity of oil &
gas industries across the world. Asphaltenes are polycondensed aromatic rings that occur as
solubilised liquid in crude oil under normal reservoir conditions. When crude oil flows through the
pores of petroleum formation rock, localized variations occur in the pressure due to non-uniform
pore distribution of rock. As a result, the pressure depletion in the flow of crude oil leads to apparent
increase in volume fraction of aliphatic hydrocarbon solvents like heptane, hexane etc. that serve as
precipitant to asphaltene due to the fact that asphaltenes are insoluble in aliphatic solvents. This
causes precipitation of asphaltene in the pore spaces of reservoir rock, leading to drop in the flow
rate of crude oil. In certain cases, the oil production might come to standstill due to pore plugging.
In this article, almond oil derived naturally from the plant resources has been used as asphaltene
inhibitor for crude oil. Crude oil under study is a medium heavy crude oil with high asphaltene
content and core sample is a sandstone rock collected from the same oilfield.Core flow studies were
carried out by pumping crude oil through the formation core under various conditions.The pressure
drop across the core due to almond oil beneficiated crude oil was much less in comparison with p-
hydroxybenzoic acid treated crude oil. In addition, application of almond oil is more economical,
environment friendly and flexible than injection of p-hydroxybenzoic acid, a chemical that is
derived from chemical reaction of another chemical compound.
1. Introduction
Organic solid deposition in the petroleum formation rock is a big challenge in the path of oil
production. Asphaltenes, one of the heavy organic compound present in the crude oil tend to remain
dissolved, under average reservoir temperature and pressure. The passage of crude oil through the
pores of rock leads to localized pressure variations owing to non-uniform pore distribution of rock.
As a result, an overall pressure drop is created in the flow path that leads to apparent increase in
volume fraction of alkane compounds like heptane, hexane etc. that are insoluble with asphaltene.
With the gradual passage of the petroleum oil, the pore spaces of rock gets deposited with solid
asphaltene leading to drop in flow rate. In extreme cases, the oil well may face shutdown and
additional expenses might burden up in cleaning the asphaltene deposits from the pore spaces of
rock using conventional industrial practices.Ebrahimi et.al (2016) found that an increase in flow
pressure leads to an increase in the asphaltene precipitation.Rocha Jr.et.al (2006) worked on the
inhibition of asphaltene precipitation in Brazilian crude oil using oil-soluble amphiphiles. It was
found that vegetable oils caused fair improvement in the viscosity of crude oil.Madhi et.al (2017)
screened asphaltene inhibitors like salicylic acid, cetyltrimethyl ammonium bromide, benzoic acid,
naphthalene etc. for crude oil. They found that the asphaltene inhibitors interacted with asphaltene
via hydrogen bonding and π-π interaction and acid-base interaction.
This paper highlights the effect of injecting almond oil, an asphaltene inhibitor derived from natural
sources on the changes in flow properties of crude oil. Asphaltene precipitation is checked by
flooding the crude oil-heptane blend and the oil-heptane blend doped with asphaltene inhibitors

through the sandstone core. Asphaltene solubilisation of the almond oil was compared to p-
hydroxybenzoic acid, an asphaltene inhibitor derived from industrial synthesis of organic chemical.
2. Experimental work
2.1 Materials
Toluene, heptane, methanol and light paraffin oil were purchased from RankemAvantor
Performance Materials (New Delhi, India). Chloroform and acetonitrile were purchased from Merck
Specialties Pvt. Ltd. (Mumbai, India). Almond oil and p-hydroxybenzoic acid were purchased from
Loba Chemie Pvt. Ltd. (Mumbai, India). All glassware was purchased from Merck Specialties Pvt.
Ltd. (Mumbai, India). Crude oil was collected from Indian oilfield and core sample was collected
from the same oilfield.
2.2 Experimental procedure

2.2.1 Determination of physicochemical properties of crude oil
API gravity of crude oil was determined with the help of pycnometer (Sharma et.al 2018). Wax
content of the crude oil was determined by mixing the oil with n-pentane. Afterwards, acetone was
added to the mixture & frozen to –200Cfor 24 hr. Sample was subjected to vacuum filtration using
Whatman filter paper 934 and washed with hot hexane (Sharma et.al 2019). Crude oil was mixed
with n-heptane, heated from 35 to 400C and cooled to room temperature for 4 hours. The solution
was vacuum filtered and thefiltrate paper was washed with hot toluene to determine the asphaltene
content (Deka et.al 2018).
2.2.2 Identification of asphaltene inhibitors as flow improvers for crude oil
50:50 mixture of p-hydroxybenzoic acid and toluene was prepared. It was labelled as P1 and used as
asphaltene inhibitor and flow improver for crude oil. Almond oil was used as another asphaltene
inhibitor and labelled as A1. Hydroxybenzoic acid, a white solid powder was soluble in aromatic
solvents like toluene. Almond oil, a clear yellow liquid was composed of esters of different fatty
acids. The different properties of almond oil are listed in Table 1 (Canadian Centre for Occupation
Health and Safety).
Table 1 Properties of almond oil

S No. Parameter Information
1. Density 0.910 g/mL
2. Boiling point > 1000C
3. Solubility Insoluble in water, soluble in alcohol
4. Flash point > 2150C
5. Chemical composition Esters of fatty acids like Palmitic acid,
Linoleic acid, Oleic acid, Stearic acid etc.
2.2.3 Determination of rheological properties of crude oil
Viscosity of crude oil-heptane blend and the same blend treated with asphaltene inhibitors was
determined at 550C with the help of Anton Paar Physica Rheometer, keeping 0.1-1200 s-1 shear
ratefor the experiments. Similarly, the rheological properties of crude oil treated with asphaltene
inhibitors were determined under the same conditions to check changes in the viscosity of crude oil.
2.2.4 Study of asphaltene deposition in the formation rock

Asphaltene deposition of heavy crude oil in the formation core was carried out using an
experimental core flow set up. It consisted of a crude oil tank equipped with electric coils for

heating, a storage tank containing Hassler core holder containing core sample, surrounded by a
rubber sleeve, a pressure gauge at the inlet and outlet section of the total flooding path with back
pressure regulator and a hydraulic pressure control system to monitor the overburden pressure.
Double acting syringe pump from Teledyne ISCO (U.S.A) was used to transfer the crude oil from
oil tank to the core sample serving as a porous medium present at a definite temperature and
pressure. Paraffin oil acted as a driving fluid in this pump. The pump had a maximum flow rate of
200 mL/min and maximum delivery pressure of 3750 psi. Core sample used in the flooding is a
sandstone rock whose properties are listed in Table 2.
Table 2 - Physical properties of core sample
S No. Parameter Magnitude

1. Length 6.45 cm
2. Diameter 4.15 cm
3. Porosity 13.05 %
200 mL of the crude oil-heptane mixture and the crude oil-heptane mixture blended with asphaltene
inhibitors was flooded through the core at pressures ranging from 200-1600 psi and at a temperature
of 550C based on the average temperature and pressure existing in this oil reservoir. For further
assessment of asphaltene precipitation, the syringe pump was operated in constant flow rate mode at
a flow rate of 50 mL/min and the pressure drop under these conditions was monitored with respect
to time. Similar experiments were carried out for crude oil heptane blend doped with asphaltene
inhibitors. Process diagram for core flooding is shown in Figure 1.
Fig 1 Experimental set up to study asphaltene deposition through the pores of rock
3. Result & Discussion

The different characteristic properties of crude oil are listed in Table 3.

Table 3 Characteristic properties of crude oil

S No. Parameter Magnitude Reference
1. API gravity 25.030 Sharma et.al (2018)
2. Wax content 12 % (w/w) Sharma et.al (2019)
3. Asphaltene content 3 % (w/w) Deka et.al (2018)
Crude oil under study is a medium heavy crude oil with high wax content and high asphaltene
content. Therefore it has capacity for both wax and asphaltene deposition. Experimental conditions
must be maintained so that the study remains confined to asphaltene deposition in reservoir
conditions only.Action of asphaltene inhibitors on the crude oil viscosity is shown in Figure 2.It was
found that crude oil has relatively lower viscosity when treated with the synthesized asphaltene
inhibitor in comparison with the commercial asphaltene inhibitor. The effectiveness of inhibitor on
the crude oil can be reasoned out on the basis of its ability to disrupt the π-π interaction between
asphaltene molecules, causing its solubilisation (Ovalles et.al 2016).
Fig 2 Rheological properties of crude oil beneficiated with asphaltene inhibitors
Dependence of injection pressure on the flow rate of crude oil, under different collected volumes at
the outlet is shown in Figure 3. It is observed at 800 psi, the flow rate of oil sample is 0.33 mL/min,
which represents 22 % of the flow rate as compared to flow rate at 200 psi. In addition, the flow rate
at 1600 psi pressure is 0.0008 mL/min, which represents 0.267 % of the flow rate at 200 psi
pressure, at 200 mL flooding collected at the outlet. It means that, elevation in the flow pressure
results in accelerated precipitation of asphaltene in the porous formation (Ebrahimi et al., 2016).

Fig 3 Effect of pumping pressure on flow rate of crude oil at different flooding volumes
collected
The effect of concentration of asphaltene inhibitors P1 and A1 on crude oil flow rate at200mL
flooding is shown in Figure 4. It is found that injection of asphaltene inhibitors cause increment in
crude oil flow rate. Further, oil sample doped with 1.5 volume percent asphaltene inhibitor A1 has
2.33 times magnitude of flow rate as compared to crude oil treated with asphaltene inhibitor P1 at
the same concentration. This observation can be confirmed from the drop in slope of plot of
pressure drop versus time at a constant flow rate of 50 mL/min in Figure 4. The significant increase
in crude oil flow rate in case of injection with asphaltene inhibitor A1 as compared to P1 can be
explained on the basis of large transition in π-π orbital overlap between asphaltene molecules with
the help of large number of unsaturated carbon bonds present in different fatty acid groups, leading
to dissolution of solid asphaltene.
Fig 4 Pressure drop across sandstone core flooded with virgin and beneficiated crude oil at 50
mL/min flow rate and 550C temperature

4. Conclusion
The experimental condition confines to the study of asphaltene deposition in the formation rock.
Increase in the injection pressure leads to rapid precipitation of solid asphaltene as evident from
99.73 % reduction in the flow rate of crude oil at 1600 psi pressure as compared to the flow rate at
200 psi, which is the initial injection pressure of crude oil. The crude oil beneficiated with almond
oil showed better improvement in flow rate of crude oil as compared to crude oil treated with p-
hydroxybenzoic acid at the same concentration. The maximum improvement in the flow rate of
crude oil occurs at its 1.5 volume percent concentration in the crude oil, under which the pressure
drop across the core is found to be significantly reduced with the injection of almond oil competing
with p-hydroxybenzoic acid. In addition, injection of almond oil is lot eco-friendlier than p-
hydroxybenzoic acid, making it suitable for use in petroleum industries.
Acknowledgement
The authors would like to acknowledge Indian Institute of Technology (Indian School of Mines),
Dhanbad for providing the necessary laboratory facilities.
References
1. Ebrahimi, M., Dehghani, S.A.M., Dabir, B., Shahrabadi, A., 2016. The effect of aromatic
solvents on the onset and amount of asphaltene precipitation at reservoir conditions:
Experimental and modeling studies. J. Mol. Liq. 223, 119-127
2. Rocha Jr., L.C., Ferreira, M.S., Ramos, A.C.S., 2006. Inhibition of asphaltene precipitation
in Brazilian crude oils using new oil soluble amphiphiles. J. Petrol. Sci. Eng. 51, 26-36
3. Madhi, M., Kharrat, R., Hamoule, T. 2017. Screening of inhibitors for remediation of
asphaltene deposits: Experimental and modelling study. Petroleum 1, 1-10
4. Sharma, R., Deka, B., Mandal, A., Mahto, V., 2018. Study the influence of sodium
dodecylsulphate on emulsification of heavy and waxy crude oils to improve their flow
ability in low temperature conditions. Asia Pac. J. Chem. Eng. 14, 1–16
5. Sharma, R., Mahto, V., Vuthaluru, H., 2019. Synthesis of PMMA/modified graphene oxide
nanocomposite pour point depressant and its effect on flow properties of Indian waxy crude
oil. Fuel 235, 1245–1259
6. Deka, B., Sharma, R., Mandal, A., Mahto, V., 2018. Synthesis and evaluation of oleic acid
based polymeric additive as pour point depressant to improve flow properties of Indian waxy
crude oil. J. Pet. Sci. Eng. 170, 105–111
7. Canadian Centre for Occupation Health and Safety 135 Hunter St E, Hamilton, Canada
https://www.ccohs.ca/oshanswers/legisl/msdss.html
8. Ovalles, C., Rogel, E., Morazan, H., Moir, M., 2016. Synthesis, characterization and
mechanism of asphaltene inhibition using phosphorylated asphaltenes. Fuel 180, 20-26

Title: “Application of Nanotechnology in Cementing High Pressure High Temperature Oil &
Gas wells.”
-Dr KishoriLal and Pradeep Kumar, Institute of Drilling Technology, Oil and Natural Gas Corporation Limited
Abstract
Cementing in high pressure high temperature (HPHT) wells is complicated due to wide ranging
temperature and pressure variations and stresses to which the annular cement sheath, located
between the casing and the formation, is subjected during its service life. The long-term integrity
and durability of the annular cement depends on providing casing support and preventing the
migration of formation fluid in liquid or gaseous form through or at the boundaries of the cement
sheath.
The primary objective of oil well cementing is zonal isolation (i.e., restricting fluid movement
across various zones within formations). To achieve successful zonal isolation requires a robust
cement slurry which provides a strong and durable cement-casing and cement-formation bonding,
precludes bulk shrinkage by inhibiting the fluid loss, has zero free water settling of cement, and
does not form a micro annulus due to stress imbalance at the interface resulting from thermal
regimes, hydraulic pressure or mechanical stresses. The hardened cement slurry should also resist
radial fracturing that may result from shrinkage stresses, thermal expansion or contraction of the
steel casing and pressure fluctuation, mechanical impact, or other conditions within the casing.
The HPHT wells have a larger probability of migration of gas and corrosive fluid and leakage.
Therefore, special attention must be paid to cementing processes, especially in HPHT wells. Studies
have shown that approximately 80% of the wells in the Gulf of Mexico have gas transmitted to the
surface through the cement casing.
High temperature gives a sensitive effect to the cement slurry, especially to the thickening time. It
reduces the thickening time which could set the cement quicker compared to average temperature
wells. High temperature could also affect the cement rheology, fluid loss, stability and compressive
strength. Because both the cement and the cement additives are very sensitive to changes in
temperature and pressure. Sensitivity and stability tests like thickening time test, Fluid loss test,
viscosity test, Density and compressibility test should always be performed before cementing in a
HPHT well.
Nanotechnology is one of the most dynamic research areas rich with both innovative science and
valuable applications. At nano-scale, the properties of an engineered nanomaterial are different from
that of a macro-material having the same chemical composition. Nanomaterials have a larger
surface area when compared to an equal mass of the same material in macro form.
Nanotechnology has provided a wide variety of solutions to resolve industrial problems, which
could not be previously addressed by customary methods. It enables researchers to alter properties
of bulk materials at the nanometer scale. Various nanomaterials have been successfully applied in
many areas of petroleum engineering, especially in drilling fluids, loss circulation, enhanced oil
recovery (EOR), and cementing.
Based on the various advantages of Nanotechnology, an extensive laboratory study was carried out
with available API Class G HSR Cement & cement additives using nano silica and new generation
nano weighing agent. A novel slurry formulations for HPHT oil well up to 230 °CBHCT and 2.5
SG were achieved with all required parameters to increase compressive strength, enhance early
compressive strength, reduce permeability and porosity, improve fluid loss, reduce transition time

from 100 lb/ft2 to 500 lb/ft2, and decrease density segregation. These innovative formulations are
cost effective, easy to handle and technically suitable, Also establishes in house advancement in
designing innovative cement slurries formulations and have become a proven approach for
cementing HPHT oil & gas wells.
Introduction:
Demand for fossil fuel is driving O&G industry to enter new ventures, as ease of finding easy oil is
a distant dream. Moreover due to present emphasis to explore deeper sequences in hostile HP-HT
environment. Growing demand to drill high pressure and high temperature (HP-HT) wells requires
improved technology to overcome HP-HT challenges. The challenges created by HP-HT
environment makes cementing in these regions difficult. The study reveals that in order to meet up
with the challenges of HP-HT cementing operations, issues such as effect of temperature and
pressure, large stresses, degradation of set cement at elevated temperature, small ECD windows,
efficient fluid design and displacement among others must be addressed for successful job execution
and excellent job delivery.
It is observed that cement design is one of the most concerning technology gaps for HP-HT
operations. The work highlights various cementing challenges associated with HP-HT wells and
provides a review of some of the best practices that have been adopted in several HP-HT wells.
Case studies in the area of HP-HT cementing examines some crucial problems associated with HP-
HT slurry design and as a way forward provides some innovative solutions based on experiments.
This will provide a learning point for successful cementation job for the emerging HP-HT
environment.
HP-HT Definition
There are various definitions of HP-HT, but the most appropriate and accepted one is given by
ArashShadravan&Mahmood Amani, SPE 163376, Dec., 2012 (Fig. 1): “High Temperature can be
defined as when the undisturbed bottom hole temperature is greater than 149 0C/ 300 0F. High
Pressure can be defined as either the maximum pore pressure of any porous formation that exceeds a
hydrostatic gradient of 0.18 bar/m (0.8 psi/ft), representing an EMW of 1.85 sg (15.4 ppg) or
needing deployment of pressure control equipment in excess of 69 MPa (10 Kpsi)”. High Pressure
need not be accompanied by High Temperature or vice versa. The HP-HT environment can be
further sub-divided into tiered levels:
Tier Temperature Pressure

300 deg F 10 Kpsi
I: HPHT
400 deg F 20 Kpsi
II: Ultra HPHT
500 deg F 35 Kpsi
III :Extreme HPHT
Fig. 1: HP-HT reservoirs Fig. 2: HP-HT Tiers

Indian Scenario
Huge potential reserves are locked up in various fields in Indian Sedimentary Basins: KG-PG,
Cauvery, Assam Arakan Fold Belt, Saurashtra Basin (Kutch offshore), Western Offshore Basin. The
discovery from HPHT environment was first established in 2007 from G-4 &Yanam fields in
shallow water areas of KG Basin.Now about 350 Mmt O+OEIP has been established. Further 1000
Mmt O+OEG is likely to be added. This has necessitated ONGC to embark upon exploration &
exploitation of these plays in a focused way.
Cementing HP-HT Challenges
Preparation & Pump-ability: Preparation of heavy weight cement slurry at drill-site is a problem
and if however it is prepared; to achieve initial consistency below 30 Bc for smooth pumping is
difficult.
The Effect of Temperature: Well cementing operations in HP-HT environment present special
system challenges as the physical and Oil field chemicals behavior of cement materials changes
greatly because of the high pressures and temperatures. These tough conditions add many
challenges not only during the well cementing operations while placement of the slurry, but also
later to the set cement sheath during the life of well.
The slurry becomes sensitive to high temperature so that thickening time of the slurry is highly
reduced, causing the cement set faster than in average temperature wells. Temperature also affects
the rheological properties of the cement slurry. Plastic viscosity and yield viscosity decrease with an
increase in temperature. Thermal degradation of cement additives also takes place at high
temperature, if thermally stable additives are not used.
The Effect of Pressure: Pressure has effects on both the well and the drilling fluid and cement
slurry. In cases where the pressure has not been properly estimated, the selected casing will not be
able to withstand the pressure from the formation, which will invariably lead to a collapse of the
casing in the well and therefore a kick is encountered.
Small ECD Window:The narrow margin between fractures and pore pressures in addition to the
tight annulus in lower zones increases the chances of lost circulation during cementation, leading to
insufficient cement rise. As the depth of well increases, the increased hydrostatic head causes an
increase in ECD due to compression and increase in temperature causes a decrease in ECD due to
thermal expansion.
Gas Migration; Migration of gas through the cement has been an industry problem for many years.
Gas is transmitted to surface through cemented casing during the critical hydration period, if the
slurry has slow development of gel strength i. e. long transition time.
Strength Retrogression;The strength of set cement also slowly starts to decrease after first two
weeks and this process of cement losing its strength is known as strength retrogression. Structural
changes and loss of water are the agents of cement degradation. When cement is set, it contains a
complex calcium silicate hydrate called tobermorite. At temperatures around 110 0C, tobermorite is
converted to a weak porous structure which causes strength retrogression.
Degradation of post set cement sheath

Cement sheath integrity is a very critical matter during the production phase. Primary cementing is a
critically important operation in construction of a well. Apart from providing structural integrity to
the well, the chief purpose of the operation is to provide a continuous impermeable hydraulic seal in

the annulus, preventing uncontrolled flow of reservoir fluids behind the casing. It is however ideal
to assume that cementing is the only consideration for effective zonal isolation.
Cementing can be a bit complicated, depending on the region drilled and sections encountered.
Therefore, special attention has to be paid to cementing processes especially in HP-HT wells. The
secret to zonal isolation is the good bonding properties of the cement with the casing and the
formation, but this can be affected by cement shrinking and stress changes induced by down-hole
variation of pressure and temperature. In HP-HT formations, the wells are subjected to high
temperature variations and these changes affect both the formation and the casings, causing casing
expansion and contraction. This expansion and contracting of casing causes cracks in the already set
cement. These cracks are a pathway for the migration of gas from the formation to the surface,
thereby shortening the life of the well because the integrity of the cement has been compromised.
Degradation of cement sheath and material takes place in HP-HT corrosive environment (in the
presence of H2S and CO2), effecting the long term integrity.
HP-HT Cementing Remedy
Accurate estimation of temperature:

Accurate prediction of bottom-hole circulating temperature (BHCT) is also very crucial in
cementing, because a change as small as 5 0C in the temperature can result in a large change in
thickening time. Computer based temperature simulators shall be used to estimate BHCT and/or
BHST.
Monitoring of down-hole conditions

It is utmost important to keep watch on the well behavior prior to cementation and review the
history of nearby wells for cementing problems encountered, e.g. lost returns, irregular hole erosion,
poor hole cleaning, poor cement displacement, etc.
Cementing Simulator
The software is used to optimize the cementing operation by recommending the best displacement
rate and slurry density (based on ECD behavior between pore and fracture density line). The
simulator can ensure that during the cementing job the down-hole pressure neither exceeds the
fracturing pressure of the formation nor drops below the pore pressure.
Efficient Displacement of Mud

The most important factor in obtaining a good primary job is properly displacing the drilling fluid.
If the mud is not properly displaced, channels and or pockets of mud may be left in the cemented
annulus, which can lead to inter-zonal communication and casing corrosion. Coatings from mud
additives (for e. g. polymers) and non-aqueous mud systems can interfere with the bonding between
the cement sheath and the pipe surface. Such poor bonding is typically reported as a micro-annulus
as viewed by a cement evaluation log and is often blamed for poor zonal isolation.
Spacers and flushesare effective displacements aids because they separate unlike fluid such as
cement and drilling fluid, and enhance the removal of gelled mud allowing a better cement bond.
Compatibility test of the mixture of the fluids with the spacer must be conducted to ensure there will
be no incompatibility problems when pumped into the well bore. For a mud to be displaced
effectively it must;
Have a low plastic viscosity to yield viscosity ratio (P.V./Y.P.),
Have a minimal gel strength development.
And the spacer should fulfill the following conditions;

To minimize cement contamination by drilling fluid i.e. prevent commingling and must be
compatible with both the drilling fluid and cement slurry.
To aid in mud displacement, density train and rheological hierarchy should be followed.
Should clean the solid surfaces and leave them water wet.
There should have ~ 10 % density difference between cement/spacer/mud.
It should have 10 min contact time.
Spacer should cover 200 m column as pre-flush and 50 m column as post-flush
Annular Velocity should be greater than 80 m/min.
Optimized Slurry Design

For successful cementing of a HP-HT well, major consideration should be given to slurry design
and slurry placement techniques. Specific characteristics of a particular well dictate the slurry
properties and performance. The slurry should develop the required properties and isolate the zones,
as well as protect the casing.
The procedure for cementing deep wells are basically the same as those for shallower wells;
however such wells are generally considered critical, because of the more severe well conditions
and higher complexity of the casing programs. A three-step design process to ensure construction of
a well that ensures a means of safe and economic production of hydrocarbons is imperative. The
three steps involve engineering analysis, cement slurry design and testing, and cement slurry
placement and monitoring respectively. Consequently, the cement system design can be complex,
involving an elaborate array of API Class G or H ‘HSR’ cement, retarders, fluid-loss additives,
dispersants, silica, and weighting materials.
Stopping of strength retrogression

Strength retrogression, a phenomenon that occurs naturally with all Portland cements at
temperatures greater than 110 0C, is usually accompanied by loss in impermeability, and is caused
by the formation of large crystals of α-dicalcium silicate hydrates (α-C2SH). Silica flour or silica
sand is commonly used to prevent strength retrogression by modifying the hydration chemistry. The
addition of 30 to 40 % silica is usually adequate to produce a set cement with low permeability (<
0.1 millidarcy) that overcomes the problems of strength retrogression, though addition can range
from 30 to 100 %. At high temperatures, silica causes the reaction with cement and water to produce
xonotlite instead of tobermorite. Xonotlite is a lot stronger and results in a significantly smaller
increase in permeability.
Anti-gas migration slurry design for HP-HT wells

Gas migration in the annular space after well cementing is the major problem for non-achieving
efficient zonal isolation. The main factor preventing the fluid from entering the cement is
hydrostatic pressure of cement column and the mud above it. This pressure must be greater than
pore pressure of gas-bearing formation to prevent fluid invasion into cement column. Besides, it
must not exceed fracturing pressure of the formation to avoid losses. The ability of the cement
slurry to transmit hydrostatic pressure, that affects the total hydrostatic pressure of the annular
column, is a function of the cement slurry gel strength. The higher the gel strength, the lower is the
transmissibility of the annular hydrostatic pressure.
The length of time from the point at which the fluid goes static until SGS (Static Gel Strength)
reaches 100 lb/100 ft2 is referred to as the “zero gel” time. When the (SGS) value reach 100 lb/100
ft2 it starts to lose its ability to transfer hydrostatic pressure.When the SGS value reaches 500 lb/100
ft2, the fluid no longer transmit hydrostatic pressure from the fluid (or the fluid above it). The time
required for the fluid’s SGS value to increase from 100 lb/100 ft2 to 500 lb/100 ft2 is referred to as
the “transition” time. To control gas migration, the “zero gel” time can be long, but the “transition”
time must be as short as possible (preferably, less than 30 minutes).

Use of expansive additive for improved cement bond

Burnt Magnesium Oxide (MgO) can be used as expansion additive. Adding these additives will
increase shear bond strength but will reduce compressive strength, although still higher than
recommended minimum value.
Cementing Techniques
Casing hardware, including float equipment, centralizers, cement baskets, wiper plugs (top and
bottom), and stage tools should be selected as necessary as part of the well design that will meet the
cement design objective and challenges and ensure isolation.
Casing centralizers should be selected to help center the casing in the hole and provide for good
mud removal and cement placement, especially in critical areas, such as casing shoes, production
zones, and groundwater aquifers.
Rotation and reciprocation of casing should be considered where appropriate to improve mud
removal and cement placement.
Cementation of HP-HT wells of ONGC

In some of the HP-HT wells of ONGC the quality of cementation was not desirable. IDT has
analyzed the following probable reasons of poor cementation with respect to the cement slurry
design used during cementation of few HP-HT wells of ONGC:
• Long thickening time
• Thermal thinning
• Low rheology
• Unstable slurry
• Settling of heavy weight material
• Poor displacement
• Channelling
• API Fluid loss > 50 ml/30 min
• Others: High initial consistency- difficult to prepare & pump the slurry.
Customized solutions by adopting Nano Technology for designing cement slurries for HPHT
wells
IDT has come out with the customized solution for application in ONGC wells to minimize the past
failures. As a proactive approach in-house technical capability & self-reliance has been developed in
designing the cement slurry for HP-HT wells for proper zonal isolation. Assimilation and
customizing them for application in ONGC wells will give thrust and confidence. In this connection,
IDT has designed ultra-high density cement slurries (2.1 sg to 2.5 sg) for extreme temperature
conditions (175 0C to 260 0C BHST).
Criteria adopted for designing HP-HT cement slurries

The designing of HP-HT cement system requires-
Special design attention: re-testing and sensitivity test (dose & temperature variation).
Modified testing procedure.
Special products - selection of right material, which are thermally stable, because quality of
chemicals defines thin line between success and failure of entire efforts. Synthetic retarders are
used, which are thermally stable and have linear characteristics of increase in thickening time with
increase in retarder concentration to achieve better thickening time control. Use of non-viscosifying
fluid loss additives for fluid loss control < 50 ml/30 min.

Particle packing concept: Four particles (coarse & fine silica and fine & micro-fine weighting
material) in variable ratio & variable sizes are used to maximize solid & minimize liquid content.
The voids in between the cement particles are filled with these fine & micro-fine particles. Less
water is used to fill the voids. Slurry and set cement mechanical properties are optimized
(mixability, consistency, gas migration, fluid loss control, compressive strength, low permeability,
etc.). To attain desired optimum rheology, raising the low-end rheology of cement slurries, avoiding
excessive thermal thinning, preventing settling and instability by use of particle packing concept
and/or anti settling agent. Control of strength retrogression: use of two blends of silica (fine &
coarse) for effective gas migration control.
Weighting material: Use of blend of Hematite & Manganese tetra-oxide, up to 2.25 sg.Short
transition time (vertical setting).
Results and Discussions

Based on the various advantages of Nanotechnology, an extensive laboratory study was carried out
with available API Class G HSR Cement & cement additives using Nano silica and new generation
weighing agent (Mn3O4). The results are presented in Table -1&2
Table -1 Cement slurry design for HPHT Well # KG Basin

Fig -1; Thickening Time and Consistency graph

Table -2: Improved cement slurry design with optimising Nano particles
Fig -2: Thickening Time and Consistency graph

Conclusions
• IDT identifies that high temperature thinning and high temperature settling of cement
slurries are most critical parameters in designing cement slurries for 175-260 0C and of sp.
gr. 2.10 - 2.50.
• The problems of gas migration, ultra HPHT fluid loss and high temperature settling were
found to be excellently controlled with the combination Nano particle packing.
• With coarse and fine silica along with Hematite and Manganese Tetra-oxide a cement design
is able to arrest gas migration and sedimentation even at ultra-high temperature of 260 0C.
• The particle range of 0.25-100 microns fine silica is critical to performance and used in
designing cement formulations for Ultra HPHT wells.
• The suggested systems have synthetic retarders, non-viscosifying fluid loss control additives
with a blend of Hematite and Manganese tetra-oxide to obtain best results.
References
1. Suyan, K. M., et al, “Ultra-high Density Cement Slurry Designing for HPHT Oil & Gas
Wells”, IDT MoU Project Report, March, 2013.
2. Yetunde, S. and Ogbonna, J., “ Challenges and Remedy for Cementing of HPHT Wells in
Nigerian Operation”, SPE 150751, Paper presented at the Nigeria Annual International
Conference & Exhibition held in Abuja, Nigeria, 30 July-03 Aug, 2011.
3. Shadravan, A. And Amani, M., “ HPHT 101-What Every Engineer or Geoscientist should
know about High Pressure High Temperature Wells”, SPE 163376, Paper presented at the
SPE Kuwait International Petroleum Conference & Exhibition held in Kuwait, 10-12 Dec,
2012.
4. API Recommended Practice 10 B-2, 2nd Edn. April, 2010.
5. Frittella, F., Babbo, M. And Muffo, A. I., “ Best Practices and Lessons Learned from 15
years of Experience of Cementing HPHT Wells in Italy”, SPE 125175, Paper presented at
the SPE/IADC Middle east Drilling Technology Conference & Exhibition held in Manama,
Bahrain, 26-28 Oct., 2009.
6. Salim, P. And Amani, M., “ Special Considerations in Cementing High Pressure High
Temperature Wells’, International Journal of Engineering and applied Sciences, Jan., 2013,
Vol. 1, No. 4.

Title: “Application of Thermally Activated Polymer for various Drilling Complications”

-Dr KishoriLal, Dr Deepak Painuly and Pradeep Kumar, Institute of Drilling Technology, Oil and
Natural Gas Corporation Limited, Dehradun.
Key words: Lost circulation treatments, Remedial casing repairs, sealing of leaking packers,,
Thermally Activated Polymer
Abstract
This paper highlights the necessary laboratory testing, field execution procedures and treatment
evaluation methods of indigenously developed polymers system so that this technology can be a key
resource for such operations in the future. This can solved many problems within the industry,
replacing conventional cement in many crucial primary cementing applications comprising filler
particulates that may be useful in subterranean operations, such as formation consolidation, zonal
isolation, lost circulation treatments, remedial casing repairs, sealing of leaking packers, well
abandonment plugs, and associated methods
One of the another major challenges when drilling oil and gas wells in offshore fields is to drill
under high pressure and in a loss circulation zone in intermediate hole sections. Heavy mud is used
to control the pore pressure in a narrow operational window that creates losses and, as a
consequence, well control issues. Several solutions/ideas have been implemented while drilling this
intermediate section, including a thermal-activated resin, rigid rapid fluid treatment, used to regain
full circulation and successfully increase the window gradient.
The solution to these challenges was developed in hose by designing a fast setting, thermal-
activated polymer LCM liquid plug with a density equal to 1.2 -1.5 SG. Polymer formulations
successfully prepared for temperatures ranging from 45°C to 150°C .Thermal activated polymer is a
nonreactive polymer with qualities that are resistant to all formation corrosives/hazard fluids.
Thermal activated polymer will reinstall a good well barrier and integrity to protect casing from
future corrosion. Similar type system has been used in serial wells in Saudi Arabia in both onshore
and offshore fields. In a small volume, with a controlled setting and short operation time, a high
success rate has been achieved
Based upon the present studies, it is evident that this novel product possesses low elastic modulus
and high flexibility in density, viscosity and fast setting time according to requirements. The
compressive strength is found to be extremely high to withstand the overburden pressure and
mechanical impacts during drilling. The well barrier elements made of this product have no risk of
shrinking, cracking, gas channeling or deterioration upon exposure to harsh reservoir environments.
Moreover have working high temperature range, cost-effective in comparison to product used by
service providers.
This system would be extremely economic as it can be applied directly after perforation if required,
saving rig time and reducing completion cost compared to Gravel pack, liner placement and
Screens, with the added advantage of no hole size reduction and better sand consolidation as
compared to other methods. .
Introduction
The present study relates to Polymer compositions comprising filler that may be useful in
subterranean operations, such as formation consolidation, zonal isolation, lost circulation treatments,

remedial casing repairs, sealing of leaking packers, Cement micro annulus, well abandonment plugs,
and associated methods.
Controlling lost circulation is a costly and time-consuming process with several possible
consequences such as stuck pipe, well control incidents, need to run additional casing strings,
formation damage and poor zonal isolation caused by poor cement coverage. Once the loss
occurred, something must be done to stop it. Bridge plugging is one of the most common
techniques. If the fluid circulation cannot be built even with a high concentration bridge material,
the cementing operation could be used, individually or mixed with bridge materials. The cement
plug is designed to penetrate into the loss zone.
Several solutions/ideas have been implemented while drilling this intermediate section, including a
thermal-activated resin, rigid rapid fluid treatment, used to regain full circulation and successfully
increase the window gradient and also have been tried out serial methods for how casing leakage
can be repaired safely and in a cost-effective manner. Casing damage/fine leakage/ cement micro-
annulus with low or non-injectivity have been squeezed and repaired with Thermal activated resin.
To address these issues, Polymer based formulations have been developed with highly tunable
specific gravity and drilling fluid-like rheology in the lab. The polymer shows applicability over the
broad temperature range of 45 - 130°C, with densities of 1.20-1.50 g/cc. In addition setting time can
also be adjusted accurately. The polymer formulation is able to be pumped easily through the drill
pipe.
The application of this novel polymer composition may be as casing repair material for successful
treatment of full losses or when there is no / low injectivity in fine leakage/ cement micro-annulus in
most of the critical oil and gas fields. Also, the report includes a discussion of the methodology,
material properties and applications.
Resin Chemistry
Resin chemistry, including epoxies, phenolics, and furans, has been widely utilized in a variety of
applications in well construction, completion, and production. This broad class of thermosetting
polymers is physically characterized as free-flowing polymer solutions that can be irreversibly set to
hard, rigid solids. The set time and ultimate strength can be chemically manipulated to offer a
powerful tool for wellbore applications. The attributes of resins have been utilized heavily in the
preparation of resin-coated proppants (Geehan 1999; Pope 1987) and in the strengthening of
unconsolidated sands (Nguyen 2004; Wasnik 2005). These chemistries have been extended to
applications in cement remediation (Sakhan 2010) and even as primary cements for zonal isolation.
Epoxy resins in particular have been developed for zonal isolation and consist of low molecular
weight pre-polymers containing multiple epoxy groups. These epoxy groups are then reacted to
form a dense, highly cross-linked matrix via addition of polyfunctional molecules (hardeners and/or
accelerators) such as amines, alcohols, thiols etc. The rate and extent of this cross-linking reaction is
determined primarily by temperature, time, and the exact chemical composition of the epoxy resin
and hardeners. These factors also largely determine the final physical properties of the cured resin.
Bisphenol A-based epoxy pre-polymers are most commonly employed;
Resin is a solid-free fluid that can penetrate tight narrow annuli, cracks, or fissures previously
inaccessible to conventional or fine cement slurries. Furthermore, this resin system can transition
from a liquid to a solid phase through crosslinking reactions consisting of stages of low-viscosity
liquid, high-viscosity liquid, viscoelastic solid, and finally forming a solid cross-linked three-

dimensional (3D) polymer network. The resin continues to transmit hydrostatic pressure to the
formation until an impermeable barrier of cured resin creates a highly ductile material that provides
resistance to liquid or gas penetration.
This novel product possesses low elastic modulus and high flexibility in density, viscosity and fast
setting time according to requirements. The well barrier elements made of this product have no risk
of shrinking, cracking, gas channeling or deterioration upon exposure to harsh reservoir
environments
The application of this novel polymer based casing repair material for successful treatment of full
losses or when there is no/low injectivity in formations in most of the critical oil and gas fields.
Also, the report includes a discussion of the methodology, material properties and applications
Methodology
Considering the merits of Resin/polymers in subterranean operations, such as formation
consolidation, zonal isolation, lost circulation treatments, remedial casing repairs, sealing of leaking
packers, well abandonment plugs, and associated methods. It was decided to do feasibility study of
Resin/polymers in house and develop in-house capabilities by using service provider’s materials
(especially from M/s Halliburton and M/s Schlumberger). Service provider refused to give the
Resin/polymers as these were their proprietary items.
Detailed market survey was done to find out similar or alternative of Resin/polymers to mitigate
existing challenges. One supplier/source was identified and was able to provide products as per our
requirement.
The materials was evaluated as per following test conditions:-.
Temperature and pressure conditions:

BHST/BHCT = 60/ 40ºC and Pressure = 2000 psi
BHST/BHCT = 90/ 60ºC and Pressure = 5000 psi
BHST/BHCT = 130/ 90 ºC and Pressure = 7000 psi
Experimental Details
An extensive experiment were carried out with an indigenously developed/ designed new Polymer
(Resin system) with various concentrations of catalyst and other additives as per testing conditions
specifiedand followed API RP 10 B-2 as standard test methods to evaluate following parameters.
• Mixing behaviour
• Specific gravity
• Thickening Time
• Compressive strength
• Rheology
Mixing Polymer and additives

The required quantity of polymer and other additives placed in the mixing container. The mixing
done at slow speed (2000 RPM) and completed within 35 seconds. Approximately 600 ml volume
of mixture was kept for testing TT parameters. Polymeric materials including catalyst are in liquid

form and can be easily mixed in tank/batch mixer with low RPM at drill site. Fluidity, mould and
drill ability can be seen in following Fig -1,2&3
Table-No.-1: Experiment with Polymer at BHST/BHCT 60/45°C, Pressure -1000psi

NB Catalys Accelerato Sp Initial 30 70 100B Compressiv Rheolog
- t –CV r Gr consistenc Bc Bc c e y
CV y strength@2
4 hrs
100 5 ml 2.0g 675 796 914 425 ND
1.2
ml 08 Mi Mi Min
1
n n
50 100 130 100
120
90 90
110
40 80 80
100
70 90 70
80
30 60 60
Consistency (Bc)
Temperature (°C)
Consistency (Bc)
Temperature (°C)
70
50 50
60
20 40 40
50
40 30
30
30
10 20 20
20
10 10
10
0 0 0 0
0:00 5:00 10:00 15:00 0:00 0:30 1:00 1:30 2:00
Time (HH:MM) Time (HH:MM)
Fig 4: Thickening graph of Polymer at 45°C Fig ;5 Thickening graph of Polymer at 130°C

Results and Discussion

Polymer system exhibited excellent properties such as highly tunable specific gravity and drilling
fluid-like rheology and enhanced compressive strengths upto 1,800 psi in 24 hrs without shrinkage
were achieved. The polymer shows applicability over the broad temperature range of 45 - 150°C,
with densities of 1.20-1.50 g/cc. Observed Rapid Right angle set, can provides a quick control over
losses. Also can helps in gas migration In addition setting time can also be adjusted accurately.
The polymer formulations are able to be pumped easily through the drill pipe. This novel product
possesses low elastic modulus and high flexibility in density, viscosity and fast setting time
according to requirements. The well barrier elements made of this product have no risk of shrinking,
cracking, gas channelling or deterioration upon exposure to harsh reservoir environments. Moreover
it has working high temperature range, cost-effective in comparison to product used by service
providers recently.
Detailed studies of the Polymer formulations at seven temperatures ranges: 45, 60, 90,110, 120
130°C were carried out in this study and TT graphs from lower range –higher range is presented in
fig 4&5.
Case Histories
Recently the use of resin/polymer system has been tried successfully for various complications by
few service providers with their products. The details are as follows,
Case # 1
First application of Thermal Activated Resin as Unconventional LCM used as field applications of
this novel polymer-based lost circulation material, for successful treatment of heavy mud losses to
formation in wells in offshore gas fields in the Middle East.One of the major challenges when
drilling gas wells in offshore fields is to drill under high pressure and in a loss circulation zone in
intermediate hole sections
The solution to these challenges was developed by designing a fast setting, thermal-activated resin
LCM liquid plug with a density equal to 152 pcf. This new treatment slurry was able to be bull-
headed and displaced with a polymer mud 152 pcf. The slurry was easily pumped through drill pipe,
measurement while drilling (MWD) and drill bits and controlled the loss. (SPE-177430-MS).
Case # 2
Casing damage/leakage with low or non-injectivity have been squeezed and repaired with Thermal
activated resin. Thermal activated resin is a nonreactive polymer with qualities that are resistant to
all formation corrosives/hazard fluids. Thermal activated resin will reinstall a good well barrier and
integrity to protect casing from future corrosion. Thermal activated resin has been used in serial
wells in Saudi Arabia in both onshore and offshore fields. In a small volume, with a controlled
setting and short operation time, a high success rate has been achieved. (SPE-182978-MS)
The solution to these challenges was developed by designing thermal activated resin casing repair
liquid plug with a density equal from 64 pcf to 152 pcf. The setting time can also be adjusted
accurately. This new treatment slurry was able to be bullheaded and displaced with polymer
mud/brine at 64 pcf to 152 pcf. The slurry was easily able to be pumped through the drill pipe. The
well barrier elements made of this product have no risk of shrinking, cracking, gas channelling or
deterioration upon exposure to harsh reservoir environments.

Case # 3
Prior to a fracturing operation on a well in the Utica Shale basin in Ohio, an operator conducted a
pressure test and found indications of a casing leak. The first squeeze operation was performed by
placing 10 barrels (bbl) of WellLock resin opposite the suspected leak and using the bradenhead
method, 2.5 bbls of resin material was squeezed into the leak. Forty-eight hours later, the WellLock
resin was milled out and the well was again pressure tested to 7,000 psi. Although the results
showed significant improvement and the well only lost 400 psi in 15 minutes, this well was not
secure enough towithstand the aggressive completion plan nor meet regulatory requirements. Four
days later a second squeeze was initiated using Well Lock resin. Using the same Braden head
method, 7 bbl of the resin was placed opposite the problem zone to squeeze 0.5 bbl into the leak,
and then the operation involved an additional step: 8,500 psi was held on the well for 6 hours,
allowing the resin to cure. After 48 hours, the resin inside the casing was milled out and the well
was pressure tested to 9,000 psi. The pressure test was successful and the well proceeded to the
completion phase. The customer successfully completed 42 hydraulic fracturing stages. The well
retained integrity, sustaining the concussive forces of the perforating operation followed by
pumping pressures of up to 10,000 psi for the fractureStimulation treatment.
Case # 4
Based on applicability of innovative application of Resin / Polymer System developed indigenously
a polymer system was designed for consideringsqueezing field problems in wells of Ankleshwar
where the challenges faced due to excess water production and gas production seized. To revive the
gas production, squeezing is required as cement cannot squeeze due to very low permeability/
injectivity. The time required for squeezing was biggest challenge as polymer set very fast
withincreasing temperature. Optimisation was done at Temp 110°C&TT extended more than 230
minutes which is adequate for placement along with all required properties. Solution is ready for
field implementation.
Conclusion
Based upon the present studies, it is evident that this novel product possesses low elastic modulus
and high flexibility in density, viscosity and fast setting time according to requirements. Further,
• Polymer formulations successfully prepared for temperatures ranging from 45°C to 150°C
but workability of polymer system observed up to 130 °C.
• Adequate compressive strengths were achieved, reaching upto 1,800 psi in 24 hrs. without
shrinkage upon cure.
• Observed Rapid Right angle set, can provides a quick control over losses. Also can helps in
control of gas migration.
• This study has demonstrated that the modified polymer system can provide both density
control from 1.20 to 1.50 SG and rheology control at 88°C.
• This concludes that the same polymer system can also be used for mud loss control, fine
casing leakage and channel repairing as it can be placed similar to cement plug and can be
injected to the small channels behind the casing very easily (up to 130 °C) and will be more
effective than squeeze cementing.
References
1. Wasnik, A.; Mete, S.; Ghosh, B. 2005. Application of Resin System for Sand Consolidation,
Mud-Loss Control, and Channel Repairing. Paper SPE/PS-CIM/CHOA 97771 presented at

SPE International Thermal Operations and Heavy Oil Symposium, Calgary, Alberta,
Canada, 1-3 November.
2. Cole, R.C. 1979. Epoxy Sealant for Combating Well Corrosion. Paper SPE 7874 presented
at SPE of AIME International Symposium on Oilfield and Geothermal Chemistry, Houston,
Texas, USA, 22-24 January.
3. Phipps, J.S.; Ladva, H.K.J.; Craster, B.; Caritey, J.P.; Dargaud, B. 2007. Design and
Evaluation of an Elastomeric Sealant for Use in Primary Cementing. Paper 106207
presented at the SPE International Symposium on Oilfield Chemistry, Houston, Texas, USA,
and 28February-2 March.
4. Patel, A.D.; Wilson, J.M.; Loughridge, B.W. 1999. Impact of Synthetic-Based Drilling
Fluids on Oilwell Cementing Operations. Paper SPE 50726 presented at the SPE
International Symposium on Oilfield Chemistry, Houston, Texas, USA, 16-19 February.
5. First Application of Thermal Activated Resin as Unconventional LCM in the Middle East by
K. Knudsen (WellCem AS) | G. A. Leon(WellCem AS) | A. E. Sanabria(WellCem AS) | A.
Ansari(Saudi Aramco) R. M. Pino (Saudi Aramco) SPE-177430-MS.

Title: “Thermic Fluid Applications & Potential in Gujarat Market”

-Dr Rajiv Srivastava, Indian Oil Corporation ltd.
Abstract:
Gujarat Industry:
Gujarat State is one of the most industrialized state of India having 202 GIDC Estates. It is hub of
Textile, Chemical & Petrochemical Industry. To maintain controlled temperature conditions
Thermic fluids are used. Heat Transfer Fluid for Heaters/Boilers used mainly in following
industries.
• Textile Industry
• Dye Industry
• Polyester Rayon Factory
• Ink Industry
• Petrochemical Plants
• Laminate / Plywood Industry
• Dehydration plant
These industries are mainly concentrated in Ahmedabad, Bharuch, Ankaleshwar, Surat, Silvassa,
Navsari, Valsad, Vadodara, Rajkot, Morbi, Jetpur, Mahuva & Kutch.
In Gujarat there is market of minimum 10,000 KL/Yr.
What is a thermal fluid system?
A Thermic fluid heater is industrial heating equipment, used where only heat transfers are desired
instead of pressure. To maintain controlled temperature conditions Thermic fluids are used. In this
equipment, a thermic fluid is circulated in the entire system for heat transfers to the desired
processes.
Thermal fluid (also known as hot oil) systems may be liquid or vapor.
Vapor phase
• Vapor phase systems may either incorporate a heater in which vaporization of the fluid takes
place within the vessel, or a flooded heater where the fluid is vaporized externally through a flash
drum.
• Vapor systems with condensing vapor provide a uniform heat source than liquid phase systems.
Liquid phase
• A liquid phase thermal fluid system uses a flooded pressure vessel (heater) in which the heat
transfer media (fluid) is heated but no vaporization takes place within the vessel.
• They are used in closed loop systems which may be open or closed to the atmosphere

Design Features
• Heaters are commonly direct-fired by combustion of a fuel, or electric resistance elements

can be used.
• Heater design may be similar to a fire-tube boiler, electric resistance heated boiler, or a
water tube boiler.
• Heaters may operate at temperatures up to 750⁰F depending on the process requirements and
fluid selection.
• Large heaters may be field erected; however, heaters less than 30,000,000 BTU/hr are
similar to packaged boilers utilized in a variety of process applications and may be found in
typical “boiler room” installations.
Thermal Fluid Heaters
Why use thermal fluid instead of steam?
• No corrosion or freezing concerns

• Simple circuit; no blow downs, steam traps, or condensate return systems
• Minimal maintenance
• No hand-hole gasket replacement
• No re-tubing
• No water treatment requirements
• High operating temperatures obtained with minimal system pressures (system pressure drop
only).
• If a process requires heating and cooling, it may be done with a single fluid.

Applications using thermal fluid heaters
System Components
A typical thermal fluid system is
comprised of four main components:
Thermal fluid heater
• Thermal fluid circulating pump
• Expansion tank
• User
Applications
• Applications using thermal fluid heaters

1. Pharmaceutical - Single Fluid Heating & Cooling
Pharmaceutical manufacturers worldwide have been using thermic fluids products for multi step
precision manufacturing processes, especially in batch processing operations.
2. Food Processing
Thermic fluids are widely used in food processing, with applications including food product
chilling and freezing, coil defrosting and cold room dehumidifying.
Thermic fluids is widely used in breweries, wineries and dairies for cooling and chilling during
processing.
3. Textiles / Nylon / POY / PFY / PSF / DMT
Synthetic heat transfer fluids have been used in the manufacturing of synthetic fibres like Nylon 6,
Nylon 6,6, Poly Oriented Yarn and Polyester Staple Fibre for over 50 years.
These fluids have been used both in the liquid and vapor phases in each step of the manufacturing
process like polymer manufacturing, spinning, annealing, heat treating and drawing.
4. Petrochemicals
Petrochemical manufacturing facilities widely use synthetic heat transfer fluids to provide heating
for reactors, crackers and distillation towers in the production of Linear Alkyl Benzene, Phthalic
Anhydride, Dimethyl Terapthylate, Terapthalic Acid and other associated downstream products.
5. Power
Thermic fluids are widely used in the power sector for cooling applications.
Thermic fluids are preferred worldwide for their reliability and extraordinary corrosion resistance.
6. Solar Concentrated Solar Power
Thermic Fluid is the preferred product for use in Solar-CSP thermal projects for its thermal stability
and operability upto 400°C
7. Plastics & Resins
For temperature control in molding, extrusion, press heating, line tracing, and coating rolls,
manufactures several specialized heat transfer fluids.
It is commonly specified in electrically heated temperature control units for molding applications
8. Paper & Plywood
In a thermal-oil-heated press, the mat is compressed and the wood and adhesive materials are
bonded and cured by heat activation at temperatures up to 550ºF.

System and Safety Considerations

• Thermal fluid selection
• Pump and proof of flow
• Fluid excess temperature protection
• Stack excess temperature limit
• Expansion tank design and fluid level
Thermal Fluid Selection

• Any fluid specifically designed for heat transfer use may be considered.
• Lubricating or hydraulic oils are not acceptable.
• Fluids must have physical property data at elevated temperatures.
• Factors to consider include:
• Maximum recommended bulk temperature
• System operation should never exceed the maximum bulk temperature of the fluid.
• Minimum operating temperature.
• Is cooling required?
• Minimum start-up temperature.
• Outdoor or indoor application.
Thermal Fluid Selection

• Vapor pressure/boiling point
• Special construction requirements if the operating temperature exceeds the boiling point.
• Some common thermal fluids include:
Thermal Fluid Maintenance

• Fluids should be tested annually.
• Lubricating oil tests that include dissolved metals are not adequate.
• Do not top off with different thermal fluid chemistry.
• Mineral oil/petroleum vs. synthetic/aromatic.
• Track heater inlet and outlet temperatures and pressures.
• Always record the date and the amount of fluid addition.
• Changing the type of fluid used in a system may require a change in the system components
(pump, expansion tank etc.).
• Chemical cleaners may also be required.
Thermal Fluid Pump

• Must be designed for use with thermal fluids at
temperature
• Standard hot water and boiler feed pumps are not
appropriate.
• Pumps may be air cooled, water cooled, canned or mag
drive designs.
• The pumps are sized to overcome the pressure drop in the
system and must be sized based on the specific gravity of
the fluid at operating temperature.

Proof of Fluid Flow

• Proof of fluid flow is critical for vessel longevity and system integrity.
• Means should be provided to prove minimum fluid flow through the heater at all operating
conditions to ensure proper velocities and film temperatures.
• A low flow condition can cause overheating, degradation of the fluid, or heater coil/tube
failure.
• Proof of flow is typically interlocked into the combustion circuitry
• Means to prove flow may include vortex shedding meters, flow switches, pressure switches,
an orifice or a differential pressure switch.
Fluid Excess Temperature Protection

• This limit prevents the fluid temperature from exceeding the maximum allowable
temperature of the specific fluid. It should be set no higher than the maximum bulk
temperature of the fluid.
• The temperature sensing device should be compatible with the fluid and the system
operating temperature and pressure and located at the heater outlet.
• It is generally interlocked into the combustion safety circuitry and often incorporates manual
reset functionality.
Stack Excess Temperature Limit

• Many installations include a high stack temperature switch interlock.
• In the event of a high stack temperature this device shuts off the burner and circulating
pump.
• The manufacturer of the heater determines the acceptable stack temperature for the heater.
• A high stack temperature indicates improper combustion (or soot build up) or a failed coil.
• Manual reset is recommended.
• The stack limit may be part of an inert gas smothering system.
Expansion Tank Design

• Fluid selection, system volume and operating
temperature will impact expansion tank size.
• Depending on the fluid selection and operating
parameters, systems may be open or closed to the
atmosphere.
• Closed systems may be pressurized with an inert gas
blanket.
• An ASME tank may be required.
When should a pressurized expansion tank be used?

• The tank is not the highest point in the piping system.
• The tank contents can be at a temperature such that exposure of the fluid to the air would
cause degradation of the fluid.
• The fluid is operated above its atmospheric boiling point.
• The fluid manufacturer recommends the use of an inert blanket.

Expansion Tank – Fluid Level

• A minimum liquid level must be maintained in the expansion tank to prevent pump
cavitations.
• A liquid level switch or similar device is typically provided and interlocked with the pump
and burner to shut them down in the event of a low fluid level condition.The switch should
be satisfied before the pump can start.
Installation
• Combustion air and ventilation requirements are similar to those of power or heating boilers
and determined by the manufacturer.
• A containment curb or seal welded drip lip on the heater skid should be considered.
• Piping, valves and system components are rated for the temperature and pressure of the
system
• Brass, bronze, aluminium and cast iron components are not recommended.
• Any sign of leaking piping is a safety concern, as the fluid or its vapors can be hazardous or
flammable.
• Piping should be welded or flanged where possible and pneumatically tested for leaks.
• Pressure relief devices
• The pressure relief valves should be a totally enclosed type with no lifting lever.
• The discharge piping of the pressure relief valve should be connected to a closed vented
storage tank.
• Insulation
• The insulation should be selected for the intended purpose.
• Where there is a potential for fluid leaks, the insulation should be non-absorbent.

Title: “Efficient Breaking of Crude Oil Emulsions: A Proper Mix of Engineering Science and
Art”
-Dr A.K. Saxena, ONGC, Vadodara
Abstract
There are a few developments which simultaneously occur when an oil field starts ageing and is so
called a mature or brown oilfield. The topmost being the increase in the water cut, others are being
changes in the characteristics of the produced crude oils and/or emulsions and final being the
increase in toughness of the produce emulsions which may also be a result of the particular
EOR/IOR process to which the oilfield is subjected.
The major challenge in a matured oil field, apart from maintaining or increasing the production
levels is to break the tough produced emulsions up to the desired levels so that they are accepted by
the crude processing refineries. The energies used in the demulsification process are heat energy,
chemical energy, kinetic energy and potential energy. All these energies are critical to the efficient
crude oil dehydration process and the total sum of the energies essential to break an emulsion may
depend upon the type and toughness of the emulsion.
The present paper discusses the various factors which determine the stability of the produced crude
oil emulsions including the crude oil characteristics, produced water characteristics and presence of
emulsifying agents. With the basic knowledge of the stabilizing factors of a crude oil emulsion , it
often becomes easier to define the emulsion breaking strategies. These strategies involve creation of
required engineering facilities, choosing a right chemical or a right combination of chemicals ,
creating the right conditions for emulsions breaking and effective segregation of the two
components, i.e., oil and water, after they have been separated.
The chemical often called as Demulsifier plays a critical role in the overall demulsification process
and developing a chemical formula for a particular emulsion requires understanding of the
characteristics and behaviour of the particular emulsion for which the chemical(s) are being
designed. The various types of chemical formulations which can be used for different crude oils and
under various conditions have also been discussed. The engineering surface facilities available for
the demulsification process also play an important role and their requirement for various types of
crude oil emulsion has also been discussed. Often, these two complement each other; however, the
deficiencies of the one can be supplemented by the efficiencies of the other.
The efficient crude oil demulsification is a process which involves appropriate surface facilities and
the right choice of a chemical . This requires a clear understanding of the characteristics of the oil
and emulsion . All of these put together help in making the process economically and technically
efficient.
Oil Field Emulsions

In the petroleum industry, the production of crude oil in the form of a water-in-oil emulsion is very
common. As the oilfields get matured , more and more oil is produced in the form of tight emulsions
with high water content. At the same time , the crude oil cannot be refined and transported, before
the water-in-oil is broken into two-phases, i.e., oil and water , and both are separated. In fact , as per
the refinery norms, the water content of the crude oil should not exceed 0.2% (v/v), while the water
content of the produced oil emulsions can go as high as 80% (v/v). Usually these emulsions are
water-in-oil emulsions.The stability of emulsion is affected by several factors including viscosity,
water content, density and element content of crude oil, asphaltenes, waxes, resins, etc. All can be
considered as surface-active materials and these elements are absorbed at the interfacial film which
prevent the water droplets from coalescence. Further, N-, O-, S-, bonding works on improving the
emulsion stability . The asphaltenes and resins are the most effective factors in enhancing the

emulsion stability. The reason that made asphaltenes and resins to enhance the emulsion stability is
due to the presence of hydrophilic functional groups in their structure. The interfacial films' rigidity
depends on what is deposited on the surface, whether asphaltenes or resins. The deposition of
asphaltenes will make the interfacial films stronger than resinous materials. Demulsification method
can be used to break emulsion by weakening the interfacial film or immobile interfacial films, and
this helps the droplets to coalescence. In addition, the elasticity and the emulsion stability are
affected by several factors and the most important factors are aromatic degree, concentration of
asphaltene and resin, resin-to-asphaltene percentage and dose of hydrophilic functional groups in
crude oil . Resin can work in high concentration with asphaltene as a destabilizing agent due to the
P-P and polar bonding . Hence, the lighter and less viscous oils are likely to form lesser stable
emulsions and the heavier viscous oils form very tight emulsions. The water phase of the emulsions
can go very high depending upon the forces and components present at the interface that stabilize
the emulsion.
Destabilization of Emulsions
Demulsification is the breaking of a crude oil emulsion into oil and water phases. From a process
point of view, the desired demulsification process may include:
• Rate or the speed at which this separation takes place

• Amount of water left in the crude oil after separation
• Quality of separated water for disposal
A fast rate of separation, a low value of residual water in the crude oil, and a low value of oil in the
disposal water are obviously desirable. Produced oil generally has to meet refinery and pipeline
specifications. For example, the oil shipped from wet-crude handling facilities must not contain
more than 0.2% basic sediment and water (BS&W) and 10 pounds of salt per thousand barrels of
crude oil. The salt is insoluble in oil and associated with residual water in the treated crude. Low
BS&W and salt content is required to reduce corrosion and deposition of salts. At downstream level,
the primary concern in refineries is to remove inorganic salts from the crude oil before they cause
corrosion or other detrimental effects in refinery equipment. The salts are removed by washing or
desalting the crude oil with relatively fresh water.
Since the stability of the water-in-oil emulsions arise from the formation of interfacial films that
encapsulate the water droplets , the resolution of the emulsion into oil and water is achieved by
destroying the films and making the water droplets to coalesce. Thus, destabilizing or breaking
emulsions is linked directly to removal of these interfacial films. The factors that enhance or speed
up the emulsion breaking process are:
• Temperature
• Agitation or Shear
• Retention Time
• Solids Removal
• Control of Emulsifying Agents
• Retrofitting
An increase in temperature has the following effects.

• Reduces the viscosity of the oil.

• Increases the mobility of the water droplets.
• Increases the settling rate of water droplets.
• Increases droplet collisions and favours coalescence.
• Weakens or ruptures the film on water droplets because of water expansion and enhances
film drainage and coalescence.
• Increases the difference in densities of the fluids that further enhances water-settling time
and separation.
A reduction in agitation or shear reduces emulsion stability. Very high shear is detrimental and
should be avoided. High shear causes violent mixing of oil and water and leads to smaller droplet
sizes. Smaller droplets are relatively more stable than larger droplets; therefore, measures that
increase shearing of the crude oil should be avoided or minimized where possible. Such measures
include:
• Mechanical chokes
• Valves
• Flow obstructions
• Pressure drops
However, a certain amount of shear is required for mixing the chemical demulsifier into the bulk of
the emulsion.
The period of time that the emulsion is held at the treating temperature is the residence, retention, or
treating time. This may be lesser for a normal crude oil , however, it may need to be much longer to
treat tight emulsions effectively. An increase in residence time increases the separation efficiency
and reduces the residual amount of water in the crude.
Solids have a strong tendency to stabilize emulsions, especially if they are present as fines or when
they are wetted by both oil and water. Removing the solids or their source is sometimes all that is
required for eliminating or reducing the emulsion problem. Oil-wet solids stabilize water-in-oil
emulsions. Water-wet solids can also be made oil-wet with a coating of heavy polar materials and
can participate effectively in the stabilization of water-in-oil emulsions. The presence of solid
asphaltenes and waxes has a definite detrimental effect on the emulsion problem,
The presence of mulsifying agents is necessary in the stabilization of emulsions, controlling them
allows for their destabilization and resolution. Some of the ways to control emulsifiers include the
following processes.
• Careful selection of chemicals that are injected during oil production. The chemicals include,
for example, acids and additives during acidization corrosion inhibitors for corrosion protection,
surfactants and dispersants for organic- and inorganic-deposition control, and polymers and
blocking agents for water-production control.
• Avoiding incompatible crude-oil blends. A crude-oil blend is incompatible if it results in the
precipitation of solids (organic and inorganic). This occurs, for example, when an asphaltic crude oil
is mixed with a paraffinic crude oil, resulting in the precipitation of asphaltenes. .
• Use of dispersants for controlling the precipitation of asphaltenes and the use of pour-point
depressants for controlling waxes.
Additional water separation can be achieved by retrofitting the existing equipment. Invariably,
emulsion problems increase after the separation equipment has been installed because of field aging,

increased watercuts, improper design, or several other reasons. Additional equipment like free water
knock-out drums and heater treaters can be installed.
Demulsification Mechanisms
Demulsification, the separation of an emulsion into its component phases, is a two-step process. The
first step is flocculation (aggregation, agglomeration, or coagulation). The second step is
coalescence. Either of these steps can be the rate-determining step in emulsion breaking.
The first step in demulsification is the flocculation of water droplets. During flocculation, the
droplets clump together, forming aggregates or "flocs." The droplets are close to each other, even
touching at certain points, but do not lose their identity (i.e., they may not coalesce). Coalescence at
this stage only takes place if the emulsifier film surrounding the water droplets is very weak. The
rate of flocculation depends on the following factors.[3]
• Water content in the emulsion. The rate of flocculation is higher when the water cut is
higher.
• Temperature of the emulsion is high. Temperature increases the thermal energy of the
droplets and increases their collision probability, thus leading to flocculation.
• Viscosity of the oil is low, which reduces the settling time and increases the flocculation
rate.
• Density difference between oil and water is high, which increases the sedimentation rate.
• An electrostatic field is applied. This increases the movement of droplets toward the
electrodes, where they aggregate
Coalescence is the second step in demulsification. During coalescence, water droplets fuse or
coalesce together to form a larger drop. This is an irreversible process that leads to a decrease in the
number of water droplets and eventually to complete demulsification. Coalescence is enhanced by
the following factors.
• High rate of flocculation increases the collision frequency between droplets.

• The absence of mechanically strong films that stabilize emulsions.
• High interfacial tension. The system tries to reduce its interfacial free energy by coalescing.
• High water cut increases the frequency of collisions between droplets.
• Low interfacial viscosity enhances film drainage and drop coalescence.
• Chemical demulsifiers convert solid films to mobile soap films that are weak and can be
ruptured easily, which promotes coalescence.
• High temperatures reduce the oil and interfacial viscosities and increase the droplet collision
frequency.
Sedimentation is the process in which water droplets settle down in an emulsion because of their
higher density. Its inverse process, creaming, is the rising of oil droplets in the water phase.
Sedimentation and creaming are driven by the density difference between oil and water and may not
result in the breaking of an emulsion. Unresolved emulsion droplets accumulate at the oil/water
interface in surface equipment and form an emulsion pad or rag layer. A pad in surface equipment
causes several problems including the following.
• Occupies space in the separation tank and effectively reduces the retention or separation
time.
• Increases the BS&W of the treated oil.
• Increases the residual oil in the treated water.

• Increases arcing incidences or equipment upset frequency.

• Creates a barrier for water droplets and solids migrating down into the bulk water layer.
Emulsion pads are caused or exacerbated by:
• Ineffective demulsifier (unable to resolve the emulsion);

• Insufficient demulsifier (insufficient quantities to break the emulsion effectively)
• Other chemicals that nullify the effect of the demulsifier
• Low temperatures
• The presence of accumulating solids
Because emulsion pads can cause several operational problems, their cause should be determined
and appropriate actions taken to eliminate them.
Emulsion Breaking or Demulsification Process
Crude oil emulsions must be separated almost completely before the oil can be transported and
processed further. Emulsion separation into oil and water requires the destabilization of emulsifying
films around water droplets. This process is accomplished by any, or a combination, of the
following methods:
• Adding chemical demulsifiers.

• Increasing the temperature of the emulsion.
• Applying electrostatic fields that promote coalescence.
• Reducing the flow velocity that allows gravitational separation of oil, water, and gas. This is
generally accomplished in large-volume separators and desalters.
Demulsification methods are application specific because of the wide variety of crude oils, brines,
separation equipment, chemical demulsifiers, and product specifications. Furthermore, emulsions
and conditions change over time, which adds to the complexity of the treatment. The most common
method of emulsion treatment is the application of heat and an appropriate chemical demulsifier to
promote destabilization, followed by a settling time with electrostatic grids to promote gravitational
separation.
The overall process involves thermal, mechanical , electrical and chemical methods.
Chemical Selection
Selection of the right demulsifier is crucial to emulsion breaking. The selection process for
chemicals is still viewed as an art rather than a science.
Demulsifier chemicals contain the following components:
• Solvents
• Surface-active ingredients
• Flocculants
Solvents, such as benzene, toluene, xylene, short-chain alcohols, and heavy aromatic naptha, are
generally carriers for the active ingredients of the demulsifier. Some solvents change the solubility
conditions of the natural emulsifiers (e.g., asphaltenes) that are accumulated at the oil/brine
interface. These solvents dissolve the indigenous surface-active agents back into the bulk phase,
affecting the properties of the interfacial film that can facilitate coalescence and water separation.
Surface-active ingredients are chemicals that have surface-active properties characterized by
hydrophilic-lipophilic balance (HLB) values. The HLB scale varies from 0 to 20. A low HLB value
refers to a hydrophilic or water-soluble surfactant. In general, natural emulsifiers that stabilize a

water-in-oil emulsion exhibit an HLB value in the range of 3 to 8. Thus, demulsifiers with a high
HLB value will destabilize these emulsions.
Flocculants are chemicals that flocculate the water droplets and facilitate coalescence.
Testing procedures are available to select appropriate chemicals.These tests include:
• Bottle tests
• Dynamic simulators
• Actual plant tests
All test procedures have limitations. Hundreds of commercial demulsifier products are available that
may be tested. Changing conditions at separation facilities result in a very slow selection process,
especially at large facilities; therefore, it is important at such facilities to maintain a record of
operational data and testing procedures as an ongoing activity.
Mixing/agitation
For the demulsifier to work effectively, it must make intimate contact with the emulsion and reach
the oil/water interface. Adequate mixing or agitation must be provided to thoroughly mix the
chemical into the emulsion. This agitation promotes droplet coalescence; therefore, the point at
which the demulsifier is added is critical. Once the emulsion has broken, agitation should be kept to
a minimum to prevent re-emulsification. There should be sufficient agitation in the flow stream to
allow the chemical to mix thoroughly, followed by a period of gentle flow inside the separator to
promote gravity separation.
Dosage and Mixing

The amount of chemical added is also important. Too little demulsifier will leave the emulsion
unresolved. Conversely, a large dose of demulsifier (an overtreat condition) may be detrimental.
Because demulsifiers are surface-active agents like the emulsifiers, excess demulsifier may produce
very stable emulsions. The demulsifier simply replaces the natural emulsifiers at the interface.
Furthermore, some of the chemicals come in different concentrations (active ingredient in a carrier
solvent). The amount or dosage of demulsifier required is very site-specific and may vary from
emulsion to emulsion.
The following are recommended for proper demulsifier mixing in the emulsion which is critical to
emulsion breaking:
• Injection quill (which injects the chemical in the stream at a location that is removed from
the wall)
• Chemical distributor
• Static mixer
Conclusions
The breaking of produced crude oil emulsions in effective manner needs proper understanding of
the emulsion forming factors and the various reasons that have stabilized the emulsion. This will
help in designing the surface facilities required for the overall demulsification process. The
optimization of heat , the time needed for breaking of emulsion and the time required for separation
of the two phases in a running system is what is required to enhance the overall efficiency. The
choice of chemical and the manner in which is added to the stream are important. Hence, an
efficient demulsification process needs good scientific understanding of the produced emulsion,

well designed engineering systems and art of choosing proper demulsifier. These combinations may
be emulsion specific and all of these put together can lead to a highly efficient process.

Title: “Monitoring of Marine Environment by ABC (Abundance-Biomass Curve) analysis - A

Case Study on Eastern Offshore area of Bay of Bengal”
-G.L.Das, Nikita Chiripal, Atul Garg, IPSHEM, ONGC
Keywords: ABC, r-selected, k-selected
Abstract:
Assessment of the variations in marine ecosystem can be effectively monitored using benthic fauna
because pollutants from any source will ultimately end in the seabed. The benthic communities play
an important role in the transfer of materials from primary production through detrital pool into
higher tropic levels, including commercially exploitable fish. They not only act as a major food
source for fish species but human also consume some of the large- sized bivalves and crustaceans.
The abundance/biomass comparison (ABC) method was proposed by Warwick in 1986 is
considered a sensitive indicator of physical and biological disturbance as well as pollution-induced
disturbance over space and time. The ABC method compares the ranked distribution of abundance
among species against the similar distribution of biomass among species. It indicates whether a
particular areas is undisturbed, moderately disturbed or highly disturbed.
A case study has been made around several sampling points in theEastern Offshore Region, Bay of
Bengal,during 2018-19,where lot of commercial activities are going on including the E&P activities
of ONGC. Benthic samples are collected from 15 different stations where operational activities of
ONGC are going on. Comparison has been made based on the dominance of k-selected species
(slow growing, large, late maturing) and r-selected species (fast growing, small, opportunistic).
Results of ABC analysis show that benthic community around the stations is not significantly
disturbed, indicating that operational activities of ONGC platforms is not creating any major
environmental stress.
Introduction
Assessment of the variations in marine ecosystem can be effectively monitored using benthic fauna
because pollutants from any source will ultimately end in the seabed. The benthic communities play
an important role in the transfer of materials from primary production through detrital pool into
higher tropic levels, including commercially exploitable fish. Majority of the benthic fauna are
sedentary and sessile in nature and cannot avoid any environmental perturbation, hence are
considered sensitive indicator of change in the environment caused by natural and anthropogenic
disturbances.
ABC curves have a theoretical background in classical evolutionary theory of r- and k-selection. In
undisturbed states, the community is supposed to be dominated by k-selected species (slow-
growing, large, late maturing), and the biomass curve lies above the abundance curve. With
increasing disturbance, slow-growing species cannot cope, and the system is increasingly dominated
by r-selected species (fast-growing, small, opportunistic), and the biomass curve will be below the
abundance curve. The difference between the two curves is given by the W-statistic, which
represents the area between them. The ABC method takes into account the number of species
included in the analysis (Warwick and Clarke, 1994: Ref: 6.2). An advantage of the method is that
an appropriate data set for any area or time should allow the status of the community to be evaluated
without the need for a spatial or a temporal control against which to compare the index obtained,
because the biomass is compared with the abundance for the same time and place (Clarke and
Warwick, 1994: Ref: 6.2).

This paper aims to explore the validity and possibility of this method by considering the abundance
and biomass data around the ONGC installations in the Eastern Offshore Region.
Study Area
Data was collected from 15 blocks of KG-PG basin of Bay of Bengal, shown in Table 1. Samples
were collected as per OSPAR Commission guidelines.
KG OSN 2004/1 Yanam PML
KG DWN 98/2 Yanam Additional Area PML
KG OSN 2009/2 Vanateyam PML
GS-49 PML Vanateyam Extension PML
GS-49 Extension PML GS-15/23 PML
GS-29 PML KG OS DW-III
GS-29 Extension PML Vasishta/G1-PML
Godavari PML
Table 1: 15 blocks sampled in KG-PG Basin
Field Sampling
During the oceanic cruise on board RV Sindhu Sankalp and Sindhu Sadhana, sediment sampling
was done as per OSPAR convention. Benthos were sieved and separated from the sediment sub-
samples collected using a quadrant core (625 cm2) and preserved in formalin - rose bengal solution.
Laboratory Analysis
Rose Bengal - formalin solution-preserved samples were passed through a set of sieves, the top
being of 0.5 mm pore size and the bottom with a 0.064 mm mesh size. The fauna retained on the
finer mesh (0.064 mm) was used for analysis of meio-fauna. The fauna present in larger mesh size
(0.5 mm) were analyzed for macro-fauna. All stained animals were picked and preserved in a 5%
seawater formalin solution. Organisms were sorted and counted group-wise under a stereoscope
zoom binocular microscope. Fauna was identified down to the group/genus level.Biomass (wet
weight) was measured by blotting the sample on a blotting paper and weight was taken by direct
weighing on balance. The biomass was calculated in g/m2
ABC Analysis
For construction of ABC curve, Primer (version 6), a software made for statistical analysis for
ecological study, was used.
Generally, a rank/abundance plot (or Whittaker plot) can be used to visualize species abundance
distributions. In this plot, the numbers of individuals of each species are sorted in descending order,
and the proportion of the total number of individuals for each species is then plotted on the log scale
against the species rank. The shape of the rank/abundance plot can provide an indication of
dominance or evenness, for example, steep plots signify assemblages with high dominance and
shallower slopes indicate higher evenness.
The paper focuses on ABC curve where dominance of abundance and biomass of species can be
compared for a particular study area and thereby helpful for assessing environmental stress.
Comparison of abundance and biomass of macrobenthos are studied here through ABC analysis.
Abundance i.e. mean density of different macrobenthic species around each stations of an
installation are counted as numbers/ meter2 and the total biomass of different stations are measured
as gm/m2 as listed tables. Now, the tables of abundance and biomass of different stations of a
particular installation are incorporated in the software (primer V6). After running the software as

“cumulative dominance curve” one ABC curve is formed where in y- axis we will get “cumulative
dominance %” and in x-axis “species rank” will appear. The difference between the two curves is
given by the W-statistic, which represents the area between them.

Most of the locations showed relatively high biomass and diversity of benthos. The highest macro
benthic biomass (av.4.1 gm-2) was found in GS-49 PML KG and the lowest in DWN 98/2 (0.02 gm-
2
). The highest macrobenthic abundance (750) were recorded in the blocks KG DWN 98/2 and the
lowest (19 No.m-2) in TGS-49 PML. Macro benthic Shannon diversity was the maximum in KG
OSN 2004 (0.98) and the minimum (0.33) in Vanateyam PML.
The ABC analysis of macro-benthos showed positive index value suggesting that the environment is
not significantly disturbed.
The ABC curves of the 15 blocks in KG-PG Basin are given as Figures 1 & 2.
Figure 1 - ABC analysis curve of macro-benthos of KG-PG basin. Green line indicates abundance
and blue line indicates biomass. Positive index value (W) indicates that the environment is
undisturbed.

Figure 2- ABC analysis curve of macro-benthos of KG-PG basin. Green line indicates abundance
and blue line indicates biomass. Positive index value (W) indicates that the environment is
undisturbed.
Conclusion
From the ABC Curve Plots, it is evident that biomass curve is above the abundance curve. Hence
W- statistic is positive for all the sampled 15 blocks in KG-PG Basin.
It can thus be concluded that benthic fauna is undisturbed in the sampled locations and so the
operational activities of ONGC installations have not caused any environmental stress.

Acknowledgement
This research was a part of the ONGC project “Offshore Environmental Monitoring of Eastern
Offshore Region (Deep Waters) 2018-19” being carried out by IPSHEM-ONGC in association with
CSIR-NIO, Goa. Authors acknowledge the contribution of everyone associated with the project.
Authors are also honestly grateful to Shri A. K. Dwivedi, Director (Exploration), ONGC, for his
encouragement for preparation of this paper.
References
[1]Warwick, R. M. (1986). A new method for detecting pollution effects on marine macrobenthic
communities. Marine Biology, 92, 557-562.
[2] WARWICK RM, CLARKE KR (1994) Relearning the ABC: taxonomic changes and
abundance/biomass relationships in disturbed benthic communities. Mar Biol 118, 739-744
[3]OSPAR Guidelines for Monitoring the Environmental Impact of Offshore Oil and Gas Activities,
2004-11.
[4] OEM report around ONGC installations in Eestern Offshore Region during 2018-19.

Title: - Some Challenges and Experiences in Upstream Chemical Treatment

- Dr. Sanjay Misra, ADNOC
Key words: - Challenges, chemical treatment, flow assurance, demulsifier, stimulation, asphaltenes,
scales, wax
Abstract
Over the years the oil and gas fields are getting matured. In search for new oil and gas the industry
is moving towards heavy, viscous, sour, tight, and unconventional fields. This has brought several
challenges in terms of flow assurance and material selection. The tight and unconventional
reservoirs demand new techniques of stimulation necessitating new chemicals and formulations to
the inventory. Further recovery from brown fields is only possible when flow assurance problems in
existing wells are addressed and EOR is implemented. Crude dehydration of heavy crude is
challenging as not only gravity separation is compromised but the component present in the crude
oil require some tweaking in chemistry. In brown fields requirement of low temperature
demulsifiers become paramount.Conventional PPDs are good enough up to 36-39oC pour point.
Many fields in South East Asia and Africa show pour point in the range of 51-57oC. These degraded
oils may requires different treatment. Hybrid chemical/engineering solutions should be tried. Mixed
scale and metal naphthenates deposition in the tubing, lines and separators also calls for improved
solutions. Present chemical EOR is cost intensive leading companies on shaky ground in view of
fluctuating oil prices. High concentration of polymer, surfactant and alkali, and challenges in water
treatment, high salinity and divalent tolerance seek new chemistries. Asphaltenes inhibition is based
on medieval asphaltenes deposition test (ADT), modifications suggested in the literature are just
different avatars. It is now established that deposited asphaltenes are structurally different than bulk
(n-heptane insolubles). In depth analytical studies are lacking at a time when human genome
analysis can be obtained from the corner shop! Acidization of tight and unconventional carbonate
stimulation is definitely a better proposition than hydraulic fracturing. But results of conventional
15% hydrochloric acid recipes are farfetched. Low reactive formulations is possible option. The
challenges faced by the industry defy the conventional chemicals and additives and warrant
paradigm shift in search of new solutions. Present talk is sharing some experiences in facing such
challenges and efforts to look for possible solutions.
Introduction
Over the years the oil and gas fields are getting matured. In search for new oil and gas the industry
is moving towards heavy, viscous, sour, tight, and unconventional fields. This has brought several
challenges in terms of flow assurance and material selection. The tight and unconventional
reservoirs demand new techniques of stimulation necessitating to incorporate new chemicals and
formulations to the inventory. Further recovery from brown fields is only possible when flow
assurance problems in existing wells are addressed and EOR is implemented. Present chemical EOR
is cost intensive leading companies on shaky ground in view of fluctuating oil prices. The
challenges faced by the industry defy the conventional chemicals and additives and warrant
paradigm shift in search of new solutions. Present talk is sharing some experiences in facing
suchchallenges and efforts to look for possible solutions.
Brown Field Woes: Demulsification and Scaling

As the fields mature more water is produced resulting into more volume to treat. More marginal
fields are added. In many cases these fields are having relatively heavy and degraded oil. Thus, the
equipment is used over the designed capacity. Poindexter et al (2005) found that solid content has

the biggest effect on emulsion stability. Degraded products like resins and asphaltenes aid to the
misery. Crude dehydration of heavy crude is challenging as not only gravity separation is
compromised but the component present in the crude oil require some tweaking in chemistry.
Because of the high volumes the desired temperature is seldom achieved. Therefore, the search for
low temperature demulsifiers become paramount. The resin content in such crudes is high. The
behavior of resins in the crude depends on their affinity towards divalent cations present. In many
fields resin fraction has significant amount of naphthenic acids. These compounds form metal
nephthenates adding misery to dehydration. Metal naphthenates migrate to interface and become
difficult to treat.
The Stroke’s Law governing the separator designassumes that water is free to settle. Thus, effective
demulsification is must. In many cases tendency to over treat is seen. For example, in fields afflicted
with metal naphthenate problems are over treated with acetic acid to reduce the pH. The choice of
demulsifier should be made with the resin faction in mind. Chelants can be used to mask divalent
cations. Use of chelants is pH restricted. Many of them are soluble in alkaline pH only. Poindexter
et al (2005) found that solid content has the biggest effect on emulsion stability. Degraded products
like resins and charged molecules likeasphaltenes aid to the misery.
The scaling problem is common in oilfields. As the fields mature, we have to deal with problems of
mixed scales. In case of inorganic scales we have some organic matter deposited in the matrix. Such
scales do not respond to aqueous formulations like acids and chelants. Conversely the organic scales
like wax and asphaltenes also show some inorganic matter co-precipitated. Such scales when treated
with organic solvents produce sludge which tends to block the tubing and prevent further progress
of the job.
Metal naphthenates is a special case of mixed scales. Metal naphthenates problem in South East
Asia, Congo, Angola, and North Sea is well known. These species tend to have deposition in the
tubing, lines and separators. The demulsification is also compromised due to presence of metal
nephthenates in the interface. Calcium and iron ions make salts with naphthenic acids. In some
cases such salts give rise to tough deposits which are not soluble in water or acid. Also, they do not
respond to organic solvents (even boiling benzene). Migration of such salts to oil water interface
gives rise to tough emulsion problems as mentioned earlier. Such deposition in the separator causes
havoc to the system.
The scales can be treated with appropriate formulations. In case of metal naphthenates organic
based solvents were used (Misra & Singh 2007). Microemulsion based formulations show
promising results. This is a way to utilize best part of water and solvent based formulations
simultaneously (Misra 2018). In case of wetted inorganic scales solvent part dissolves the organic
species to enable inorganic surfaces for acid or chelant scale. In case of organic mixed scales the
aqueous part of the formulation is able to dissolve calcite or sulfate to prevent formation of sludge.
Surprisingly, microemulsion based formulations showed good response towards dissolving tough
iron naphthenates scales. This could be a major breakthrough in dealing with such scales and related
problems.
It is seen that barite scales do not respond to diethylenetriamine penta aceticacid (DTPA) solutions.
Oxalate catalysts reported in the patent literature (Moris & Paul 1990) have failed to salvage the
situation (Shende 2012). In most cases lab work is conducted on powdered scale samples but
experience show poor response to bulk scales. Our study show that microemulsion based
formulations can tide the balance. It calls for further work since making appropriate microemulsion
with solvent and highly alkaline DTPA solution is difficult. The cloud point is reached at high
temperatures. Therefore, formulations targeting temperature of interest are required. The science of

microemulsion has taken big leaps in medicine delivery and synthetic chemistry. We can surely get
formulations to address our issues.
Conventional PPDs, EVA polymers,linear alcohol ethoxy polymers and other chemistries, are good
enough upto 36-39oC pour point. Many fields in South East Asia and Africa show pour point in the
range of 51-57oC. Some fields in Ahmedabad and Mehsana (Nandej, Dholka, Balol and Sobhasan)
show high pour point viscous behavior.Fields like Mangla have pour point of 45oC (Zalwadia &
Pawde 2013). The line transporting this crude requires special heating system. There are instances
of trunk line failures due to irreversible oil congealing. Ragbir (2014) describe irreversible
congealing of Puteri line in Malaysia. The degraded crude showed a pour point of 48o C. During the
shutdown the congealing in 12 Km line was made defunct. The line was subsequently replaced with
a pipe-in pipe heating system. We require hybrid (chemical plus engineering) solutions to overcome
this situation.Treating such crudes like conventional waxy crudes may be catastrophic as they have
high degree of degradation.Thermochemical upgradation of heavy crude oilin-situ/ in production
flow pathor heattracing of the lines along with chemicals may offer the best solution.
Experience with asphaltenes deposit inhibition presented surprising results. The existing chemistries
did not work. The lab screening methods also require review. The conventional asphaltenes
deposition test (ADT) is still in operation. Recent research shows the same test is conducted in
different avatars in tube blocking or packed column. There are indications that bulk asphaltenes (n-
heptane insolubles) are quite different than their deposited counterparts. It was observed that double
bond equivalent (DBE) and molecular weight of deposits species is always higher than n-heptane
precipitated species. Juyal (2010) conducting Fourier Transform – Ion Cyclotron Resonance Mass
Spectroscopy (FT-ICR-MS) on asphaltenes samplesrevealed that functional group distribution of
deposited species is way different. Some of the compounds having, for instance, O-functional
groups may be present in trace amount in bulk but they seem to amplify in deposits. One wonders
that while testing inhibitors we are ignoring this fact. It is also possible that interactions may
not be so significant in formation of asphaltenes deposits. Polar interactions may also have some
play. The deposited asphaltenes composition changes with pressure and temperature. FT-ICR-MS
technique has evolved over time. It shows that there may be over 30,000 different molecules in the
asphaltenes band. The molecular weight goes as high as 300-800 amu. But some statistical
techniques can be applied to have an idea of model asphaltenes molecule for a field. In depth
analytical studies are lacking at a time when human genome analysis can be obtained from the
corner shop!
We tried to simulate asphaltenes deposition in a concentric cylinder-cup geometry, like in the case
of wax deposition studies (Akbarzadeh et. Al. 2008). But the results were not conclusive, probably
due to the fact that asphaltenes deposition is not temperature related. Some researchers are trying to
deposit asphaltenes in quartz crystal microbalance deposition (QCMD) experiments (Joonaki et al
2018). This technique shows some promise to capture actual depositing species. Once proven this
technique may offer a good alternate to inhibitor screening. Low temperature QCMD experiments
showed that the depositing species have much lower DBE-molecular than field deposits. That again
proves a case against ADT which is performed at ambient conditions.Jijo et. al. (2017) have tried to
look at asphaltenes structure using atomic force microscopy and demonstrated that the mechanism
of deposition on different surface may differ. Thus there are advances in analytical chemistry, we
need to utilize them for our advantage.
Future of our industry depends on successful EOR implementation as substantial reserves can be
unlocked. Implementation of natural gas and CO2 water alternating gas (WAG) is considered
achievable. ln case of natural gas a resource is committed while cost of CO2 capture is major

consideration for the other. Cost of CO2 captures hovers somewhere US$ 50/t which requires
considered efforts to bring it down. Chemical EOR is facing big technical hurdles due to fluctuating
oil prices. It is a good case for low temperature good quality clastic reservoirs. The available cost
intensive technology is not at all viable for the offshore. With polymer concentration at 1500-2000
ppm, surfactant concentration from 3000-8000 ppm and, in some cases alkali concentration in the
range of 1-2% has made the technology a pipedream for onshore operators also. Implementation of
such technology in giant fields require high CAPEX and OPEX. The logistics of chemical provision
and water treatment is challenging. Limitations of high temperature, high salinity and divalent
tolerance remain largely unattended. Requirement of low salinity water for EOR also comes in the
way of economics. In case of sea water projects sulfate removal is required. But present-day
membrane filtration technology for sulfate removal are akin to costly reverse osmosis. Why can’t
we have selective sulfate removal? It is true that many EOR success stories are not available in
challenging reservoir conditions. In view of this we require some out of box thinking. Short chain
surfactants is considered an option. May be pore volume injection requirement can be reduced with
good conformance monitoring. It is pertinent to note that EOR schemes will further add to chemical
treatment challenges in the produced fluid. Studies for demulsification, corrosion, flow assurance
etc. should be carried out in advance. We must work hard to make EOR a success as our future is at
stake.
Acidization of tight and unconventional carbonate stimulation is definitely a better proposition than
hydraulic fracturing. But results of conventional 15% hydrochloric acid recipes are farfetched.
Optimized wormholing is the key to carbonate acidization. Since pioneering work of Hoefner and
Fogler (1988) many researchers have established that ideal wormholing is achieved when reaction
rate of the formulation and pumping rate is at a balance. In tight carbonate reservoirs high pumping
rates cannot be achieved thus low reactive formulations must be considered. Punappala et al (2014)
demonstrated that required pumping rate for optimal wormholing can be calculated for a well in a
reservoir based on diffusivity coefficient of the formulation. It was established that low reactive
acids may prove better. In case of chelants the diffusivity coefficients are one order lower than 15%
HCl. But most chelants like EDTA are soluble at low pH. It was therefore proposed to use acid
soluble chelants like GLDA. It was also found that even these chelants cannot achieve optimal
wormholing in horizontal wells drilled in sub mD reservoirs. Further reduction of reaction rates is
required. If the chelating species is dispersed in a solvent forming microemulsion, then the
diffusivity coefficient can be further reduced by one order or more. This is because the reaction rate
is of a dispesed phase in microemulsion is governed by Brownian motion rather than diffusion.
Studies conducted by Sazali et. al. (2018) demonstrated this hypothesis for a high temperature (130o
C) reservoir. Optimum wormholing was achived at 1.5 ml/min injection rate in a 3” core. We can
further play with ratios of dispersed and continuous phases.
Conclusion:
There are many challenges faced by the industry in respect of chemical treatment of brown fields.
Over time difficult to treat oils are getting into inventory. Implementation of EOR schemes may
further aggravate the situation. Collaborative researchis the order of the day. This culture must be
imbibed in here. We can look at the western model for this purpose. It is the time to come together,
look at the history, contemplate our failures, see the emerging trend with new light and embark on a
journey of innovation with renewed vigor.
References:
1. Akbarzadeh, K., Ratulowski, J., Eskin, D. and Davies, T.; “The Importance of Wax Deposition
Measurements in the Simulation and Design of Subsea Pipelines”, SPE 115131 PP, 2008.

2. Hadirah, N. Ibrahim, J.M., Rohaida, S., Misra, S. andSingh, K.; “System for Removing Organic
Deposits”, US20160340567A1. Malaysia Patent MYPI20093108, 2009
3. Hoefner, M.L. and Fogler H.S.; “Pore Volume Evaluation and Channel Formation During Flow
and Reaction in Porous Media”, AIChE Journal 1988, 34(1):45-54
4. Joonaki, E., Buckman, J., Burgass, R., and Tohidi, B., Exploration of the Difference in
Molecular Structure of n ‑ C7 and CO2Induced Asphaltenes, Ind. Eng. Chem. Res. 2018, 57,
8810−8818.
5. Jijo, R., Lesimple, A., Whelan, J. and Pance, N.; “Direct Observation of Asphaltenes Nano
Particles on Model Mineral Substrates, Langmuir 2017, 33, 25, 6248-6257.
6. Juyal, P., McKenna, A., Fan, T., Cao, T., Rueda-Velasquez, R., Fitzsimmons, J., Yen, A.,
Rodgers, R., Wang, J., Buckley, J., Gray, M., Allenson, S. and Creek, J.; “Joint industrial case for
asphaltene deposition”, Energy & Fuels, 2013, Vol.27, pp. 1899 – 1908.
7. Misra, S. and Singh, K.; “Compositions for Removal of Deposits in Oil Well Production and
Transport System”Malaysian Patent – MY-143762 – A, 2007.
8. Misra, S.; Ibrahim, J.M. and Saleh, I.K.; “Microemulsions and uses thereof” Malaysian Patent,
Appl No. 2018001571, 2018
9. Morris, R.L. and Paul, J. M.;”Method for Removing Alkine Sulfate Scale”, US Patent
4,980,077, 1990.
10. Poindexter, M. K., Chuai, S., Marle, R. A., and Marsh, S.C.; “Solid Content Dominates
Emulsion Stability Prdiction”, Energy & Fuel, 2005, 19, 1346-52.
11. Punnapala, S., Abdul Rahman, M. andMisra, S.; “Challenge of Acidizing Horizontal Wells in
Tight Carbonate Reservoirs - Weak Acid and Non-acid Alternates, SPE 171766,2014. Published in
JPT, June 2015 pp 97-99.
12. Ragbir S.D., “Offshore Installation of Puteri Heated Pipe-in-pipe System in Malaysia”, OTC
25057, 2014
13. Sazali, Y., Misra, S., Sazali, W.L., Ibrahim, J. M., Graham, G.M., Kidd, S.L., Ohen, H.A. and
Gӧdeke, S. ;”Evaluation of the Effectiveness of Matrix Stimulation Recipes for High CO 2
Carbonate Reservoirs for Bypassing Formation Damage”, SPE-189567, 2018
14. Shende, V. A.; “Dissolution of Barite Scale using Chelating Agents”, Master of Science Thesis,
Texas A&M University, 2012.
15. Zawadia, H., and Pawde, C.; “Case Study on Handling Paraffinic and Viscous Crude of
Mangala Oil Field of Rajasthan – India”, SPE 164670, 2013.

Title: “Effect of Reservoir Minerals and Fluids on Alkali Transport”

-Himanshu Sharma, Department of Chemical Engineering, Indian Institute of Technology Kanpur
Key Words: Alternate alkali, ASP flooding, Ammonia, Sodium Metaborate, Clays, Anhydrite
Abstract
Geochemical interactions between injected fluids and reservoir fluids/minerals can alter the
composition of injected fluids andthe reservoir properties. Geochemical interactions are important
particularly when alkali is used in chemical enhanced oil recovery (EOR) formulations. This is
because the alkali can undergo chemical reactions with reservoir fluids and minerals resulting in
high alkali and surfactant consumption. Additionally, this can also affect surfactant phase behavior
and reservoir properties. Laboratory experiments are carried out to access the potential of alkali
interactions on the effectiveness of an EOR process. However, these experiments are not always
helpful because the time-scale involved in lab experiments is much less than in the field.
Simulations are helpful in such cases to access the impact of geochemical interactions.In this study,
simulations were performed to understand the interaction of various alkalis with reservoir fluids and
minerals using PHREEQC, the US Geological Survey (USGS) geochemistry software. The effect of
clays and gypsum (or anhydrite) on alkali transport was investigated.The modeling results were
compared with the experimental results available in the literature. The effect of change in brine
composition on geochemical reactions was investigated. Our simulations show that geochemical
interactions of alkali with gypsum (or anhydrite) severely hampered alkali transport. The cation
exchange reactions, in case of clays, introduced divalent cations which not only consumed alkali but
could potentially also affect the surfactant phase behavior if alkali and surfactant selection is not
done carefully. Similarly, chase polymer slugs must be carefully prepared else geochemical
interactions could severely affect the success of a surfactant flood.
Introduction
Due to an increase in our energy demand and a constant depletion of easy oil, enhanced oil recovery
(EOR) techniques are being developed to increaseoil recovery from our existing reservoirs.
Surfactant-based EOR techniques involving wettability alteration or reduction in interfacial tension
(IFT) have huge potential to increase recovery from many of our existing oil reservoirs.An alkali is
often added along with the surfactants in these formulations to reduce surfactant adsorption on the
rock and to generate in-situ surfactants in case of acidic crude oils. While an alkali helps in reducing
the amount of surfactant required for a given process and thus making the process more economical,
it also adds to thecomplexity due to its potential to undergo geochemical interactions with reservoir
fluids and minerals. These interactions could be not only detrimental to an EOR process but also for
the reservoir. Earlier studies, which were mainly focussed on sandstone reservoirs, found that the
alkali should be able to give a high pH to avoid pH propagation delays in sandstones as a result of
ion exchange with clays. Strong alkalis such as sodium hydroxide and sodium silicate were
therefore investigated. However, these alkalis were found to be detrimental to reservoirs,particularly
at high temperatures. Dissolution/precipitation reactions were observed on using these strong alkalis
in sandstone reservoirs which resulted in consumption of alkali, pH propagation delays and
reservoir permeability damage. Since these reactions were slow reactions, kinetic studies were
performed to understand the impact of these reactions at the field scale. Due to limitations of strong
alkalis, relatively weaker alkalis, particularly sodium carbonate, became an alkali of choice for EOR
formulations. Sodium carbonate was found to lower surfactant adsorption on sandstones and
generate in-situ soap in case of acidic crude oils. Sodium carbonate was therefore, technically, a
suitable alkali candidate for sandstone reservoirs. However, various other factors including alkali

handling, transportation, storage, etc demanded alternate alkalis to be looked into. Another factor
that demanded alternate alkalis was the application of these EOR methods to carbonate reservoirs.
Carbonate reservoirs are much complex than sandstones in terms of their mineralogy, among other
factors. Sodium carbonate was found to react extensively with gypsum (or anhydrite); a mineral
which is often encountered in carbonates. Even a small amount of gypsum (~0.1%) in the rock was
found to have an extremely detrimental effect of EOR processes developed using sodium carbonate
as the alkali.1As a result, sodium metaborate and ammonia were investigated to address these
issues.2,3Sodium metaborate was found to give the required pH, lower surfactant adsorption on
sandstones and carbonates, and show limited reactivity towards gypsum (and anhydrite). High pH
propagation and negligible change in rock permeability were observed when sodium metaborate
was used as alkali in EOR formulations. Ammonia, on the other hand, gave the desired pH values,
did not react with gypsum (or anhydrite), and lowered surfactant adsorption mainly on sandstones.
A major advantage that ammonia offered was due to its low molecular weight which enabled a huge
reduction in the amount of alkali which needed to be transported and stored for field operation. The
following alkalis have therefore emerged as the key candidates for an EOR operation: sodium
carbonate, sodium metaborate and ammonia. Recently, sodium hydroxide has been proposed as an
alternate alkali for limestone reservoirs.4 In this study, geochemical interactions of these alkalis with
reservoir fluids and minerals were investigated through one-dimensional simulations and results
were compared with the literature.This study was focussed on understanding the role of gypsum and
clays. Clay minerals are commonly encountered in sandstone reservoirs and may result in
introducing divalent cations into surfactant slug and affecting its success.A list of simulations
conducted in this study is given in Table 1.
Table 1: List of simulations performed in this study
Simulation Description
Case 1: Alkali injection in gypsum containing carbonate rocks
(a) Sodium carbonate solution
(b) Sodium metaborate solution
(c) Ammonia solution
Case 2: Effect of cation exchange on surfactant floods prepared in
(a) Soft brine
(b) Soft brine + ammonia as alkali
(c) Soft brine + ammonia + small amount of sodium carbonate
Modeling& Simulation Techniques

One-dimensional flow simulations were performed to investigate interactions of an aqueous
solution, containing alkali, with reservoir minerals. The simulations were performed using
PHREEQC, the USGS geochemistry software, assuming isothermal conditions. Changes in the
composition of the injected solution and reservoir minerals, as a result of geochemical interactions,
was obtained from simulations and compared with data available the literature. Two problems were
investigated in this study, that is, the effect of gypsum (we will refer both anhydrite and gypsum as
gypsum in this paper) on alkali transport and theeffect of cation exchange on surfactant floods. The
results obtained for simulation case 1 were compared with experimental results published in the
literature.2,5,6No systematic set of experiments could be found in the literature to compare simulation
case 2.

Results & Discussion

1. Alkali injection in gypsum containing rocks:
(a) Sodium carbonate: Sodium carbonate is commonly used in chemical EOR formulations. However, it
undergoes the following reactions in the presence of anhydrite (or gypsum) which result in alkali
consumption, pH propagation delay, and permeability damage.
CaSO4 (s) = Ca2+ + SO2−

4
Ca2+ + CO3 = CaCO3 (s)
Simulation 1(a) was conductedto study the effect of these reactions on the pH, effluent ions and in-
situ mineral composition. In this simulation, a sodium carbonate solution was continuously injected
in a carbonate core, containing gypsum, which was initially saturated with the formation brine (see
Table 3). Local equilibrium assumption was made in this simulation. Figure 1(a) shows that
although the pH of the injected sodium carbonate solution was 10.9, the effluent pH did not increase
more than 9.3 even after injecting 2 pore volumes of sodium carbonate. Figure 1(b) shows that this
was because of a continuous reaction of the injected solution with gypsum that resulted in the
formation of calcium carbonate. The simulation results were compared with a similar experiment
reported in the literature.6 The properties of the core used in the experiment are given in Table 2.
Our simulations were in good agreement with the effluent sulfate, calcium and pH data reported in
this study. The effluent sulfateconcentration increased while calcium concentration decreased due to
the reaction of sodium carbonate with gypsum. Note that the effluent pH in this experiment slowly
reached around 10 after 2 pore volume injection which was in contradiction to our simulation result
where the effluent pH was around 9.3. This discrepancy is because the experiment was conducted at
a high flow rate which did not allow enough time for alkali to react. This highlights a limitation of
lab experiments. Our simulations were conducted accordingly to obtain a good agreement with the
experimental results.
(b) Sodium metaborate: Recent studies have shown that sodium metaborate can potentially be used as
an alternative to sodium carbonate in cases when gypsum is present in an oil reservoir. Simulations
1(b) were carried out to understand the transport of sodium metaborate solution in the presence of
gypsum and results were compared with the experiments reported in the literature.6 Figure 2(a)
shows effluent pH, calcium, and sulfate concentration reported in the literature and obtained from
our simulations. Note that the injection rate was slowly increased in this experiment which resulted
in changing the effluent sulfate concentration. The effluent pH, however, remained around 10.3 and
effluent sulfate ions did not increase as much as it did in the previous case. The simulation and
experimental results were in good agreement. Figure 2(b) shows that due to sodium metaborate
injection, some amount of calcium borate precipitated on interacting with gypsum. This resulted in a
slight increase in the effluent concentration of sulfate and a small reduction in the effluent pH
(compared to the injected pH).
Table 2: Properties of the cores into which alkalis were injected

Length Diameter Porosity Permeability Temperature
Simulation Gypsum
(inches) (inches) (%) (md) (°C)
1(a) 3.0 1.5 24 101 50 Yes
1(b) 7.93 1.485 19.3 68 55 Yes
1(c) 12 1.48 19.5 453 22 Yes

Simulation 1(a) Simulation 1(b) Simulation 1(c)

Salts (ppm) FB AS FB AS FB AS
NaCl 30,000 30,000 10,000 10,000 80,000 -
Na 2 CO 3 - 30,000 - - - -
NaBO 2 - - - 30,000 - -
NH 3 - - - - - 0.3 wt%
TDS (ppm) 30,000 60,000 10,000 40,000 80,000 10,000
pH 7.8 10.9 7.0 10.8 7.5 11.1
Table 3: Composition of formation brine (FB) and injection solution (IS) for simulations 1a-c
pH without gypsum pH with gypsum
12
11
Effluent pH
10
9
8
7
6
0.0 0.5 1.0 1.5 2.0
Pore Volume
4.0E-03 Calcium carbonate Anhydrite pH 12

Solid concentration (moles)
3.5E-03
11
3.0E-03
2.5E-03 10
pH
2.0E-03
1.5E-03 9
1.0E-03
8
5.0E-04
0.0E+00 7
0 0.2 0.4 0.6 0.8 1
Dimensionless distance (xd)

Calcium Sulfate Calcium-Model

Effluent concentration (ppm)
Sulfate-Model pH pH-Model
30000 11
10
25000
9
20000 8
7
pH
15000
6
10000 5
4
5000
3
0 2
0 0.5 1 1.5 2 2.5 3
Pore Volume
Figure 1: (a) Effluent pH on injection sodium carbonate in carbonate reservoir with and
without gypsum (b) In-situ mineral composition after injecting 2 pore volumes of sodium
carbonate solution in a carbonate core containing gypsum (c) Comparison of effluent pH,
calcium, and sulfate concentration of the simulations with experimental results reported by
Sharma (2016)
Calcium Borate Anhydrite pH

1.E-02 12
Solid concentration (moles)
1.E-02 11
8.E-03
10
pH
6.E-03
9
4.E-03
2.E-03 8
0.E+00 7
0 0.2 0.4 0.6 0.8 1
Dimensionless distance
Ca-Model SO4-Model Ca SO4 pH pH-Model

5000 12
Effluent calcium and sulfate
4000 10
concentration(ppm)
8
Effluent pH
3000
6
2000
4
1000 2
0 0
0 1 2 3 4 5 6
Pore Volume

Ca SO4 Ca SO4 pH pH
6000 12
5000
Effluent concentrations (ppm)
10
4000
Effluent pH
3000 8
2000
6
1000
0 4
0 0.5 1 1.5 2
Pore Volume
Figure 2: (a) Change in in-situ mineralogy on injecting 2 pore volumes of sodium metaborate
in gypsum containing carbonate core (b) Comparison of simulation results of sodium
metaborate injection in carbonate core containing gypsum with experimental results reported
by Sharma (2016) (c) Comparison of simulation results of ammonia injection in carbonate
core containing gypsum with experimental results reported by Sharma (2016)
(C) Ammonia injection: Recent studies have shown that ammonia has minimal interactions with
gypsum. Simulations 1(c) were conducted to study the transport of ammonia in a carbonate core
with gypsum. The effluent sulfate, calcium and pH reported in the literature and obtained through
simulations are given in Figure 2(c). Ammonia addition resulted in increasing the pH of the solution
but did not react with gypsum. Note that calcium ions dissolved from gypsum is due to the solubility
of gypsum in water and not due to ammonia addition. Calcium remained soluble in the ammonia
solution, unlike in sodium carbonate or sodium metaborate solution, because calcium hydroxide
precipitation occurs at a higher pH. These simulations were performed assuming local equilibrium
and agree well with experimental results.
2. Effect of cation exchange on surfactant flood

Cation exchange typically occurs in sandstones due to the presence of clays in these reservoirs.
These reactions can result in alkali consumption and introducing divalent cations into the injected
solutions as shown below (where M is the exchange site). Three different scenarios (Table 1) were
simulated and the effect of ion exchange in each case was investigated. A cation exchange capacity
(CEC) of 0.125 meq/mL is assumed.
MH + NaOH = MOH + H2 O
2Na+ + M2 Ca = 2MNa + Ca2+
a) Surfactant injection in soft brine: The ionic composition of effluents when a surfactant
solution prepared in soft brine is injected into a reservoir containing formation brine
(containing hardness) is shown in Figure 3a. The sodium and chloride ions reach the injected
concentration within 1.15 pore volumes. However, even after 1.5 pore volumes, the
concentration of calcium ions is around 200 ppm. These divalent cations can interact with
surfactants and have an unfavorable effect on the phase behavior unless the surfactants are
tolerant to some hardness.

b) ASP slug prepared using ammonia: This case is similar to the previous case except for the
addition of 0.5 wt% ammonia to the surfactant slug. The effluent ionic composition for this
case is shown in Figure 3b. Similar to the previous case, the sodium and calcium ions reach
their injected values around 1.15 pore volumes. The concentration of magnesium ions
decreases much faster in this case compared to the previous case. This is because
magnesium gets precipitated as magnesium hydroxide in the presence of ammonia.
However, the effluent profile of calcium ions remains the same as the previous case and can
have a detrimental effect on the surfactant formulation unless the formulation has some
tolerance for hardness.
c) ASP slug prepared using ammonia-sodium carbonate-hybrid-alkali: In this case, a small
amount of sodium carbonate is also added to the surfactant slug along with ammonia. Note,
that ammonia is the primary alkali while sodium carbonate addition was done to test if it can
lower divalent cation concentration. As seen from Figure 3c, the addition of a small amount
of sodium carbonate with ammonia results in precipitating divalent cations exchanged from
clays and hence protecting surfactants against their detrimental effects. Such a scheme has
been recently proposed.3
Table 4: Composition of formation brine and injection solutions
Simulation 2(a) Simulation 2 (b) Simulation 2(c)

Ions FB IS FB IS FB IS
(ppm)
Na+ 41411 23590 41411 23590 41411 23590
Ca2+ 11686 36410 11686 36410 11686 36410
Mg2+ 2700 0 2700 0 2700 0
Cl- 103000 0 103000 0 103000 0
SO 4 2- 200 0 200 0 200 0
NH 3 - - - 0.5 wt% - 0.5 wt%
Na 2 CO 3 - - - - - 10,000
TDS 148,740 60,000 148,740 60,000 148,740 70,000
Na+ Ca2+ Mg2+ Cl-

1000000
100000
Effluent ions (ppm)
10000
1000
100
10
1
0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00
Pore Volume

Na+ Ca2+ Mg2+ Cl- pH

1000000 12
100000 11
Effluent ions (ppm)
10000 10
Effluent pH
1000 9
100 8
10 7
1 6
0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00
Pore Volume
Ca2+ Mg2+ Na+ pH

100000 12
11
10000
10
Effluent ions (ppm)
1000
Effluent pH
9
100
8
10
7
1 6
0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00
Pore Volume
Figure 3: Effluent ionic composition on injecting a surfactant slug in a sandstone rock

containing formation brine when the surfactant slug was prepared in (a) Soft brine-No Alkali
(b) Soft brine-Ammonia as alkali (c) Soft brine-Ammonia and sodium carbonate as alkali
Conclusions
In this study, simulations were performed to understand the interactions of various alkalis with
rocks containing gypsum (or anhydrite) and clays. The effect of these interactions on alkali transport
and surfactant phase behavior was investigated. Key conclusions from this study are given below:
1. Simulation results showed that sodium carbonate reacts excessively with gypsum. This
causes pH propagation delay and precipitation of calcium carbonate which can result in
permeability impairment.
2. Sodium metaborate was found to interact only moderately with gypsum. High pH
propagation was observed. However, precipitation of calcium borate was also observed.
3. Ammonia did not react with gypsum and a high pH propagation was observed.
4. Injecting a surfactant slug prepared in soft brine into sandstone reservoirs (with high clay
content) containing high hardness formation brine is not favourable unless the surfactant
slug has some tolerance for divalent cations. Injecting ammonia alone with surfactants in

such reservoirs is not favorable as calcium ions are not precipitated by ammonia. Addition of
a small amount of sodium carbonate with ammonia can address this problem.
Acknowledgement
The authors are thankful to the Indian Institute of Technology, Kanpur and the University of Texas
at Austin for financial support.
References
[1] Lopez-Salinas, J. L., Hirasaki, G. J., & Miller, C. A. (2011, January 1). Determination of
Anhydrite in Reservoirs for EOR. Society of Petroleum Engineers. doi:10.2118/141420-MS
[2] Sharma, H., Dufour, S., Weerasooriya, U., Pope, G. A., & Mohanty, K. (2014, April 12). ASP
Process for Anhydrite-Containing Oil Reservoirs. Society of Petroleum Engineers.
doi:10.2118/169065-MS
[3] Southwick, J. G., van den Pol, E., van Rijn, C. H. T., van Batenburg, D. W., Boersma, D., Svec,
Y.,Raney, K. (2016, February 1). Ammonia as Alkali for Alkaline/Surfactant/Polymer Floods.
Society of Petroleum Engineers. doi:10.2118/169057-PA
[4] Wang, D., Maubert, M., Pope, G. A., Liyanage, P. J., Jang, S. H., Upamali, K. A. N., … Morel,
D. (2019, February 1). Reduction of Surfactant Retention in Limestones Using Sodium Hydroxide.
Society of Petroleum Engineers. doi:10.2118/194009-PA
[5] Sharma, H., Weerasooriya, U., Pope, G. A., & Mohanty, K. K. (2014, October 27). Ammonia-
Based ASP Processes for Gypsum-Containing Reservoirs. Society of Petroleum Engineers.
doi:10.2118/170825-MS
[6] Sharma, H. (2016). Study of Geochemical Interactions during Chemical EOR Processes. PhD
Dissertation. The University of Texas at Austin

Title: “Linear and Poly Alpha Olefins: Precursors to Synthetic Lubricants”

-Gopal Tembe, Consultant, Reliance Technology Group, Reliance Industries Limited
Keywords: Catalytic oligomerization, linear alpha olefins, synthetic lubricants, poly alpha olefins
Abstract
Poly Alpha Olefins (PAO’s) are oligomers of Linear Alpha Olefins (LAO’s) that are used as base
stocks for synthetic lubricants for automotive and industrial applications. Synthetic base stocks
exhibit better performance properties such as kinematic viscosity, viscosity index, pour point,
thermal and oxidative stability compared to conventional mineral base stocks. Synthesis of PAO’s is
primarily carried out through oligomerization of lower alpha olefins employing well designed
homogenous oligomerization catalysts. The majority of commercial processes use decene (1-C 10 )
as the monomer of choice. However, other LAO’s such as 1-octene,1-dodecene etc. are also
reported. Proper combination of catalysts and co-catalysts along with appropriate reaction
conditions lead to either PAO’s or LAO’s. The present work describes some of the work carried out
on selective catalytic oligomerization of ethylene to (C 4 -C 18 ) LAO and 1-decene to (C 30 -C 40 ) PAO.
Introduction
Linear Alpha Olefins
The production of alpha olefins by catalytic oligomerization of ethylene is of great technical
importance in petrochemical industry [1,2]. These low molecular weight alpha olefins find
applications as co-monomers for commodity polymers and also as precursors to a wide spectrum of
consumer products like biodegradable detergents, non-ionic surfactants, plasticizers, lubricants, fine
chemicals etc.
Such processes typically generate a mathematical distribution (Schulz-Flory or Poisson) of α-olefins

to match market demand. Examples of selective ethylene oligomerization reactions include the Shell
Higher Olefin Process (SHOP) with a nickel-based catalyst, Albermarle and Chevron Processes
with aluminum, and the Idemitsu Process, which employs an Aluminum / Zirconium catalyst. In
our laboratories we had studied the ethylene oligomerization using a homogeneous catalyst system
containing Zr(OR) 4 and Alkylaluminum halide complexes. The typical statistical distribution of a
mixture of LAOs, shown in Scheme 1, implies that separation by distillation is required when
isolating LAOs for specific applications. With the high cost involved with separating mixtures of
olefins comes the inevitable limitation in yield of a particular olefin, hallmark of a statistical
distribution.Interest in the development of selective ethylene oligomerization processes has thus
increased tremendously over the last decade. It is noteworthy to point out that while it is desirable to
increase selectivity towards an olefin with a specific carbon number, it is even more crucial to
maximize the purity of the α-olefin within its fraction. Indeed,separation of terminal olefins from
their internal isomers is more challenging and expensive than the separation of α-olefin homologs.

Typical distribution
CH2=CHCH2CH3 , Butene-1, 1-C4 35
28
M-Cat CH2=CHCH2CH2CH2CH3, Hexene-1,1-C6
C
2 CH2=CHCH2CH2CH2CH2CH2CH3, Octene-1, 1-C8 18
CH2=CHCH2CH2CH2CH2CH2CH2CH2CH3 , Decene-1, 1-C10

09
C12H20 + C14H28 + C16H32 + C18H36 , 1-C12 – 1-C18

10
Scheme 1: Typical α-olefin distribution during catalytic ethylene oligomerization.
The following table (Table 1) highlights the selectivity of individual carbon number olefin observed
in commercial processes.
Table 1: Comparison of commercial LAO processes and AO distribution
Process Gulf/Chevron Amoco Shell Sablin RIL *
α-Olefin Heavy Light Typical Medium Light

C4 13.9 22.9 12 24 40.2 30
C6 14.6 20.6 13 27.1 28.1 33.5
C8 13.7 16.2 12 13.2 14 18.5
C 10 12 12.3 12 11.2 8.4 9.1
* US Pat 6930218
C 12 10 8.9 10 8.3 5 8.6
C 14 8.2 6.2 8 5.8 2.3
C 16 6.2 4.3 7 4.8 1.4
C 18 5.2 2.9 6 2.9 0.5
C 20 14.9 5.3 20 2.8 0.1
Poly Alpha Olefins

Poly alpha olefins are a class ofsynthetic hydrocarbon base fluids which are essentially produced by
oligomerization of higher α-olefins. The hydrogenated PAO’s exhibit excellent thermal and
oxidation stability, low volatility, pour point and high flash points. These physical properties permit
PAO’s to have applications as engine, gear, turbine and compressor oils, hydraulic and power
steering fluids, heat transfer media etc.

Research in this area has been mostly focused on oligomerization of 1-decene as the monomer of
choice for producingfunctional fluids. Among 1-decene oligomers the ideal one is the trimer.
Synthetic blends of dimers (C 20 ), trimer(C 30 ) and tetramer(C 40 ) of 1-decene are commercially
available that meet the desired properties of synthetic lubricants. Some of the global producers are:
Mobil Oil, Lubrizol, Gulf oil, Emory Corp, Uniroyal .
The oligomerizaton of 1-decene can be achieved by differentcatalysts. They include Friedel-

Crafts,free radical and Ziegler type catalysts. Heterogeneous catalysts such as BF 3 /SiO 2 , BF 3 /Al 2 O 3
,HKL zeolites have also been used for higher α-olefin oligomerization. In our laboratories we have
investigated the oligomerization of 1-decene using Lewis acid and Ziegler Natta based catalysts.
The results are described in the following paragraphs.
Experimental:
Typical oligomerization with cationic catalysts : 0.26g(1.95mmol) anhydrous AlCl 3 ,
0.28g(0.66momol) LiCl, 9.99g(71.4mmol) 1-C 10 and 25mL (34.2g) dry 1,2-dichloroethane were
taken in a 100mL two necked RB flask fitted with a reflux condenser and a CaCl 2 guard tube. The
reaction mixture was stirred for 1h. An aliquot of 1.63g sample was withdrawn from the reaction
mixture and analyzed by GC (3% Dexil on Chromosorb P, 1M, column temp. 60-300 0C, flow rate
30mL N 2 /min) for conversion. To the rest of the reaction mixture was added 1mL of saturated
NH 4 Cl solution with continuous stirring. The organic phase was decanted out from the inorganic
solids, diluted with 50mL 1,2-DCE. The diluted organic phase was washed with 50mL of sat.
Solution of NaCl and dried over anhydrous Na 2 SO 4 . After removal of the solvent 8.5g of pale
yellow, viscous product was obtained.
Oligomerization with Z-N catalysts:Ti(OPri) 4 (0.28g) dissolved in 30 mL toluene was mixed with
10mL 1-C 10 and ethylaluminumsesquichloride (EASC, Et 3 Al 2 Cl 3 , 1.13mL) was introduced by
means of a syringe (note: the neat Al-alkyls are pyrophoric in nature and must be handled in a good
fume hood in the absence of air).The contents of the reaction mixture were agitated for 2h and the
active catalyst was quenched by adding 2mL BuOH. The liquid samples were analyzed by GC as
before.
Hydrogenation of the PAO :The above solution containing the oligomers of 1-decene were
transferred to a distillation unit. Unreacted monomer, solvent and other volatiles were removed by
distillation under vacuum. The material in the flask was then transferred to a 300mL high pressure
Parr autolclave. 6 wt% freshly prepared Raney nickel in 60mL ethanol was then added. H 2 was
introduced into the reactor until a pressure of 500-600psi was reached. The temperature was raised
to 1600C and agitated. After 3-4 hrs the reactor was cooled and H 2 gas was carefully vented and the
contents filtered. The solvent was removed and the neat product collected did not decolorize Br 2 in
CCl 4 solution suggesting that hydrogenation of the oligomers was complete.
Kinematic Viscosity: The measurement of kinematic viscosity of the hydrogenated PAO was carried
out by ASTM D445-83 and D2270-79 procedures. The Ubbelhode viscometer used in the present
experiments were calibrated with viscosity oil standards, S-60, S-20 and S-60 at 40 and 1000C. The
kinematic viscosity, ν(cSt) was calculated using the relation, ν=Ct, where C=calibration constant of
the viscometer in cSt/S and t= measured flow time in secs.
Gel Permeation Chromatographic analyses of selected samples were carried out on a Waters GPC
instrument in conjunction with an RI detector. Two cross linked polystyrene gel columns were used

in series (50A0 and 500A0).The analyses were compared with authentic samples of PAO’s obtained
from Emory Industries USA having 4, 6& 8 cSt viscosities.
Results and Discussion:

Conventional Ziegler-Natta catalysts which are known to polymerize ethylene to high molecular
weight polyethylene were used for the catalytic oligomerization of 1-decene. Apparently as the
carbon number (chain length) increases the reactivity of the olefin decreases in the order C 2 > C 4 >
C 6 > C 8 > C 10 . The transition metal complexes of Ti(IV), V(V) and Zr(IV) combined with Et 3 Al 2 Cl 3
were investigated for oligomerizing 1-decene [3,4]. The results are presented in Table 2. The
kinematic viscosity and pour points of representative hydrogenated PAO’s are compiled in Table 3.
Table 2. Oligomerization of 1-decene by cationic and Z-N catalysts
Ex. Cat(g) Co- Time %Conv Product Distribution (%)

No. cat(g) (h) C 20 C 30 C 40 Higher Oligo
1a AlCl 3 LiCl 1 99 22.1 26.7 51.1
(0.26) (0.028)
2a AlCl 3 LiCl 1 98 11.3 22.7 53.4 12.5
(0.26) (0.066)
3a,b AlCl 3 LiCl 1 80 14.2 37.1 27.1 21.4
(0.26) (0.038)
4c Ti(OPr i) 4 EASC 1 45.1 68.0 10.4 6.9
5 Ti(OPr i) 4 EASC 6 77.6 76.4 9.4 14.1
6 Zr(OPr n) 4 EASC 6 67.5 81.4 12.2 6.4
7 VO(OPr n) EASC 1 29.3 78.6 17.3 3.2 0.6

3
8 VO(OPr n) EASC 6 61.5 71.3 20.3 7.6 0.6

3
9 Co(acac) 2 EASC 6 15.5 89.0 10.9

a
Temp. 26 0C; b without solvent EDC; c All Z-N catalysts screened at 500C

Table 3. Comparison of kinematic viscosity and Pour point of representative samples
Cat / Expt No. KV cSt ( 100 0C) Pour Point 0C
Ti(OPr i) 4 – EASC (5) 3.92 -47
Zr(OPr n) 4 – EASC (6) 3.54 -44
VO(OPr n) 4 – EASC (8) 4.10 -53
PAO 4 (standard) 3.95 -60

PAO 6 (standard) 5.92 -63
From Table 2 it is clear that the cationic catalysts are active at room temperature and the best
activity was observed with the AlCl 3 -LiCl catalyst system. Trimer of 1-decene (C 30 ) is the
predominant oligomer with this catalyst. The AlCl 3 catalysts can be easily separated using saturated
NH 4 Cl solution making this process much simpler and relatively cost effective.
With regard to Z-N catalysts system, Ti(IV)alkoxide - EASC catalysts showed better activity with
increase in temperature from ambient to 500C (runs 4 &5). However, the dimer formation (C 20 ) is
higher than the other fractions. Similar trend in product selectivity was observed in the case of
Zr(IV)n-propoxide - EASC catalyst. In the case of Vanadiumtripropoxide a range of decene
oligomers from C 20 -C 50 were observed within 1h though the conversions were lower than at higher
temperature. This higher oligomerization activity may be attributed to low isomerization of 1-
decene during the reaction.
Mechanism of Oligomerization:
A mechanism of oligomerization as suggested by Keim et.al.[5] shown in Scheme 2 can be
Scheme 2: Mechanism of oligomerization of decene by Z-N catalysts, R = --(CH 2 ) 7 CH 3

proposed for 1-decene oligomerization by Z-N catalysts. The essential feature of this mechanism
involves i) formation of an active metal-hydride speciesii) insertion of olefin into the M-H bond by
a Markownikoff addition iii) chain propagation by either primary or secondary insertions of the
olefin into the metal-carbon bond and iv) chain termination by β-hydride elimination.
Conclusions
LAO’s and PAO’s are a class of high performance functional hydrocarbon fluids whose properties
can be adjusted to meet the specific end use applications. Depending on experimental conditions
and the type of catalysts ‘tailor-made’ PAO’s can be prepared. Both cationic and homogeneous
Ziegler-Natta catalysts have been effectively shown to produce the trimers and tetramers of 1-
decene which is the olefin of choice for most synthetic lubricants. There is thus tremendous scope to
utilize other lower α-olefins like1-hexene and 1-octene for production of synlube for special
applications.
Acknowledgment:
The technical and financial support provided by R&D Divn., Reliance Industries Ltd., Vadodara, for
this project is gratefully acknowledged.
References
1. Henrici-Olive G, Olive S, Adv.Poly.Sci., 1974; 15: 1 and references therein

2. Keim W, Behr A and Röper A in Comprehensive Organometallic Chemistry, Wilkinson G
&Stone FGAeds. Pergamon Oxford 1982; vol.8 : 371
3. Tembe GL and Ravindranathan M, Ind., Engg.Chem. Res. 1991; 30: 2247-2252
4. Tembe GL, Bandyopadhyay AR, Pillai SM and Ravindranathan M, Die. Angew.
Makromol.Chem. 1995; 225: 51-61
5. Keim W,Hoffmann E, Lodewick R, Peuckert M, Schmidt G, Fleishhauser J, and Meier U,
J.Mol.Catal. 1979; 6:79-83.

Title: "Silane Coated Silica Nanop Articles As An Additive for Water Based Drilling Fluid"
-Himanshu Kesarwani1, Viswakanth Kandala2, Shivanjali Sharma*1
1
Department of Petroleum Engineering, Rajiv Gandhi Institute of Petroleum Technology,
2
Department of Petroleum Engineering, Indian Institute of Petroleum and Energy, Visakhapatnam
Keywords: Drilling fluid, rheology, silane, nanoparticles
Abstract
Drilling fluid is one of the most important utility during the drilling of petroleum wellbore. It a
mixture of several chemical additives in a base fluid so as to obtain the desired properties. Water
based drilling fluids are most widely used across the globe because of its cost effectiveness, easy
disposal without harmful effects on environment when compared to oil based mud. The major
functions of drilling fluid include the withstanding of the formation pressure by providing required
hydrostatic head as well as lifting the cutting from the wellbore to the surface.
In this study, industrially prepared silica nanoparticles coated with AEAPTS ([3-(2-
Aminoethylamino) propyl] trimethoxy silane) was used as an additive to enhance the rheology of
the water based mud. Silica nanoparticles were coated separately in a two-step process. In first step
the silica nanoparticles were coated with hydroxyl group which were further coated with AEAPTS.
The coating was confirmed with the shifting in the peaks of the FTIR spectra of the sample. Base
mud was prepared with 5 wt % of bentonite, 1 wt % of xanthan gum, 0.5 wt % of poly anionic
cellulose and 3 wt % of potassium chloride. Three different mud samples were prepared with 0.2,
0.3 and 0.4 wt % of nanoparticles in the base mud. The rheology of the mud samples was done
using Fann VG Metre model 35 in which the shear rate was varied and shear stress values were
recorded both before and after hot rolling of mud in the roller oven at 105 °C for 16 hours.
The viscosity of the drilling fluid was found to be increasing with addition of silane coated silica
nanoparticle reaching up to a value of approximately 26 cp and 23.5 cp before hot rolling at 600
shear rate at 30 °C and 60 °C respectively. The degradation in the rheology of the base mud without
nanoparticles was found to be around 60 % which was reduced to around 20 % with the addition of
silane coated silica nanoparticle which clearly indicates that the silane coated nanoparticles can be
used as a viscosifier for high temperature well in water based drilling fluid.
1. Introduction
Oil and gas are the important commodities in our daily life. They are extracted from earth by
drilling process, which has a major share in exploitation of hydrocarbons and costs nearly 75 % of
the total well expenditure[1]. During drilling, a drilling fluid (mud) is continuously circulated into
wellbore.The drilling fluid is a heavy viscous fluid mixture that is circulated in the borehole in order
to carry out the drilled cuttings from the well to the surface. The diverseapplications of this
drillingmud makes it an essential part of rotary drilling system. Drilling fluid has several functions
such as, removal and transport of cuttings from bottom of wellbore to the surface through the
annulus, cooling and lubricating the drilling string and bit, controlling the formation pressure by
providing sufficient hydrostatic pressure, preventing formation from collapsing, suspending the
cuttings, while mud is in static condition and many more.

They are many varieties of drilling fluid and are broadly classified based on their base fluid.
1. Water based muds (WBM): The solid particles (clays and colloids) are suspended in the
water and in case of emulsions, water is a continuous phase.
2. Oil based muds (OBM): The solid particles are suspended in the oil and in case of
emulsions, oil is a continuous phase.
3. Gas fluid: High speed air streams are used to remove cuttings.
The drilling fluid is an important component of drilling on which the well costs are highly
influenced. WBM is the most common type of drilling fluid and is used in approximately 80% of
the wells drilled worldwide [2] because it is economical when compared to OBM and it is easily
disposable without having much effect on environment which is exactly opposite in case of
OBM[3]. Water based drilling fluid is a generally a mixture of many additives like viscosifiers,
weighing material, filtration control material, polymers etc. The right selection of drilling fluid and
maintenance of its properties in desired range is dependent on the choice of additives.In the previous
research the nanoparticles of different metal oxides like copper oxide (CuO), zinc oxide (ZnO),
titanium dioxide (TiO 2 ), iron oxide (Fe 2 O 3 ), silicon oxide (SiO 2 )have beensuccessfully used as an
additive in water-based fluid for improving rheological and filtration properties [2].The drilling
fluid with these Nano additives is referred as ‘Nano Fluid’ and is a colloidal dispersion of Nano
additives in the base fluid [2].
The ubiquitous influence of the term Nano Technology in many areas of science has inspired the oil
and gas industry to apply it. In the recent years, the application of Nano-particles in the field of oil
and gas industry has gained a lot of attention. The term Nanotechnology deals with the matter at the
nanoscale (ranging 1 to 100 nanometres).The high area to volume ratio of nanoparticles gives them
a high surface area for interaction with surrounding medium, hence for any application the quantity
of nanoparticles required will be less. These unique characteristics enabled researchers to use it as
an additive in drilling fluid for several years to optimize its performance in the area of rheology,
fluid loss and shale stabilityespecially in the case of water sensitive formation[2].
Abdoet al. reported that pipe sticking can be reduced by the addition of Nano particles inWBM and
they also mentioned, addition of nanoparticles in WBM lessen the degradation of polymer chains at
higher temperature and makes the fluid thermally stable[4].
Alshubbar et al. demonstrated that Nano-additives can increase the drilling fluid lubricity and
rheology[5]. Taha et al. reported that the Nanographene in water-based mud has reduced the torque
up to 80% and increased its rheology by 40-60%[6].
Zhanget al. has used, Micro Nano Particles (MNP) as an additive in oil-based mud for formation of
ultra-thin impenetrable mud cake on wellbore wall to prevent the fluid loss[7].Presently, Mixed
Oxides are in consideration as an additive,Shama et al.have used Zinc titanate (ZnTiO3)
nanoparticles as an additive for the improvement in rheological and fluid loss properties of water-
based drilling ﬂuid[8].Thebehaviour of nanoparticles is quite different from the large-scale particles,
usually the surface modification or coating is donned on the nanoparticles either to enhance or
hinder the particle-particle interactions depending upon the requirement [9].
In the present study,commercially procured silica nanoparticleswere coated with [3-(2-

Aminoethylamino) propyl] trimethoxy silane (AEAPTS)and the product was confirmed by
FTIR(Fourier transform infrared spectra)spectra. A base mud was prepared with bentonite, xanthan
gum, polyanionic cellulose and KCl solution.Then concentration of the silane coated nanoparticle

were varied from 0.2 to 0.4 wt/v % to investigate the effect of nanoparticle on the rheological and
filtration properties of the WBM. The mud was kept for ageing at 110˚C for 16 hours in the roller
oven. Rheology of the Nano mud both before and after ageing was analysed using Fann VG meter
model 35 and the filtration properties were analysed by using API Filter Press (LPLT).
2. Experimental Procedure
2.1 Materials
SiO 2 nanoparticle of average particle size 15 nm and specific surface area of 650 m2/g with purity of
99.5% wasprocured from by Sisco research Laboratories Private Limited, India. Sodium Hydroxide
of purity 97 % was procured from SD Fine Chem Limited, India, AEAPTS ([3-(2-
Aminoethylamino) propyl] trimethoxy silane) of purity 97 % was procured from TCI, Japan.
Ammonium Hydroxide and methanol of purity 95 % and 99 % respectively were procured from SD-
Fine Chem Limited, India. Xanthan Gum, Polyanionic Cellulose and Bentonite clay were also
procured from SD-Fine Chem Limited, India.Deionized water from ELGA LAB water purifier was
used for all the experiments with resistivity >18 MΩ-cm. All the chemicals were of analytical grade
and were used without further purification.
2.2 Silane Coating of Silica Nano Particle

The coating of AEAPTS on the silica nanoparticles was done in two steps. In the first step 2.5 wt%
of silica nanoparticles was added in the 20ml aqueous solution of the 0.5M sodium hydroxide. The
mixture was continuously stirred at 600 rpm for 24hrs in magnetic stirrer at ambient conditions.
This results in the adding of hydroxyl group on the surface of the silica nanoparticles[10]. After
stirring the product was centrifuged at 12,000 rpm for 20 min and then washed thrice withwater at
12,000 rpm for 20 min each. Then the product obtained wasdried out for 24hrs in a desiccator.
In the second step, the coating of AEAPTS on hydroxylgroup attached to the silica nanoparticles
was done. The200 mg of Si-OH (step-1 end product) nanoparticles were dispersed in an aqueous
medium containing 80ml of water + 2ml of ammonium hydroxide + 20ml of methanol + 1ml of
AEAPTS. The resulting mixture was stirred at 600 rpm for 2hrs at ambient conditions and then
temperature was increased to 70˚C and was maintained for 24 hrs followed by centrifuge at 13000
rpm for 25 min. The product thus obtained was washed with the isopropyl alcohol (33% dilution) in
centrifuge for three times at 12000 rpm for 15 min each and the resultant solution wasdried for
24hrs in desiccator. The Schematic of the process is given in Fig 1.
2.3 Characterization of coated nanoparticles

Fourier Transform Infra-red (FT-IR) spectroscopy was done which basically confirms the presence
of the functional group in the sample. The FT-IR identifies the chemical bonds in a molecule by
producing an infrared absorption spectrum and helps in detecting the functional groups present in
the sample. Distinct functional group has distinct peaks in the FTIR spectra and on that basis the
respective functional groups are analysed in the sample. It uses the Fourier transformation technique
to convert the raw data to spectra. In this study, FTIR spectra was recorded using PerkinElmer
Spectrum PIKE MIRacle single reflection horizontal ATR (attenuated total reflectance) equipped
with zinc selenium crystal. A thin film of the powdered sample was pressed against the ATR crystal
to record the FTIR spectra of wavelength. The shift in the peaks in the obtained spectrum were
studied and the wavelengths of the peaks wereanalysed.
2.4 Preparation of Mud Samples

Pre-hydrated bentonite was used in the process of preparation of mud samples by preparing 5 %
bentonite solution using Hamilton beach mixer and was kept undisturbed for 24 hours. This solution

was used to prepare the base mud with an addition of XG (0.25 w/v %) used as viscosifier, PAC
(0.5 w/v %) used as fluid loss reducer and KCl (3.0 w/v %) used as clay stabilizer. Octanol was used
as defoamer. The concentration of silane coated nanoparticle was increased in this base mud up to
0.4 wt/v % and its rheology and filtration properties were analysed.
2.5 Rheological and Filtration Properties

Rheology of the mud is one of the key parameter in its selection. The better will be the rheology
data, the better will the performance of the drilling mud. Rheology is greatly affected by the
pressure, temperature and solid content in the mud sample. Solid content directly affects the plastic
viscosity of the mud. After the preparation of mud samples its rheology was tested using Fann VG
Meter model 35. The working principle of the instrument is basically varying shear rate is applied
by a motor on rotating assembly which is dipped in the sample, the sample starts moves by virtue of
rotor movement and it applies the torque on the stator because of which the stator also moves and
gives the reading. The shear rate is controlled by changing gear assembly in Fann VG meter. The
more resistance the fluid offers, the more torque it will provide on the rotor which in result will
show greater dial reading and hence more will be its viscosity. Fann VG meter gives the direct dial
reading based on which the rheological parameters such as apparent viscosity, plastic viscosity and
yield point can be calculated. It can also measure the gel strength of the drilling mud which
describes the cutting carrying capacity of the drilling mud under the static conditions.
The Filtration properties of the mud samples were tested through the API Filter Press of the Fann
Company, USA. The mud sample is kept in a cylindrical cup of area 45.8 cm2 which has an opening
in the centre. The mesh used in the assembly is of 60 US mesh size and the filter paper used was of
2.7 microns. A pressure of 100 psi is applied across the mud from the top at the room temperature
for 30 minutes and the filtered volume is reported as the API filter loss. It basically gives an idea
about the ability of the drilling to refrain the water from entering into the formation.
2.6 Thermal Stability of the Mud Samples

The rheology of the mud follows a general trend and are inversely proportional to the temperature.
So it becomes necessary to find out the effect of temperature on the rheology of the mud i.e. its
thermal stability. Dynamic Aging Test method was used to determine the thermal stability of the
mud. In this method a sample is kept in a sealed cell which is kept inside the roller oven for 16
hours. The cell keeps rotating throughout the time and the temperature is maintained. The
rheological parameters are measured both before and after hot rolling and compared.The
degradation in the rheological parameter desired to be minimum which indicated the thermal
stability of the mud.
3. Results and Discussions
3.1 FTIR Characterization

The silane coating on the nanoparticles was characterized by the FT-IR absorption spectra which is
shown in Fig 2. The peaks corresponding to 990-1050 cm-1 are attributed to the alkyl-substituted
ether whereas the peaks at 1080 cm-1 and 880 cm-1 are attributed to the Si-O-Si and Si-OH
absorption. The absorption spectra in the range of 3200-3400 cm-1 corresponds to the OH functional
group. The peaks from 813-981 cm-1 are due to the C-C stretching whereas 2877-2967 cm-1 are
attributed to the C-H stretching. The absorption peak at 1642 cm-1 is due to the presence of NH 2 as a
functional group in the compound whereas the wide spectra at 3300-3500 cm-1are attributed to the
N-H stretching. All these peaks manifest the successful coating of silane on the silica nanoparticles.

3.2 Rheological and Filtration Experiments

Rheological parameters such as apparent viscosity, plastic viscosity, yield point and gel strength are
important for the drilling mud and directly affects the performance of the drilling mud and hence is
monitored continuously. The apparent viscosity of the fluid is basically the ratio of the shear stress
to the shear rate which is constant for the Newtonian fluid. Since the drilling mud are Non-
Newtonian fluids, their apparent viscosity is directly affected by the shear rate applied. The apparent
viscosity of such fluids decreases with increase in the shear rate. Plastic viscosity of the drilling mud
is the resistance to its flow offered by the solid particles present in it. Plastic viscosity directly
affects the rate of penetration which is the crucial parameter in deciding the economics of the
complete drilling process and hence the monitoring of plastic viscosity becomes important as well.
For maintaining a good rate of penetration during drilling the plastic viscosity of less than 30cp is
desired [11]. Yield point is necessary for the drilling mud to carry the drilled cutting in the well
under dynamic conditions. Too high yield points are also not desirable as it will increase the
pumping pressure which in return will directly affects the costs. Previous studies suggests that
normally the value of yield point in the range of 9-15 Pais desired [12]. The gel strength also affects
the cutting carrying capacity of the drilling mud but at static conditions. The rheological parameter
of the drilling mud samples were measured both before and after hot rolling at 105 °C for 16 hours
and the data obtained are tabulated in table 1. The rheology of all the mud samples were measured
at two different temperature i.e. at 30 °C and 60 °C. The apparent viscosity of the base mud was
found to be 21 cp at 30 °C and 19 cp at 60 °Cwhich was reduced approximately 58 % after hot
rolling for 16 hours at 105 °C. The data obtained clearly shows the improvement in the rheological
parameters on addition of the silane coated silica nanoparticles. The degradation in the mud
rheology was reduced up to 19 % after ageing, although the effect of addition of nanoparticles was
significant observed when it was added in lesser concentrations. The fluid loss in case of base mud
was found to be 32.6 ml which was reduced up to 11.2 ml with an addition of 0.4 wt/v % in the mud
sample.
3.3 Thermal Stability of Mud

Thermal stability is one of the most important property that a drilling fluid must possess. Since the
drilling fluid are used in the wellbore that have significantly high temperature as compare to the
surface temperature so it becomes necessary to design the fluid that can sustain at subsurface
temperature. The general trend of the viscosity follows an inverse relationship with temperature and
hence the drilling fluid must be designed keeping in mind the subsurface temperature. Although the
decrease in the viscosity of the mud with increasing temperature cannot be avoided but it can be
decreased with the addition of proper mud additives that can thermally stabilize the drilling mud. In
the experiment the rheological parameters of the base mud was found to be reduced up to 56 % of
their original value after ageing whereas after an addition of only 0.2 wt/v % silane coated silica
nanoparticles the changes in the rheological parameters were quite significant which can be seen in
Fig 3. After hot rolling these parameters were around 80 % of their respective before hot rolling
values. This clearly reflects that the addition of silane coated silica nanoparticle thermally stabilized
the water based drilling mud system.
4. Conclusions
Silane coated silica nanoparticle can work as a rheological as well as fluid loss control agent in the
water based drilling mud. They thermally stabilize the drilling mud and helps in keeping the
rheological property of the drilling mud intact even at subsurface temperature.The degradation in
rheological parameters of the base mud was found to be around 55 % which was reduced up to a
value of 20 % as well as the fluid loss was reduced by 65 % upon adding the silane coated silica
nanoparticle which clearly shows that this additive can be used for the rheology and fluid loss
control in water based drilling mud system.

5. Acknowledgements
The authors of this paper gratefully acknowledge the Rajiv Gandhi Institute of Petroleum
Technology for providing the required funds and facility of the research.
6. Reference
[1]S. N. Shah, N. H. Shanker, and C. C. Ogugbue, “Future Challenges of Drilling Fluids and Their
Rheological Measurements,” in AADE Fluids Conference and Exhibition.
[2]M. Sadeghalvaad and S. Sabbaghi, “The effect of the TiO2/polyacrylamide nanocomposite on
water-based drilling fluid properties,” Powder Technol., vol. 272, pp. 113–119, 2015.
[3]S. M. Almudhhi, “Environmental impact of disposal of oil-based mud waste in Kuwait,” Pet. Sci.
Technol., vol. 34, no. 1, pp. 91–96, 2016.
[4]J. Abdo and M. D. Haneef, “Nanoparticles : Promising Solution to Overcome Stern Drilling
Problems Mechanical and Industrial Engineering Department,” Nano Sci. Technol. Inst. -Nanotech,
vol. 3, pp. 635–638, 2010.
[5]G. D. Alshubbar, T. N. Coryell, A. Atashnezhad, S. Akhtarmanesh, and G. Hareland, “The Effect
of Barite Nanoparticles on the Friction Coefficient and Rheology of Water Based Mud,” in 51st US
Rock Mechanics / Geomechanics Symposium 2017, vol. 1.
[6]N. M. Taha, S. Lee, and S. Kmc, “Nano Graphene Application Improving Drilling Fluids
Performance,” in International Petroleum Technology Conference, no. December.
[7]J. Zhang et al., “Novel Micro and Nano Particle-Based Drilling Fluids: Pioneering Approach to
Overcome the Borehole Instability Problem in Shale Formations,” in SPE Asia Pacific
Unconventional Resources Conference and Exhibition.
[8]S. Perween, M. Beg, R. Shankar, S. Sharma, and A. Ranjan, “Effect of zinc titanate nanoparticles
on rheological and filtration properties of water based drilling fluids,” J. Pet. Sci. Eng., vol. 170, no.
July, pp. 844–857, 2018.
[9]M. F. Fakoya and S. N. Shah, “Rheological Properties of Surfactant-Based and Polymeric Nano-
Fluids,” in SPE/ICoTA Coiled Tubing & Well Intervention Conference & Exhibition.
[10]N. K. Maurya, P. Kushwaha, and A. Mandal, “Studies on interfacial and rheological properties
of water soluble polymer grafted nanoparticle for application in enhanced oil recovery,” J. Taiwan
Inst. Chem. Eng., vol. 70, pp. 319–330, 2016.
[11]M. Khodja et al., “Shale problems and water-based drilling fluid optimisation in the Hassi
Messaoud Algerian oil field,” Appl. Clay Sci., vol. 49, no. 4, pp. 383–393, 2010.
[12]J. Guo, J. Yan, W. Fan, and H. Zhang, “Applications of strongly inhibitive silicate-based
drilling fluids in troublesome shale formations in Sudan,” J. Pet. Sci. Eng., vol. 50, no. 3–4, pp.
195–203, 2006.

Fig 1. Reaction Schematic of the coating of silica nanoparticles
Fig 2: FTIR Spectra of silane coated silica nanoparticles

Fig 3: Rheology of mud with increase in the concentration of silane coated silica nanoparticles, a)
BHR @30 °C; b) AHR @30 °C; c) BHR @60 °C; d) AHR @60 °C
Table 1 (a): Rheology data of mud @30 °C

Rheological Concentration of Silane Coated Silica Nanoparticle
and Fluid Base Mud 0.2 wt/v % 0.3 wt/v % 0.4 wt/v %
loss
Parameters BHR AHR BHR AHR BHR AHR BHR AHR
AV 19.5 11 23.5 19 25 20 26 20.5
PV 13 7 16 13 17 13 18 13
YP 13 8 15 12 16 14 16 15
Table 1 (b): Rheology data of mud @60 °C

Rheological Concentration of Silane Coated Silica Nanoparticle
and Fluid Base Mud 0.2 wt/v % 0.3 wt/v % 0.4 wt/v %
loss
Parameters BHR AHR BHR AHR BHR AHR BHR AHR
AV 16.5 8.5 21 14 22.5 16.5 23.5 18
PV 11 5 14 9 15 10 16 11
YP 11 7 14 10 15 13 15 14

Title: “Kinetic Study of Exothermic Reaction Mixture for Paraffin Removal”

-M. Q. Zaman, J. Joseph, Tej Pal, M. Mandal, T. K. Banerjee, B. Deuri, Institute of Oil and Gas
Production Technology
Keywords: In situ heat generation; Down hole Heat Generation; wax removal; Job Design;
Numerical Simulation
Abstract
Deposition of paraffin in wellbore may drastically decline the oil production in mature and low
temperature reservoirs. In-situ heat generation through chemical reaction is a technique, in which
large amount of energy is liberated by exothermic reaction of aqueous nitrogenous salts. This has
been used in the industry to mitigate the issue of wax deposition in the wellbore, crude oil pipelines
and oil tanks. The success of such technique relies heavily on controlling the rate of reaction such
that majority of heat is liberated at the targeted zone and heat loss is minimized. Towards achieving
this goal, the paper presents a chemical kinetics based mathematical model which may be used to
predict the variation of temperature with respect to time for exothermic reaction between sodium
nitrite and ammonium chloride. The model has been validated with the experimental data obtained
in lab. Suitable charts have been prepared from numerical simulation of the developed model to
predict the delay time and peak temperature with reasonable accuracy. Lastly, based on the
developed charts a design methodology has been proposed to optimize the formulation of
exothermic reaction mixture depending on the area of application.
Introduction
Crude oil contains dissolved paraffin which may separate out and precipitate if the temperature falls
below a threshold value. Depending on the nature of crude, paraffin deposition may occur in
production tubing, surface equipment and even in the near well bore of matured fields having low
reservoir temperature. Conventional methods of paraffin removal include solvent treatment, hot
oiling, scraping and pigging.
As industry moved towards more difficult oil, a unique method of melting the wax deposit by
utilizing the energy liberated from exothermic chemical reactions was developed. This involves
pumping of two chemical mixtures which react together, generate energy and melt the paraffin
deposits. Broadly, they can be classified as organic and inorganic. Organic formulations utilize the
energy liberated from acid – base neutralization reaction. Typical organic acids include alkyl
substituted analogues of benzene sulphonic acid and naphthalene sulphonic acid while organic
amines are used as the base for exothermic reaction Error! Reference source not found.. The energy
released is usually sufficient to raise the fluid temperature beyond melting point of wax deposit.
Also, the by – products of the chemical reaction act as paraffin dispersant and provide easy
cleaning. However, the major limitation on their use is limited control on reaction rate, chemical
toxicity and higher cost.
As an alternate, inorganic formulations comprising of aqueous solution of sodium nitrite (NaNO 2 )

and ammonium chloride (NH 4 Cl) were developed which have higher enthalpy of reaction, easy
handling, lower cost and most importantly ability to control the reaction rate through use of suitable
catalyst. The time taken by the reaction mixture to acquire the peak temperature, henceforth termed
as ‘delay time’, can be changed by changing the pH of the solution. This allows for customizing the

formulation so that majority of energy is released at the target zone in the wellbore or pipeline. This
has been successfully applied for removal of paraffin deposits from wellbore Error! Reference source
not found., pipelines Error! Reference source not found. And even oil tanks Error! Reference source not
found.. In India, the technique was recently used to stimulate low temperature paraffinic reservoirs
Error.
The reaction between NH 4 Cl and NaNO 2 is not spontaneous and requires [H+] ions as catalyst to
proceed at an appreciable rate. It has been observed that the reaction rate is highly nonlinear with
respect to pH of the solution. It is negligibly small at pH above 6 and extremely fast at pH less than
4 Error! Reference source not found.. As a result, small changes in pH cause large changes in delay
time. Due to this nonlinear behavior, it becomes difficult to theoretically calculate and predict how
the temperature would vary for a given concentration of reactants and catalyst. Thus, large number
of experiments are required varying the concentration of reactants and catalyst individually to
understand the behavior of the chemical reaction and design the job suitably.
To bring a sense of predictability and prevent time and cost consuming experiments, this paper
presents a robust mathematical model based on chemical kinetics and reaction equilibrium.
Depending on the initial concentrations of the reactants, amount of catalyst and heat transfer
parameters, the developed set of equations can be solved numerically to yield the expected
temperature profile of the reaction mixture. A small scale batch reactor was developed in lab to
observe the reaction behavior experimentally. The results from simulation and experiments have
been compared and the model has been validated. Lastly, suitable charts have been developed which
can be used as an easy reference for designing of wax removal jobs using exothermic chemical
reaction with reasonable accuracy
Technology Description
Application of in – situ heat generating reaction mixture for paraffin removal is done by preparing
aqueous solutions of NH 4 Cl and NaNO 2 of desired molarity in two separate tanks as shown in Fig
1. Suitable acid catalysts like citric acid, acetic acid or a mixture of acetic acid and sodium acetate is
added to either one of the tanks. Other additives like non emulsifiers, wax dispersants, clay
stabilizers, etc. may also be added in any one of the tanks. To further enhance the effectiveness of
the job, a preflush of aromatic solvent can also be included before pumping of the exothermic
reaction mixture or it can be emulsified with the aqueous exothermic formulation.
The two solutions are pumped down the well by using two separate pumpers as shown in Fig.
1. For ease of operation, solutions of NaNO 2 and NH 4 Cl are prepared of equal molarity
and then pumped at same flow rate (1:1) using Pumper A and Pumper B. The two
solutions mix at the well head and react according to the following chemical reaction
Error! Reference source not found.
NaNO2 + NH4 Cl → NaCl + N2 + 2H2 O; ∆Hr0 = −334.5 kJ/mol (1)

The amount of acid catalyst is selected in such a way that the bulk of the reaction occurs down hole and the
temperature peak is attained some 200 ft. above the target zone of deposition Error! Reference source not found.
(Shown schematically at z = −L in Fig. 1). The high temperature of the incoming fluid melts the paraffin
deposits. The liberated nitrogen helps in pushing the solvent preflush further deep in the formation and also
assists in well activation. Upon flowing back, the solvent contacts the heated rock and further clears the
deposited paraffins.
As can be seen, it is desirable that the reaction must be suitably delayed to maximize its efficiency and prevent
excessive heat loss in the tubing. For this, it is important to know about the mechanism of chemical reaction at
play. This has been studied in great detail by Nguyen et. al in 2001 Error! Reference source not found. and 2003
Error! Reference source not found.. The reaction mechanism is found to have a rate-limiting step involving the
S N 2 reaction between aqueous molecular ammonia and nitrogen trioxide to form nitrosamine. It was also found
that the activity of hydrogen ion does not affect the mechanism of the reaction but changes the reaction rate by
changing the concentration of reactants involved in the rate limiting step Error! Reference source not
found..Accordingly, two rate laws have been proposed for chemical reaction (1) whose details may be found in
Appendix – A.
Fig. 1: Schematic of paraffin removal from wellbore using exothermic reaction mixture

Mathematical Formulation
A mathematical formulation was developed to predict changes in temperature, concentrations and pH of the
solution for given initial concentration of reactants and catalyst and heat transfer parameters. The details of the
development are provided in Appendix – A for flow systems and in Appendix – B for batch system. It can be
seen from Appendix – A and Appendix – B that the governing differential equations and the boundary
conditions for both the cases are of the same form. Both of them can be represented by the following set of
differential equations
dCi
� � = −νi r1 (2)
dt′
dT (∆Hr )r1 4U(T − Ta )
� �= − (3)
dt′ ∑ Ci Cpi D ∑ Ci Cpi
Subjected to the condition that

Ci (t ′ = 0) = Cio (4)
T(t ′ = 0) = To (5)
Where,
t, batch system
2
t = � πD
′
(6)
� � z, flow system
4V̇
Thus for identical conditions of heat transfer, the change in temperature with respect to time for a batch reactor
(as the one used in laboratory investigations) can be transformed to the change in temperature of a flow system
such as pipeline or wellbore by substituting z = (4V̇ /πD2 )t. This result has been used while preparation of
charts and in the proposed methodology of job design. Eqn. (2) – (6) for batch reactor have been solved
numerically using Runge – Kutta method Error! Reference source not found.. The results have been compared
with the experimental data obtained from lab experiments. This is discussed in the following section.
Laboratory Investigations
A small scale batch reactor was developed to study the evolution of temperature with time for various
combinations of reactant concentrations and pH. A schematic of the setup is shown in Fig. 2.
Fig. 2: Small scale batch reactor used for laboratory investigations

The contents in the reactor were well mixed with magnetic stirrer and it had the provision to measure the
temperature and pH of the solution as the reaction progressed.
Following cases were investigated in lab and simulated using mathematical model for batch reactor described
in Appendix B.
Case Number 1 2 3 4
Initial NaNO 2 3.0 M 3.0 M 3.5 M 3.5 M
Concentrations NH 4 Cl 3.0 M 3.0 M 3.5 M 3.5 M
(𝐂𝐂𝐢𝐢𝐢𝐢 ) CH 3 COOH 0.05 M 0.04 M 0.04 0.02
M M
CH 3 COONa 0.01 M 0.08 M 0.05 0.10
M M
o o o
Initial Temperature(𝐓𝐓𝐨𝐨 ) 17 C 17 C 18 C 20 oC
Ambient Temperature(𝐓𝐓𝐚𝐚 ) 24 oC 24 oC 23 oC 23 oC
Buffered pH 5.11 5.38 5.40 5.69
Table – 1: Parameters used for laboratory validation of developed model
The external diameter of the reactor was 6.7cm while the average value of overall heat transfer coefficient was
found to be around 10 W/m2K. The variation of temperature with time for the four cases mentioned in Table –
1 was recorded using the experimental setup shown in Fig. 2 and compared with the simulation results obtained
from the model described in Appendix B. This is shown in Fig. 3 below.
Fig. 3: Experimental versus simulated temperature profiles for cases described in Table - 1
It can be seen that the temperature profile predicted by the mathematical model is in good agreement with the
experimental results. The mixture undergoes through a delay time after which the temperature spike is
obtained. Also, the sensitivity of the reaction with pH can be readily observed from the two figures. The
mathematical model thus developed may be used to predict the temperature profile depending on the
concentration of reactants and heat transfer parameters. This can help in designing of suitable jobs for wellbore
treatment and/or surface facilities.

As the solution to the developed equations requires numerical techniques, it is of advantage to develop suitable
charts covering wide range of system parameters that can be easily used by a practicing engineer for reference
and design purpose. The same has been done in the following section.
Preparation of Design Charts

Although numerical simulation of equations (2) to (6) yields more accurate solution, suitable guidelines in the
form of charts have been prepared for field engineer for job design. For this the governing differential
equations have been non-dimensionalised and important dimensionless numbers have been identified. A more
detailed explanation of this is provided in Appendix – C.
As can be seen in Fig. 1, to achieve a desired concentration of NaNO 2 and NH 4 Cl in the final mixed reaction
mixture (at the well head), a concentration of double that amount has to be stored in the tanks as both the
pumpers are usually operated at the same flow rate. For example, to achieve 3.0 M solution of each NaNO 2 and
NH 4 Cl at the well head, 6.0 M solution each of NaNO 2 and NH 4 Cl is required in Tank B and Tank A
respectively for pumping at equal rates. While NaNO 2 is highly soluble in water, up to 12M at 25 0C, solubility
of NH 4 Cl is relatively less up to 7M at 25 0C Error! Reference source not found.. Also, the process of dissolution
of NH 4 Cl in water is highly endothermic which results in cooling of the solution while mixing whichfurther
decreases the solubility. It has been observed that up to 7M solution of NH 4 Cl is easy to make at ambient
conditions without heating. This also limits the maximum concentration of NaNO 2 to 7M as any excess amount
will remain unreacted and won’t be useful. Thus, the charts have been prepared for two commonly used
concentration of reactants in each tank: 7.0M and 6.0M. This gives the final concentration as 3.5Mand 3.0M
after mixing at wellhead for each NaNO 2 and NH 4 Cl. Ambient temperature of 300K has been taken as the
initial temperature of the reaction mixture. Subjected to these conditions, it can be seen from Appendix – C that
for given Co and To , the non-dimensional delay time (τp ) and peak temperature (θp ) depend only on Za
andCH + . Where,
160.026U
Za = (16a)
5.6 4174.66
DCo � − 107.36�
Co
Variation of τp and θp with CH + and Za has been plotted for various initial concentrations in Fig. 4 to 7 by
numerically solving equations C.4 to C.7 of Appendix – C.Following equations may be used to convert non
dimensional variables to their dimensional form
4V̇ τp V̇ τp
Lp = � 4.6 � = 50938 � � for flow systems (16a)
πD2 k o Co D2 Co4.6
τp
t p = 40006 � 4.6 � for batch system (16b)
Co
Tp = To �1 + θp � (16c)
The extent of conversion i.e. X(τ → ∞) has also been plotted in Fig. 4 and 5.This can be used to estimate the
total amount of energy released per liter of formulation using the following equation
Qg ≈ Co X∞ (∆Hro ) (16d)

Fig. 4. Variation of τp , θp and Xe with pH and Za for Co = 3.0M
Fig. 5. Variation of θp and Xe with pH and Za for Co = 3.0M

Fig. 6. Variation of τp , θp and Xe with pH and Za for Co = 3.5M
Fig. 7. Variation of θp and Xe with pH and Za for Co = 3.5M

Proposed Methodology for Job Design
The utility of the design charts developed in the paper is shown by considering the following two examples of
job design viz., treatment of near well bore and pipeline.
Example – 1: Job designing for near well bore treatment
S. No. Parameter Value Unit

1 Tubing ID (D) 0.062 m
2 Pumping Rate (V̇ ) 0.005 m3/s
3 Average heat transfer coefficient (U) 15 W/m2K
4 Initial concentration of 3.5 M
NaNO 2 /NH 4 Cl after mixing (Co )
5 Payzone Depth (Lp ) 2500 m
As a safety margin of 300m, it is desirable that the peak temperature be achieved at Lp = 2200m. Using
L p D 2 C 4.6
o 160.026U
equation 16, τp = 50938 V̇
= 10.6 and Za = 4174 .66 = 0.03. For these values of τp and Za, the
DC 5.6
o � C −107.36�
o
desired value of buffered pH from Fig. 6 comes out to be 5.88. To achieve this buffered pH, desired buffer
concentration can be calculated from equations A.7a to A.7h of Appendix – A. Alternatively, approximate
values can be obtained from Henderson– Hasselbalch equation Error! Reference source not found. from which
the final formulation becomes 3.5M NaNO 2 , 3.5M NH 4 Cl, 0.005M CH 3 COOH and 0.066M CH 3 COONa.
Other buffers like citrate, etc. may also be utilised. From Fig. 7, θp and Xe comes around 0.93 and 0.96. Thus
from equation 16, around 1124 kJ/liter of energy would be released from the chemical reaction.
Example – 2: Job designing for pipeline treatment
S. No. Parameter Value Unit

1 Pipeline ID (D) 0.1 m
2 Pumping Rate (V̇ ) 0.013 m3/s
3 Average heat transfer coefficient (U) 12 W/m2K
4 Initial concentration of 3.0 M
NaNO 2 /NH 4 Cl after mixing (Co )
5 Location of paraffin deposit 3000 m
With safety margin of 300m, peak temperature should be achieved at Lp = 2700 m. From equation 16,
L p D 2 C 4.6
o 160.026U
τp = = 6.4 and Za = 4174 .66 = 0.03. For these values of τp and Za, the desired value of
50938 V̇ DC 5.6
o � −107.36�
Co
buffered pH from Fig. 4 comes out to be 5.46 which can be achievedusing 0.005M acetic acid and 0.025M
sodium acetate Error! Reference source not found..

Unlike wellbore treatment, in case of pipelines, the fluidized mixture of paraffin and reaction mixture has to
travel large distances to reach the treatment facilities. It is desirable therefore to emulsify the exothermic
formulation with suitable solvent which can prevent the re-solidification of melted paraffin. The type and
amount of solvent to be added has to be optimized from laboratory experiments. Since solvent acts as a
different phase, its effect on kinetics of reaction may be neglected and the charts developed in this paper may
still be used with reasonable accuracy.
Conclusion
A mathematical model has been developed that can be used to predict the variation of temperature with respect
to time for exothermic reaction between NaNO 2 and NH 4 Cl. This can be used to design paraffin removal jobs
effectively for well bore and surface facilities.The model has been validated with laboratory experiments and a
good agreement has been found between predicted and experimental temperature profile. While a more
accurate solution is obtained from numerical simulation of the developed differential equations, suitable charts
have been developed to predict peak temperature, delay time and energy released which can be used by a field
engineer to design the job with ease. The same has been demonstrated with the help of twoexamples for
pipeline and well bore treatment.
Acknowledgement
The author is heartily obliged to ONGC for providing the opportunity as well as requisite administrative
support for the fruitful completion of the study. This study was carried out under able guidance and support of
various experts of Institute of Oil and Gas Production Technology whose excellent expertise and experience in
the oil industry as well as invaluable suggestions immensely helped the author in improving the knowledge and
skills. The views expressed in this paper are of author and not necessarily those of ONGC.
Nomenclature
T:Temperature of reaction mixture (K)
Ta :Ambient temperature (K)
To :Initial temperature of reaction mixture (K)
Tp :Peak temperature (K)
Tm :Mean surface temperature (K)
Fi :Molar flow rate of ith species (mol/s)
Ni :Number of moles of ith species (mol)
t:Time (s)
t p :Time to achieve peak temperature (s)
z:Axial location (m)
Lp :Axial location of peak temperature (m)
Ci :Concentration of ith species (mol/l)
Cio :Initial concentration of ith species (mol/l)
CH+:Concentration of H+ ion (mol/l)
V̇ :Volumetric flow rate (m3/s)
νi :Stoichiometric coefficient of ith species in chemical reaction (1)
ri :Rate of appearance of ith species in chemical reaction (1) (mol/l-s)
k:Reaction rate constant (s-l4.6-mol-4.6)

h� i :Molar specific enthalpy of ith species (J/mol)

ΔHr :Enthalpy of reaction (J/mol)
ΔHro :Standard enthalpy of reaction (J/mol)
Cpi :Molar specific heat capacity of ith species (J/mol-K)
∆Cp :Change in molar specific heat capacity of reaction mixture, ∑ νi Cpi (J/mol-K)
ρi : Density of ith species (kg/m3)
MWi : Molecular weight of ith species (kg/mol)
Q̇ l : Rate of energy loss to surroundings by heat transfer (W)
Qg : Total energy generated from chemical reaction (J/liter)
D: Diameter of tubing/pipeline/reactor (m)
H: Height of reactor (m)
V: Volume of reactor (m3)
U: Overall heat transfer coefficient (W/m2K)
k a : Thermal conductivity of air (W/mK)
g: Acceleration due to gravity (m/s2)
νa : Kinematic viscosity of air (m2/s)
θ: Non-dimensional temperature
θp : Non-dimensional peak temperature
X: Non-dimensional concentration
Λ: Non-dimensional reaction rate constant
τ: Non-dimensional time
τp : Non-dimensional time to attain peak temperature
X∞ : Non-dimensional concentration for τ → ∞
Nu: Nusselt number
Pr: Prandtl number
Ra: Rayleigh number
References
[1]J. M. Brown and J. B. Dobbs, “A Novel Exothermic Process for Removal of Paraffin Deposits in
Hydrocarbon Production,” NACE International, no. 233, 1998.
[2]N. O. Rocha, C. . N. Khalil, L. C. Leite and R. M. Bastos, “A Thermochemical Process for Wax Damage
Removal,” International Symposium on Oilfield Chemistry, Houston, Texas, 2003 (SPE 80266).
[3]C. Khalil, L. Neumann, C. Linard and I. Santos , “Thermochemical Process To Remove Paraffin Deposits In
Subsea Production Lines,” Offshore Technology Conference, 1994 (OTC 7575).
[4]N. d. O. Rocha, C. N. Khalil, L. F. Leite and A. M. G. Ferreira, “ThermoChemical Process To Remove
Sludge From Storage Tanks,” International Symposium on Oilfield Chemistry, Houston, Texas, U.S.A., 2007
(SPE 105765).
[5]S. K. Goenka, J. Singhal, M. D. Kothiyal, A. Parasher and S. Tiwari, “Near Wellbore Asphaltene and Wax
Remediation Using In-Situ Heat Generation in Both PCP and Non-PCP Wells: Concept, Operational
Challenges & Remedial Solutions,” SPE Asia Pacific Oil & Gas Conference and Exhibition, 2014 (SPE
171497).
[6]D. A. Nguyen, H. S. Fogler and S. Chavadej, “Fused Chemical Reactions. 2. Encapsulation: Application to
Remediation of Paraffin Plugged Pipelines,” Ind. Eng. Chem. Res., vol. 40, pp. 5058-5065, 2001.

[7]J. P. Ashton, L. J. Kirspel, H. T. Nguyen and D. J. Credeur, “In-Situ Heat System Stimulates Paraffinic-
Crude Producers in Gulf of Mexico,” SPE Production Engineering, vol. 4, no. 02, 1989 (SPE 15660).
[8]D. A. Nguyen, M. A. Iwaniw and H. S. Fogler, “Kinetics and mechanism of the reaction between
ammonium and nitrite ions: experimental and theoretical studies,” Chemical Engineering Science, vol. 58, p.
4351 – 4362, 2003.
[9]D. F. Griffiths and D. J. Higham, Numerical Methods for Ordinary Differential Equations: Initial Value
Problems, Springer London Ltd, 2010.
[10]P. Patnaik, Handbook of Inorganic Chemicals, McGraw-Hill Professional, 2002.
[11]G. W. Castellan, Physical Chemistry, Narosa, 2004.
[12]H. S. Fogler , Elements of Chemical Reaction Engineering, Prentice Hall India Learning Private Limited,
2008.
[13]R. G. Bates and G. D. Pinching, “Acidic Dissociation Constant of Ammonium Ion at 0° to 500 C, and the
Base Strength of Ammonia,” Journal of Research of the National Bureau of Standards, U. S. Department of
Commerce, vol. 42, 1949.
[14]J. Y. Park and Y. N. Lee, “Solubility and Decomposition Kinetics of Nitrous Acid in Aqueous Solution,” J.
Phys. Chem., vol. 92, pp. 6294 - 6302, 1988.
[15]H. S. Harned and R. W. Ehlers, “The Dissociation Constant of Acetic Acid from 0 to 60° Centigrade,” J.
Am. Chem. Soc., vol. 55, no. 02, pp. 652 - 656, 1933.
[16]Y. A. Cengel, Heat Transfer: A Practical Approach, Mcgraw-Hill (Tx), 2002.
Appendix –A: Development of Mathematical Model for Flow Systems
The mathematical model for flow systems viz. for pipeline and well bore treatment has been developed
subjected to the following assumptions:
The flow is in steady state and one dimensional (Plugged flow).
The reaction mixture behaves as an ideal solution.
No significant changes in potential and kinetic energy of flow.
No significant changes in the volumetric flow rate, specific heat capacities and densities
The chemical reaction is given by
NaNO2 + NH4 Cl → NaCl + N2 + 2H2 O (A. 1)
Additionally, following equilibrium equations are considered for calculation of [H+] when using a mixture of
acetic acid and sodium acetate as catalyst:
NO2− + H2 O ↔ HNO2 + OH − (A. 2a)

NH4+ ↔ NH3 (aq) + H + (A. 2b)
CH3 COOH ↔ CH3 COO− + H + (A. 2c)
H2 O ↔ H + + OH − (A. 2d)

Fig. A.1: Schematic for development of mathematical model
Following index notation has been adopted for the chemical species for ease of writing equations
Species Index Stoichiometric

(i) Coefficient(νi )
NaNO 2 1 -1
NH 4 Cl 2 -1
NaCl 3 1
N2 4 1
H2O 5 2
CH 3 COOH 6 0
CH 3 COO- 7 0
Table A.1: Index notation used for various chemical species
Referring to Fig. A.1, following equations can now be writtenError! Reference source not found.:
1. Mole Balance:
dFi π
= − νi r1 D2 , for i = 1, 2, … , 7 (A. 3)
dz 4
2. Rate Law: Any of the two following rate laws may be used
Rate Law – IError! Reference source not found.

−r1 = kC13.1 C22.5 (A. 4a)

k = k1 + k 2 CH1.8+
+ k 3 CH−0.7
+ (A. 4b)
9
k1 = 8 × 10 exp⁡(−12000/T) (A. 4c)
13
k 2 = 5 × 10 exp⁡(−7000/T) (A. 4d)
5
k 3 = −8 × 10 exp⁡(−13000/T) (A. 4e)
Rate Law – II Error! Reference source not found.
−r1 = kCH0.91 1.81 0.95
+ C1 C2 (A. 4f)
10
k = 5.33 × 10 exp⁡ (−7599/T) (A. 4g)
3. Energy Balance
7
d δQ̇ l
�� Fi h� i � + =0
dz δz
i=1
This may be expanded as
dh� i dFi δQ̇ l
� Fi + � h� i + =0
dz dz δz
Substituting dFi /dz from equation A.3 and usingdh� i /dz = Cpi dT/dz, following equation is obtained for
energy balance:
dT π δQ̇ l
�� Fi Cpi � � � − � r1 D2 � �� νi h� i � + =0 (A. 5)
dz 4 δz
Where ∑ νi h� i is the enthalpy of reaction ∆Hr
4. Heat Transfer
δQ̇ l
= πDU(T − Ta )(A. 6)
δz
5. Chemical Equilibrium
Following equations can be written for equation A.2a to A.2d using equilibrium constants:
K NH +4 = CNH 3 CH + /CNH +4 (A. 7a)

K NO −2 = CHN O 2 COH − /CNO −2 (A. 7b)
K AA = CCH 3 CO O − CH + /CCH 3 COOH (A. 7c)
K w = CH + COH − (A. 7d)
Additionally, from conservation of chemical species, 3 additional equations can be written
CNO −2 + CHN O 2 = C1 (A. 7e)
CNH +4 + CNH 3 = C2 (A. 7f)
CCH 3 COOH + CCH 3 CO O − = C6 + C7 (A. 7g)
From neutrality of charge
CNH +4 − CNO −2 + CH + − COH − − CCH 3 CO O − = C2 − C1 − C7 (A. 7h)

Expressions for K NH +4 , K NO −2 , K AA and K w are available in literature [13], Error! Reference source not found., Error!
Reference source not found.and are summarized below:
1500.65
−log K AA = + 6.50923 log T + 0.0076792T − 18.67257 (A. 8a)
T
4470.99
−log K w = + 0.017060T − 6.0875 (A. 8b)
T
2835.76
−log K NH +4 = + 0.001225T − 0.6322 (A. 8c)
T
4121.01
−log K NO −2 = + 0.017060T − 8.0737 (A. 8d)
T
Equations (A.7a) to (A.7h) may be solved simultaneously to get concentration of H+ ions i.e. CH + for given
C1 , C2 , C6 and C7 . Further, equations A.3, A.5 and A.6 can be simplified using the fact that Fi = Ci V̇ and
∑ νi h� i = ∆Hr The overall set of governing differential equations for temperature and concentration of chemical
species thus obtained is summarized below
4V̇ dCi
� � = −νi r1 , for i = 1, 2, … , 7 (A. 9)
πD2 dz
4V̇ dT (∆Hr )r1 4U(T − Ta )
� �= − (A. 10)
2
πD dz ∑ Ci Cpi D ∑ Ci Cpi
∆Hr = ∆Hro + ∆Cp (T − 298.15)(A. 11)
Ci (z = 0) = Cio , for i = 1, 2, … , 7 (A. 12)
T(z = 0) = To (A. 13)
Where −r1 is the rate at which NaNO 2 is consumed and can be calculated either from Rate Law – I (Eqn. A.4a
– A.4e) or Rate Law – II (Eqn. A.4f – A.4g). CH + required for calculation of r1 can be obtained by
simultaneously solving Eqn. A.7a to A.7h. The value of heat transfer coefficient may be calcultaed from
following correlations of natural convection Error! Reference source not found.
2
⎡ ⎤
⎢ 1 ⎥
UH ⎢ 0.387Ra6 ⎥
Nu = = ⎢0.825 + 8⎥ (A. 14)
ka 9 27
⎢ ⎥
⎢ 0.492 16
�1 + � Pr � � ⎥
⎣ ⎦
Where,
g|T − Ta |H 3
Ra = Pr (A. 15)
Tm ν2a

Appendix – B: Development of Mathematical Model for Batch Reactor
The mathematical model for batch systems has been developed subjected to the following assumptions:
1. The batch reactor is well stirred and the concentrations are uniform throughout.
2. The reaction mixture behaves as an ideal solution.
3. No significant changes in specific heat capacities and densities.
The same index notation has been followed as in Appendix – A.Chemical reaction and equilibrium equations
also remains the same as in Appendix – A. The schematic of the batch reactor used for laboratory investigation
is shown in Fig. B.1.
Fig. B.1: Schematic of the batch reactor used for laboratory investigation
Following equations may be written for reaction mixture in Fig. B.1Error! Reference source not found.
1. Mole Balance:
dNi
= −νi r1 V, for i = 1, 2, … , 7 (B. 1)
dt
2. Energy Balance:
7
d
�� Ni h� i � + Q̇ l = 0 (B. 2)
dt
i=1
• Heat Transfer:
Q̇ l = πUDH(T − Ta ) (B. 3)
Expressions for chemical equilibrium and methodology for calculation of r1 i.e. rate of consumption of NaNO 2
is same as in Appendix – A. Following a procedure similar to Appendix – A, equations B.1 to B.3 can be
π
simplified using the fact that Ni = Ci V andV = 4 D2 H. The resulting governing differential equations thus
obtainedfor temperature and concentration of chemical species are summarized below

dCi
= −νi r1 (B. 4)
dt
dT (∆Hr )r1 4U(T − Ta )
= − (B. 5)
dt ∑ Ci Cpi D ∑ Ci Cpi
∆Hr = ∆Hro + ∆Cp (T − 298.15)(B. 6)

Ci (t = 0) = Cio , for i = 1, 2, … , 7 (B. 7)
T(t = 0) = To (B. 8)
The value of heat transfer coefficient can be calculated by equation A.14 and A.15 of Appendix – A.
Appendix – C: Non dimensionalisation of generic differential equation
The generic differential equation has been non-dimensionalised for the following special case
1. Initial composition of reaction mixture consists of equal moles of NH 4 Cl and NaNO 2 in water and no
other reaction products (C1o = C2o = Co , C30 = C40 = 0)
2. Initial temperature of the reaction mixture is equal to the ambient temperature (Ta = To )
3. Rate Law – I Error! Reference source not found. is used for calculation of rate of reaction.
Subjected to the above conditions,C1o = C2o = Co , C3o = C4o = 0 andTa = To . Non dimensional variables
used throughout are defined as
T − To Ci − Cio k
θ= , X= , Λ= , τ = k o Co4.6 t′ (C. 1)
To νi Co ko
Where the value of characteristic reaction rate constant k o = 2.4996 × 10−5 mol−4.6 dm4.6 s−1 istaken as the
value of kat T = 298 K and pH of 4.5. Concentration of any chemical species i can then be written as
Cio
Ci = Co (γi + νi X), γi = (C. 2)
Co
Reaction rate constant can be expresses as
3 3 Ej
Ej
nj − n
k= � A j e− T CH + = � Aj e o
T (1+θ) CHj+ (C. 3)
j=1 j=1
Values of Aj , Ej andnj are given in Appendix – A. Using the non-dimensional variables defined by equation C.1,
the generic differential equations (2) to (6) become

dX
= Λ(1 − X)5.6 (C. 4)
dτ
dθ dX
= −Zaθ + Ji (C. 5)
dτ dτ
3 Ej
1 − n
Λ = � Aj e T o (1+θ) CHj+ (C. 6)
ko
j=1

X = 0 at τ = 0 and θ = 0 at τ = 0 (C. 7)
Where the non-dimensional groups are given by
4U 160.026U
Za = 5.6 ∑ = (C. 8)
1000Dk o Co γi Cpi DCo5.6 ∑ γi Cpi
−∆Hr
Ji = (C. 9)
To ∑ γi Cpi
ρ5 Cp5 MW1 MW2
� γi Cpi = Cp1 + Cp2 + �1000 − Co � + ��
Co MW5 ρ1 ρ2
Substituting the values of molecular weights, densities and specific heats Error! Reference source not found.
4174.66
� γi Cpi ≈ − 107.36 (C. 10)
Co
From equation C.4 to C.7, it is evident that

Λ = Λ(τ, Za, Ji, CH + , To ) (C. 11a)
X = X(τ, Za, Ji, CH + , To ) (C. 11b)
θ = θ(τ, Za, Ji, CH + , To ) (C. 11c)
It can be seen from C.9 and C.10 that by fixing the value of Co andTo , value of Ji gets fixed. Hence, for a given
initial concentration Co and ambient temperature To
X|C o ,T o = X(τ, Za, CH + )(C. 12a)

θ|C o ,T o = θ(τ, Za, CH + ) (C. 12b)

Title: “Green Corrosion Inhibitor for Biofuels Blended Gasoline and Diesel: A Quality Control
Viewpoint”
-P. K. Mondal, Dr. Sourav Bhunya, Haldia Installation, Indian Oil Corporation Limited & Retired Prof. B.S.
Saraswat, Department of Chemistry, School of Sciences, Indira Gandhi National Open University, New Delhi
Key Words: Fossil-fuel, Bio-fuel, Biodiesel, Ethanol, Corrosion, Inhibitors, Phyto-chemical, Vedas,
tailadhãuta, green chemistry.
Abstract:
Nowadays automotive fuel industry is grappling with shrinking margins and increasing pressure to comply with
environment norms. Industry has started seeing green chemistry as a tool that can enable them to achieve both
economic and environmental competitiveness. Seeing that the amount of bio-fuels (biodiesel & ethanol) being
incorporated into the fuel stream is increasing, bio-fuels became an attractive alternative for fuel marketing
companies. Introduction of bio-fuels made the blended fuel more environmentally friendly as bio-fuels do not
produce any pollutant. Receiving optimum performance from the blended fuel remains a huge challenge for the
oil marketing companies and the automobile companies as bio-fuels are not chemically inert like the
conventional fossil fuels. Biodiesel is more susceptible to oxidation, microbiological attack and sensitive to
temperature and humidity changes, which cause variation in pH and water content. The water content in bio-
fuels may condense over the metal surface or accelerate the hydrolysis reactions to affect the quality of blended
fuel. Also, these blended fuels can negatively affect the storage tanks, transportation or distribution modes.
Degradation of the mechanical integrity of ethanol piping and steel tanks is established due to the well-known
phenomenon of ethanol stress corrosion cracking. The significant corrosion issues associated with bio-fuels like
stress-corrosion cracking (SCC) have occurred in carbon steel in contact with fuel grade ethanol and corrosion
and microbiologically influenced corrosion (MIC) have been reported in tanks storing biodiesel. So, devising a
method for reduction of the corrosive property of bio-fuels has garnered lot of attention in recent times.
The present work is aimed to study the physico-chemical properties of Biofuels blends and corrosion of
materials like metals by them, minimizing their corrosiveness by addition of some naturally occurring phyto-
chemicals from different tree gums, rosins, fungus extract as green corrosion inhibitor.
1. Introduction
Fuels occupy a significant place in human history. More than ever today, it is impossible to imagine our life
without fuels [1]. The high energy demand in the industrial world and domestic sector as well as the pollution
problems caused by emission from the use of fossil fuels has led to intensive research in alternative fuel sources
with lesser environmental impact. The history of human civilization is a continuous endeavor to learn the use of
natural resources and this quest for knowledge helped in the progress of material science and technology [2].
There is an alarming concern about the depleting petroleum reserves of the world. This has led to global search
for alternative fuels. Biofuels are derived from renewable sources [3]. Biofuels (Bio ethanol and biodiesel) has
gained progressive importance as alternative fuel for automobiles because they can significantly reduce
environmental pollution and dependence on fossil fuel [4]. Bioethanol and Biodiesel represent an important
renewable fuel for gasoline or diesel engine without any engine modification to replacing the fossil fuels.
However change in fuel composition and the introduction of alternative fuels often create material
compatibility issue in terms of corrosion and degradation of the automobile parts [5]. Utilization of biodiesel in
automotive application imposed in direct contact of biodiesel or biodiesel blends which can be grouped in the
three categories i.e. (i) ferrous alloys, (ii) non-ferrous alloys and (iii) elastomers [6]. Cursaru et. al. describes the

corrosion behavior of biodiesel, diesel fuel or mixtures biodiesel-diesel fuel. It was evaluated by conventional
electrochemical techniques. It was found that corrosion rates of metal immersed in commercial diesel fuel were
relatively lower than corresponding to the corrosion rate of the metals immersed in biodiesel. In addition it was
observed that by rising the percentage of bio-diesel in diesel fuel the corrosion raise [7]. The interest in the
investigation of materials compatibility in ethanol is top priority due to the increase demand for ethanol cause
by its growing application as fuel, a fuel additive for automobiles. Many countries including India have already
mandated use of ethanol blended petrol (IS 2796:2017) or biodiesel blended diesel (IS 1460:2017). During
production, transportation and usage/ storage, ethanol comes in contact with various materials. Therefore, it is
important to understand the influence of ethanol on materials as well as the influence of materials on ethanol,
so that the design and construction of systems handling biofuels can be carried out in cost effective manner [8].
It was also researcher observed that corrosion rate appears to be directly dependent on the percentage of alcohol
and moisture content of blended gasoline fuel.
In automobile engine, fuel comes in contact with a wide variety of engine parts including fuel pump, gaskets,
fuel injector, filters, fuel liners, bearings, piston, piston ‘O’ rings etc. Among them, Copper alloy based part
like fuel pump bearing, bushes etc are mostly affected by the fuel [9]. The two most common biofuels are
biodiesel and ethanol. The use of biofuels is considered to be environmentally friendly [10]. With the
introduction bio-ethanol and biodiesel fuels and newer engines requiring higher quality fuels, getting optimum
performance can be a challenge for distributor as well as marketer and end user i.e. automobile owners. While
these new fuels are designed to improve emissions and our environment, they can also negatively affect storage
tank, transportation or distribution modes. Pipelines offer significant safety advantages and improved cost-
effectiveness compared to other shipping methods if the corrosive effects are predictable, especially with
respect to their mechanical integrity. Conversely, degradation of the mechanical integrity of ethanol piping and
steel tanks is established due to the well-known phenomenon of ethanol stress corrosion cracking [11]. Regular
tank maintenance is also much more important when using these new fuels [12]. The electrical conductivity of
biofuels is low, so it was initially assumed that they are noncorrosive; however, field experience has been
different [13]. The significant corrosion issues associated with bio-fuels like stress-corrosion cracking (SCC) has
occurred in carbon steel in contact with fuel grade ethanol and Corrosion and microbiologically influenced
corrosion (MIC) have been reported in tanks storing biodiesel [14]. Corrosion mainly occurs due to the entry of
moist air during storage & contamination of the blended bio-fuel with water during transportation. As stated by
Singh et al. the rate of corrosion is influenced by temperature, water content, microbial growth, and type of
feedstock used for synthesis of biodiesel[15]. In order to ensure smooth and uninterrupted flow of oil and gas to
the end users, it is imperative for the field operators, pipeline engineers, and designers to be corrosion
conscious as the lines and their component fittings would undergo material degradations due to corrosion [16].
However, the corrosion problem and few limitations of using biofuels are overcome by incorporate corrosion
inhibitor (CI) in the fuel composition. But it increases the cost and difficulty to handle due some toxic nature
of commercial chemical corrosion inhibitor. Most of the inorganic inhibitors used are toxic substances. The
safety and environmental issues of corrosion inhibitors has become a global concern. Nowadays automotive
fuel industry is grappling with shrinking margins and increasing pressure to comply with environment norms.
Industry has started seeing green chemistry as a tool that can enable them to achieve both economic and
environmental competitiveness [17]. The changing hydrocarbon industry needs and continues stringent pollution
control requirements to protect our environment we face intensification of process system & new product
developments [18]. A good numbers of published literatures found in present days on study of phyto-chemical as
corrosion inhibitors in different medium for various metals & metal alloys. Environmental friendly corrosion
inhibitors range from rare earth elements to organic compounds and are used as alternative corrosion inhibitors

to reduce the harmful effects on humans, animals and environment. In ancient India people are using naturally
occurring plant product on surface preparation. The Delhi pillar has not rusted to a marked degree, and this
resistance to corrosion is ascribes by the different authors the composition of the iron, which is free from
manganese and sulphur, and contains a tolerably high percentage of phosphorus [19]. The Mahabharata and
some Puranas have referred to ferrous arrowheads, which were subjected to ‘tailadhauta’ treatment [20-21].
Arrows rubbed with oil shine like snakes that have just cast their skins (tailadhauta vyarajanta nirmukta
bhujagopamah 6.92.48) [22]. The use of inhibitors is a well-known strategy when metal corrosion needs to be
controlled, prevented or retarded [23]. Among the great number of patents related to corrosion prevention actions
and corrosion inhibitors uses, however, just few of them directly deal with green corrosion inhibitors [24].
Mondal et al. describe the process for preparing Rust Inhibitors from Cashew nut shell liquid (CNSL) in Patent
No. US 6548459 B2 [25]. Although most of organic molecules tend to adsorb on metal surfaces, usually, when
aiming at the corrosion inhibition effect, the most desirable features are specific and related to: the metal
electrostatic attraction on the charged inhibitor molecules; the interaction of double/triple bonds or lone pair
electrons of (N, S, P or O) with the vacant d-orbital of the metal; or a combination of some of the previous
mechanisms [26]. Large Numbers of heterocyclic synthetic compounds have been reported as corrosion
inhibitors and the screening of synthetic heterocyclic compounds is still being continued, for example
Thiadiazole, Amine, Pyridine, pyrrole, phenoxoy acetic acid. A novel thiadizole type corrosion inhibitor
derived from refinery waste streams was described by Bhatnagar et al. in Patent US 6,362 137 B1 and Mondal
et al in patents WO 2004/011578 A1, US 2005/0032654 A1 & US 7396802 B2 [27-30]. From the Vedic age
utilization of natural resources and managing waste or reuse of waste was ancient Indian civilization practice.
Consuming juice extracted from sugarcane and using its rind after drying and then again using its ashes as
manure in farms. Its ash also comes in use for cleaning utensils etc. Such description of sugarcane is also
available in Vedas. Indian lifestyle is against wastages. Managing our daily chores with minimum resources is
especially inherent in our lifestyle, because we have always considered it as our sacred duty to preserve nature.
That is why, nature was worshipped in the first adage of our ancient sacred Rigveda – there is a description and
resolve to protect the five basic elements of nature contained in these mantras [31]. Today lot of technical
research articles demonstrate the use extract of different plant parts and food waste like peal, seeds, straw as
corrosion inhibitors for metals in various media [32-38]. The interest on green inhibitors in the last few decades
increasing significantly, it can be explained by the number of publications for a period during 1990s and after
2010. Although numbers of publication on green corrosion inhibitor mounting very first, among them only few
are related to the petroleum industry.
The present work is aimed to study the physico-chemical properties of Biofuels blends and their corrosion
behavior on materials like yellow metals and iron, minimizing their corrosiveness with addition of some
naturally occurring phyto-chemicals from different tree gums, latex, fungus, rhizome extract as green
corrosion inhibitor. A preliminary search to develop Laboratory Test method for Biofuel blends Corrosion
tendency study, which is based on two international standard test methods (i) ASTM D-7548-16 and (ii) ASTM
D7577-12 for Iron. Inhibition performance evaluation for various substances recovered from ethanolic
extraction of Araucaria heterophylla (A. excelsa) gum, Boswellia serrata rosins, Ganoderma lucidum
(Reishi mushroom) and Sesamum indicum L Oil(Til oil) as Green Corrosion Inhibitor in deferent
percentage of gasoline-alcohol blended and blended biodiesel fuels for mild steel specimens or coupon. In
addition copper corrosion as per ASTM D130-12 in deferent gasoline-alcohol blended and blended biodiesel
fuel hydrocarbon media.

2. Corrosion
Corrosion is a natural phenomenon where metals and alloys try to revert to their more stable thermodynamics
form i.e. ores (naturally occurring mineral from which metals are extracted) due to reaction with the
environment that surrounds them. Corrosion is expensive due to loss of materials or their properties, which
leads to loss of time during maintenance, the shutting down of systems, and severe failure of some structures,
which in some cases may be hazardous and cause injury.
2.1 Corrosion problem in Petroleum Industry

Corrosion is more than just an inevitable natural phenomenon; it happens in every industrial on their
infrastructure, equipments and others facility. Corrosion is very important from the points of view of
economics and tragic accidents involving huge loss, even some time life threatening. May corrosion become
very expensive as well as unsafe in our daily work life? The answer is yes, because petroleum industry contains
a wide variety of corrosive environments. And few of these are unique to this industry. Therefore it is
convenient to group all these environments together. Corrosion problems occur in the petroleum industry in all
the three general areas like (i) upstream (ii) midstream (iii) downstream sectors. The possibility of corrosion
occurs in case of upstream business during crude oil exploration drilling and storage activity where as in
midstream it appeared during transportation & storage. But in downstream petroleum business corrosion
problem seen during product refining, storing, transportation and when finish product in service. Thus we can
broadly summarize the category as (1) Oil exploration, (2) Transportation and storage, and (3) Production or
refinery operations and (4) Product in serving & service.
2.2 Mitigation of the corrosion

Corrosion mitigation has become more challenging as we move toward complex fuel producing technology &
hydrocarbons from highly corrosive environments. National Association of Corrosion Engineers (NACE), USA
reportedly projected the global cost of corrosion to be US$2.5 trillion to emphasis the cost management of the
corrosion effects, not limited to environmental damage and safety, in global society. Meanwhile, proper
implementation of corrosion control measures can save about $875 billion annually. Traditional methods of
monitoring corrosion include the use of metallic coupons fluid analysis, ultrasonic testing and radiography.
Early detection of corrosion initiation and replacement or reorientation of the metal, metal alloys & altering
hostile /corrosive environment is the best way of corrosion mitigation. Corrosion inhibitors are effectively
altering the hostile /corrosive environment. Corrosion chemistry is changing at a rapid pace and every chemical
process is viewed very critically from the points of view of safety, environmental impact, and economics.
2.3 Corrosion inhibitors

A corrosion inhibitor is a chemical compound that, when added to a liquid or gas, decreases the corrosion rate
of a material, typically a metal or an alloy. One of the methods of combating corrosion is the use of corrosion
inhibitors that decrease the corrosion rates to the desired level with minimal environmental impact. The field of
corrosion inhibitors is undergoing dramatic changes from the viewpoint of environmental compatibility.
Environmental agencies in various countries have imposed strict rules and regulations for the use and discharge
of corrosion inhibitors. Strict environmental regulations require corrosion inhibitors to be environmentally
friendly and safe.
2.4 Green Corrosion Inhibitors

Green corrosion inhibitors are biodegradable and do not contain heavy metals or other toxic compounds. Green
corrosion inhibitors are of interest because there has been an increase in environmental awareness and a change
in regulations that restrict harmful chemical corrosion inhibitors due to their toxicity. Natural products are an

excellent source of environmental friendly green corrosion inhibitors, where most of the various plant parts
extracts is used, containing the necessary elements such as O, C, N, and S generally called heteroatom, which
are active in organic compounds, assist in adsorption of these compounds on metals or alloys to form a film
that protects the surface and hinders corrosion. Numbers of expert in the field have reported the successful use
of naturally occurring substances to inhibit the corrosion of metals in acidic and alkaline environment. Some
recent plant extracts evaluate as green corrosion inhibitors for different metals and alloys by the various
researchers are exhibited as Table-1 in summarized form. Corrosion inhibitors further categorized as following
types in the basis of their origin and mode of action.
Table-1: Some recent plant extracts as green corrosion inhibitors of different metals and alloys
Sr Plant Name Portion of Plant Use Medium Ref No.

No.
1 Chestnut Peel Antioxidant for DPPH free -- [32]
radical
2 Mangifera indica leaves and bark Prevent corrosion of mild diluted [34]
steel (H2SO4) medium
3 Zenthoxylum alatum fruit extract Prevent corrosion of mild Phosphoric acid [34]
steel medium
4 Justicia gendarussa leaves Corrosion inhibition of mild hydrochloric acid [34]
steel medium
5 phyllanthus leaves, seeds & their corrosion of HCl and H2SO4 [34]
amarus combination extract mild steel
6 Opuntia stem extract Corrosion inhibition of HCl acid solution [34]
aluminium
7 Mentha pulegium Leave estact corrosion inhibition of steel HCl acid solution [34]
8 Jojoba oil Oil seeds Prevention of steel HCl medium [34]
and Artemisia oil corrosion
9 Datura metel Leave estact Corrosion inhibition of mild HCl as well in [34]
steel H2SO4
10 Strychnos nux- seeds Corrosion inhibition of mild HCl as well in [34]

vomica steel H2SO4
11 Ammi visnaga seeds Corrosion of SX 316 stainless HCl solution [34]
steel
12 Solanam Leaves Corrosion Inhibition of Acidic medium [35]
Xanthocarpum Carbon Steel
13 Tridax procumbens Leaves corrosion resistance of CO2-saturated [36]
and Chromolaena super austenitic stainless steel acidizing oilfield
odorata (UNS S31254) environment
14 Allium Sativum Aq. extract bulbus Corrosion inhibition of mild well water [38]
steel environment
.
3. Experimentation & Results

3.1 Study Corrosion Behavior of Biofuels
Ethanol–gasoline blends can easily absorb large amounts of water because of the presence of ethanol. Acidic
compounds and ions can be dissolved in water, and these substances can have corrosive effects on metallic
construction materials. With the increasing content of ethanol in fuels, the conductivity and ability of fuel to
absorb water increases, and the resulting fuel is becoming more corrosive. The ethanol–gasoline blends E10,
E40, E60, E85, and E100 fuels were prepared in the laboratory and checked for their corrosive behavior.
Similarly biodiesel –diesel blends B5, B10, B20, B40 and B100 fuels were prepared in the laboratory and
checked for their corrosive behavior. To predict the corrosion behavior of the blended fuels initially check the
conductivity of deferent blends of biofuels. It was observed that the conductivity increase proportionally with
blend percentage of Biofuels in petro fuel, indicating probability of corrosive behavior increases due to
increasing corrosive current.
The corrosive nature of biofuels was at first investigated by copper strip corrosion test according to ASTM D-
130:2012. ASTM D-130 test method covers the determination of the corrosiveness to copper of aviation
gasoline, aviation turbine fuel, automotive gasoline, kerosene, diesel fuel, distillate fuel oil, lubricating oil, and
natural gasoline or other hydrocarbons having a vapor pressure no greater than 124 kPa (18 psi) at 37.8°C. The
results of these investigations are analyzed with standardized references; we observed a slight tarnish, which
classify our samples in 1a corrosion class. This method indicates only marginal corrosion and cannot make a
convincing distinguish level of corrosion between different concentrations of biofuels in blends. Therefore, the
copper strip corrosion test was coupled with total acid number (TAN) test according to EN ISO 6618:1987
color indicator titration test method. Total acids number (TAN) was determined with remnant sample after
corrosion test with immersion of metallic specimen in blended fuel & completing prescribed testing hours at
particular temperatures, it was found increase the TAN value with increasing percent blend level as showing in
Table-2.
Biodiesel Copper Strip Copper Strip Total Acid number TAN Result mg
Blends corrosion Test Test Result (TAN) Test Methods KOH/g
Methods
B0 ASTM D-130 1a EN ISO 6618 -
B1 ASTM D-130 1a EN ISO 6618 0.175
B5 ASTM D-130 1a EN ISO 6618 0.198
B7 ASTM D-130 1a EN ISO 6618 0.203
B10 ASTM D-130 1a EN ISO 6618 0.212
B100 ASTM D-130 1a EN ISO 6618 0.303

Table-2: TAN of different Biodiesel Blends determined with remnant sample after corrosion test
During reporting and analysis of the rating of metallic specimens (simulated ASTM D-7548:2016 & ASTM
D7577:2012 for accelerated corrosion check) after corrosion test in deferent blends of biofuels same trend was
observed in TAN increasing. If more than 7-10 % biofuels blended in petro fuel corrosion tendency increase
rapidly. Hence addition of corrosion inhibitor essentially requires in sufficient concentration for all biofuels
blended fuels.
3.2 Study Green Corrosion Inhibitor for Biofuels Blends

Green Corrosion Inhibition derived from renewable sources by ethanolic extract of various parts of plants likes
(i) Araucaria heterophylla (A. excelsa) gum (ii) Ganoderma lucidum (Reishi mushroom) (iii) Boswellia
serrata rosin (dhoop) and (iv) Boswellia serrata rosin [dhoop, shallaki] & Sesamum indicum L (Til oil or
Sesame oil) adduct (BTTA) shown in Figure-1. The extracted materials & said adduct are doped at ppm (100 to
1100) level in deferent percentage of gasoline-alcohol blended and blended biodiesel fuels for mild steel
specimens or coupon. Copper corrosion as per ASTM D130:2012 in deferent percentage of gasoline-alcohol
blended and blended biodiesel fuel hydrocarbon media was performed. Araucaria heterophylla gum,
Ganoderma lucidum mushroom ethanolic extract and said adduct of dhoop and til-oil are successfully protect
copper corrosion at 500C for 3hr. All these three compounds are effectively protecting Copper even in presence
of 0.01% active elemental sulfur. The ethanolic extract of Araucaria heterophylla gum (APGE), Ganoderma
mushroom (GLME) & dhoop and til-oil adduct protect mild steel corrosion at 37.80C in petroleum media in a
promising extent as per two international standard test methods (i) ASTM D-7548-16 and (ii) ASTM D7577-12
for determination of Accelerated Iron corrosion in petroleum products and Iron corrosion rating of denatured
fuel ethanol and ethanol fuel blends. It observed that corrosion protection by ethanolic extract A.
heterophylla gum for mild steel is exceptionally high which may visualized from the Figure-2.
Figur-1: Various sources for natural green corrosion inhibitors

Figure-2A: Copper Strip re-2B: Iron specimen Corrosion Test at 390C with 60 ml E10 Biofuel blended MG
Corrosion Test at 500C with 30ml or Gasoline) in presence of 1ml distilled water.
E10 Biofuel blended MG (Motor a.)
Gasoline) in presence of 0.01% 0% Ethanol + 90% MG Without CI
active elemental Sulfur. b.)
10% Ethanol + 90% MG Without Ethanol + 90% MG With PPM BTTA
CI c.)
10% Ethanol + 90% MG With 0% Ethanol + 90% MG With PPM APGE
800 PPM BTTA d.)
10% Ethanol + 90% MG With 0% Ethanol + 90% MG With PPM GLME
800 PPM APGE
10% Ethanol + 90% MG With
800 PPM GLME
3.3 Corrosion Prevention by Green CI
Adsorption is the first step in forming a corrosion protective film or coat by green corrosion inhibitors in the
presence of aggressive environment that occurs on metallic surfaces on the active sites. Various factors affect
the adsorption of inhibitor on the metallic surface and isolate it including adsorption mode, chemical and
electronic characteristics of the inhibitor, temperature, type of electrolyte employed, stirrer effects, and the
nature and surface charge of metals. Adsorption on the metal or alloy surfaces approximates to a steady-state
adsorption that may be physical adsorption (physisorption) or chemical adsorption (chemisorption), or a mixed
adsorption mechanism that is considered ideal for effective corrosion inhibition.
3.3 Mechanism of adsorption and inhibition

In the various literature researchers already identified Isocupressic acids, 13C-symphyoreticulic acid present in
A. heterophylla gum and Ganoderic acids, Lucidenic acids; Steryl esters (ergosterol) are present in Reishi
mushroom. Boswellia serrata rosin contains Boswellic acids. Sesamolin, Sesamin, sesamol dimer, sesamol-
dimer quinine, Sesangolin present in the Sesamum indicum L oil. Most probably presences of above organic
molecules in the concerned extract tend to adsorb on metal surfaces. When considering the corrosion inhibition
effect, the most desirable features are specific and related to: the metal electrostatic attraction on the charged
inhibitor molecules. The interaction of double/triple bonds or lone pair electrons of oxygen atom present in the
molecule and with the vacant d-orbital of the metal. Some time take place a combination of the both
mechanisms.

Isocupressic acids, Ganoderic acids, Lucidenic Boswellic acids from Boswellia serrata
13C-symphyoreticulic acids; Steryl esters (ergosterol), rosin
acid,
11-Keto β Boswellic acids adsorption shown in the Figure-3 on

metal surface by physisorption trough lone pair electron of
oxygen and interaction of double bonds Figure-3: Boswellic acids adsorption on
metal surface.
6. Direction of Future Study
In the present work having little limitations it required further correlation of present findings/ observation with
advance analytical techniques like SEM & Electro-gravimetric analysis of Corrosion inhibition performance
and chemical structural evidence of absorbed active compound on metal surface by NMR or IR and FD-mass
spectroscopy.
7. Conclusion
The changing hydrocarbon industry needs and continues stringent pollution control requirements to protect our
environment we face intensification of process system & new product developments. With the improving
process & products we required an exhaustive quality control process & quality control professional having
good knowledge on product and its chemistry and physicochemical behavioral interaction of product. The test
method developed for evaluation of green corrosion inhibitor may use for blended biofuels corrosiveness
properties testing, Quality control checks for corrosion inhibitor performance during purchase, evaluation of
corrosion inhibition potential during vendor selection. The ethanolic extract of A. heterophylla gum, Reishi
mushroom and Boswellia serrata rosin [dhoop] & Sesamum indicum L oil (Til oil) adduct (BTTA) may use
in biofuels blend composition as low cost environmental friendly green corrosion inhibitor. Reishi mushroom
i.e. Ganoderma lucidum a Marvelous Lucky Fungus that can be cultivated easily at our rural region it having
pharmaceutical important also. A. heterophylla we can grow at our hilly area and Boswellia serrata may be
cultivate in dry mountainous zones of India. Sesamum indicum L a wild plant may cultivate any waste land or
beside road & railway track. The close look on environment & pollution control requirements, social
obligation, rural development everything are include in single point that how much importance we are giving
on production & use of Alternative fuel and additives from renewable recourses.
8. Acknowledgements
Authors express their sincere gratitude to Ms. Shefali Das from Malda (Pundra town in ancient Indian
civilization) presently a district of West-Bengal, India for shearing secrete technique of preparation a surface
active compound from Boswellia (dhoop) Indian frankincense, an resin made from Boswellia serrata tree and
Vegetable oil, which was successfully use in severe burn wound healing from ancient time. Authors are
thankful to Dr Manish Jain, SQCM, Haldia Refinery of IOCL for providing various Laboratory facility & help
in experimental work for these studies. Authors also express their gratitude to Management of Quality Control

Department, Marketing Division, Indian Oil Corporation Limited, and thankful for the permission to present
this work in the conference.
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Title: “Series of Failure and Success Trails of Offshore Well Cement Plugs Leads to challenge of effective
NDDF removal, Optimization of WOC & Reduction in NPT-Case History.”
-R.K. Raigar, Dr.Kishori Lal, AbhinavHazra, Parvinder Singh & Pradeep Kumar, Institute of Drilling
Technology, Oil and Natural Gas Corporation Limited Dehradun.
Abstract
The most deleterious effects on cement by contamination, which tend to extend thickening time (TT), reduction
& delay in ultimate compressive strength (CS) development and finally leading to micro channelling and poor
cement bonds. Ultimately all this leads to potential impact on long term integrity of cement sheath.
Optimization of waiting on cement (WOC) time has been a persistent problem that has bothered oil industry
especially for offshore wells. To achieve better cycle speed of rig, operator tags in green cement resulting in
loss of rig time & further complications. An extensive lab study was carried out for failure cement plug jobs of
Mumbai offshore which led us to develop an innovative solutionfor proper removal of Non Damaging Drilling
Fluid (NDDF), WOC optimization and overall NPT reduction.
In this study thermal simulator was used to accurately predict the increase in bottom hole static temperature
(BHST) after WOC rather than using standard tables to predict the same. Adetailed laboratorystudies were
carried out for compatibility of cement slurry with NDDF & spacer. Series of neat and contaminated cement
samples were tested to compare with the field results. Further contamination and compatibility tests with used
mud and spacer systems were carried out to find out probable reasons for plug failures.
It has been found out that the NNDF could not be removed properly and the temperature required for slurry to
reach BHST is longer than that depicted by the standard tables, resulting in delay of TT and slower rate of CS
development. The simulated cement job condition and temperature scheduling after WOC depicts green cement
effect even in uncontaminated cement slurries in some cases. NDDF removing efficacy by innovative
formulation was evaluated on piece of 3-1/2’’ drill pipe keeping one end blind with metal plate at ambient as
well as at 85OC, the prevalent BHCT in Mumbai offshore fields.
Considering the constraints of field conditions, a holistic approach needs to be adopted while planning for a
plug job and accordingly cement job parameters has to be optimized, moreover proper removal of NDDF to be
assured to minimize contamination. Designed cement formulation was based on above optimized parameters.
This study further emphasise that for determining the CS of cement formulations with at least 10% mud /
spacer contamination should be used as a valuable input for WOC optimization by using Ultrasonic Cement
analyser (UCA).
Introduction
It is well known fact that any type of contaminations in cement slurry alters the designed parameters which
further depend on the nature and proportion of contaminations. Probability of contamination is also depend on
hierarchy of the fluids in terms of specific gravity, rheology and shear rate while displacing the mud,
preflushand / or spacer ahead of cement slurry. Mud used during drilling should be removed properly to avoid
intermingling with cement slurry to get the good cement bond & to attain CS in very short span of time after
placement. Generally preflush or spacer are being used for effective removal of mud & mud cake from
formation, inner & outer surface of tubulars & its efficiency further depend on the nature of mud. Even after

use of spacer, still there is a chance of sticking of mud (depending on type and composition of mud) on the
surface of formation and tubulars.
Similar problems were faced by the Mumbai High in many wells during cement plug jobs & cement plug was
not found. Since NDDF was used, it was assumed that incompatibility of NDDF with cement slurry might have
played a key role which prevented cement from getting set & gaining strength. This problem has been observed
in secondary cementation jobs only where NDDF mud system were in use whereas no any such behaviour has
been observed in primary cementation wherever NDDF was in use.
Case Histories
In well No. SMH#A ofMumbai High, cement plug job was carried out on 4 occasions after drill down to 2525
m ( 13 3/8” Casing Shoe at 1601 m, 9 5/8” Casing Shoe at 2285.72 m, F/C of 9 5/8”Casing at 2249.68 m).
1. The first cement plug job was conducted with 16 bbl spacer of 1.56 SG, 24 bbl cement slurry of 1.90
SG followed by 5.8 bbl of spacer 1.56 SG (NDDF 1.16 SG) keeping OEDP at 2185 m (Planned plug
interval 2085 - 2185 m). When run into the hole to tag cement plug after 12 hrs. WOC, no cement plug
was found and while mud circulation contaminated NDDF mud with cement on shale shaker at 2291 m
was observed.
2. In 2nd cement plug of 30 bbl cement slurry of 1.90 SG using 56 bbl drill water as preflush 20.5 bbl drill
water as after flush keeping OEDP at 1685.While tagging after 12 hrs. WOC, cement plug was not
found and observed contaminated NDDF mud with cement on shale shaker.
3. In 3rd cement plug of 48 bbl cement slurry of 1.90 SG using 56 bbl drill water as preflush& 35 bbl drill
water as after flush keeping OEDP at 1590 m. While tagging after WOC, cement plug took load of 20
Kips at 1542 m and during bottoms up found cement contaminated mud on shale shaker.
4. The4th cement plug of 48 bbl cement slurry of 1.95 SG using 34 bbl bentonite gel ahead of slurry as
spacer, 11 bbl bentonite gel behind the slurry as after flush keeping OEDP at 1538 m. While tagging
after WOC, finally cement plug tagged at 1390 m and it took load of 30 Kips at 1000 psi.
In view of above problem faced in the well SMH#A, IDT has carried out extensive compatibility studies.
Evaluated the designed slurry and worked on optimization of WOC via simulation. Compressive strength
development of all the above first 3 jobs, where the job were failed was investigated by contaminating cement
slurry with NDDF & experiments were carried out. The final 4th plug job executed was also evaluated to see
whether lab results conform to the actual results obtained in field conditions. Comparison of contamination of
NDDF &Bentonite gel mud was done to see the delayed development behaviour in gain of CS.
Contamination during plug cementing has long been recognized as a serious problem, and sets of preventive
guidelines have been proposed (Dees and Spradlin, 1982; Heathman et al., 1994).The primary consequences of
cement contamination are a dramatic setting-time change and deterioration of mechanical properties.
Probable reasons for contamination of cement plugs may occur at different times and for different reasons.
• During placement, inside the drill pipe, at the front and rear interfaces of the cement slurryunstable base
or top, owing to density differences (heavy fluid on top of a lighter fluid)during placement with drill
pipe (downward flow at the drill pipe tip can cause mixing of the cement slurry with other wellbore
fluids).
• Contamination caused by over displacement.

• To adhere mud removal guidelines (cement may be contaminated by a mud channel or by a mud layer
ifnot being displaced properly).
• Swabbing action while pulling out.
• Reversing out the excess cement.
Experimental Work
For preparation and conditioning of cement slurryAPI RP 10 B-2, 2013 standard was used and as per API RP
10B2 simulated BHST or API table is being used to know actual BHST and in turn the final CS. But the BHCT
from API table doesn’t take into consideration for formations heat transfer rate. Cemcade software of
Schlumberger was used along with all available data to simulate BHST.
After carrying out simulation using Cemcade software, following temperature schedule & graph was obtained.
Time Temperature (°C)

30 minute 60.7
Next 01 65
hour
Next 01 69
hour
Next 01 72
hour
Next 01 75.4
hour
Next 01 77.8
hour
Next 01 80
hour
Next 01 82
hour
Next 01 84
hour
Next 01 85
hour
Next 01 86.7
hour
Next 01 88
hour
Next 01 89
hour

Testing Procedure
At first step, weight empty glass beakerwas taken then pouredNDDF (1.16SG) upto a specific mark and keptit
idle for few hours.Pour out the above NDDF into a container, and then decant as much liquid as possible from
the beaker by keeping it upside down.After an hour measured the weight of this beaker which only contains a
layer of NDDF surrounding it.Then poured the prepared formulation into the beaker gently up to the same mark
as NDDF was poured previously.Then put the entire system under coaxial cylindrical Rheometer, and give
shear rate for 5 mins at 100RPM.After it entire solution was again decantedfrom above beaker, and kept it
upside down.
The same procedure was applied on piece of 3 1/2’’ drill pipe keeping one end blind with metal plate at
ambient as well as at 85 OC temperature. The effectiveness of NDDF removal is calculated as per formula
below
% Removal of NDDF= (A - B)X100
A
A=Net weight of NDDF on beaker before treatment
B=Net weight of NDDF leftover on beaker after treatment
Composition of NDDF used
Caustic Soda XC PAC Weighting

Composition KCl SG
Soda Ash Polymer LC Agents
LSP (Lime Stone
Power)
1.16 MCC
Percentage 0.015% 0.015% 4% 0.6% 1.16
% (Micronized
Calcium
Carbonate)
Results&Discussion
Using the above simulated temperature profile; it was obtained that slurry design was over retarded, so one
must always use simulated temperature profile instead of using standard API tables. After simulation using
cemcadesoftware it was found that CS was determined at higher temperature 96 0C instead of 89 0C as
predicted by thermal simulator. An overestimated temperature of slurry results is shown below Table -1.

Table 1: Slurry Design Parameters & NDDF Contamination study.
Compressive Strength Fluid Free

Cement % NDDF % Water TT Initial
in PSI at BHST (12 Loss water
Slurry Contamination Contamination (min.) Bc
Hrs.) (ml) (%)
Observed No
100 - - 660 11 1119 13.5
Strength
100 5 - 801 10 Not set - -
Observed No
100 - 5 686 10 - -
Strength
100 - 10 803 09 Not set - -
Similarly other plug jobs were explored in details,simulation was done using the same Cemcade software,
temperature schedule was used to carry out laboratory testing of slurries that include TT & CS tests.
When analysed the 3rd plug failure results, it was found sufficient CS despite of the fact that the slurry
temperature was overestimated, this confirmed that there must be some contamination with NDDF. With only
5% contamination of NDDF no strength was found. Detailed results are summarized in theTable - 2.
Table 2: Slurry Design Parameters & Different % of NDDF Contamination.
Fluid Free
Cement % NDDF % Water TT Initial CS in PSI at BHST
Loss water
Slurry Contamination Contamination (min.) Bc (12 Hrs.)
(ml) (%)
100 - - 386 8 1265 1458 13.3
Observed No
100 5 - - - - -
Strength
Observed No
100 10 - 598 7 - -
Strength
100 20 - - - Not set - -
100 - 10 - - 801 - -
It was observed no compressive strength in cement when the same neat cement slurry design were
contaminated with 5% NDD for even higher, this confirms that minute contaminations of NDDF is detrimental
to cement.
But in the final plug job where satisfactory results were obtained, the mud was bentonite gel instead of NDDF.
The results are summarized below. It was clear where there was 20% bentonite gel contamination with cement
slurry it was showing adequate compressive strength. Detailed results are summarized in the Table - 3.

Table-3: Slurry Design Parameters with Bentonite Contamination study.
Bentonite Gel % Reduction

Cement NDDF % TT CS at BHST
% in CS w.r.t Free Fluid
Slurry Contamination (min.) (12 Hrs.)
Contamination Neat
100 - - 386 1680 - Nil
100 10 - - 1475 12.20 -
100 20 - - 1137 32.32 -
It was becoming somewhat clear that NDDF could be one of the reasons for delayed setting or green cement.
After analysing the results in details, an innovative formulation was explored so that NDDF doesn’t leave on
the walls of tubulars and causes any change in cement slurry design parameters. A series of 9 different
chemical formulations were explored to find out their removal efficiencies.(Data presented in Fig -1 &2).
Fig 1: Before Treatment with chemical formulation
Fig 2:After Treatment with chemical formulation
Improved results were obtained using chemical formulation 4 and5 as shown in beaker by numbers in (Fig -2).
The best formulation was shortlisted and tried out on surface & BHCT. The results obtained at BHCT were
better as compared to that of surface temperature.
Table 4: Different % of Formulations to remove NDDF layer at BHCT 85 OC
Leftover net wt. of % Removal of

Net wt. of NDDF
Sl. NDDF layer on NDDF layer from
Formulation layer on beaker wall
No. beaker after treatment beaker = (A-B) / A
(gm) (A)
(gm) (B) * 100
1 1% 6.6 1.1 83.3

Solution
2%
2 6.6 0.2 97.0
Solution
3%
3 6.4 0 100
Solution
4%
4 6.6 0 100
Solution
Fig -3: Before Treatment
Fig 4: After treatment (Dosage from 1%-4% as mentioned in table -4 )
The 2% solution gave best results to remove the NDDF in comparison to the other solvents and
formulations(Presented in Table -4). The results were very encouraging & could be a solution to secondary
cementation jobs wherever NDDF is used. After carrying out the tests in beaker, the tests were carried out in
drill pipes to simulate the actual environment where job was carried out. So drill pipes were fabricated and
similar experiment as in case of beaker was carried out (Results presented in Fig – 5&6).

Fig -5: Before Treatment@85OC
Fig 6: After Treatment @85OC
Table 5:Removal efficiency of NDDF layer on drill pipe @85OC.

Leftover net wt. of % Removal of
Net wt. of NDDF
Sl. Formulation NDDF layer on beaker NDDF layer from
layer on beaker
No. Conc. (%) after treatment (gm) beaker = (A-B) / A
wall (gm) (A)
(B) * 100
1 2 4.6 0.1 97.4
2 2 3.8 0.2 96.5
3 2 4.2 0.2 95.2
4 2 4.0 0.3 92.5
As results shown in (Table- 5),it was found that with 2% formulation removal efficiency is highest
i.e97.4%.This innovative solution should be pumped prior to spacer to remove NDDF completely from surface
of tubulars.
CONCLUSION AND RECOMMENDATIONS

Based on the study carried out, following conclusions can be drawn,
• Experiments shows that NDDF might not be removed effectively by using water as preflush, spacers
and bentonite gel mud ahead of cement slurry,
• In most common practice the CSis determined at BHST after it is raised from ambient temperature
directly to BHST in 3 or 4 hrs as per API schedule. But in actual field conditions temperature increases
gradually step wise as found by simulation. This stepwise temperature rise is dependent on discharge
rate, formation heat transfer rate & capacity.
• Chemical incompatibility between the drilling fluids (NDDF) with cement slurry is the main reason for
contamination.

• The study shows that any type of contamination (mud, spacer or formation fluid) with cement slurry
definitely leads in delayed CS development.
• Optimization / reduction of WOC of the designed slurry may determine by using of Ultrasonic Cement
Analyzer (UCA).
• While designing cement slurry for plug jobs special precautions needs to be taken likeTT needs to be
adequate for placement&CS should develop rapidly.
• Slurry sedimentation or free water should be avoided.
• Adherence to standard recommended cementing practices is suggested.
• It is alsorecommended to use mechanical separators between the cement &mud so as to reduce the
contamination in the drill pipe.
• Lesser diameter tubulars to be used as a tail pipe for future jobs to reduce the swabbing effect while
pulling out. 5” D/P used for the job (9 5/8’’ Casing ID=8.681” and tool joint OD of 6 5/8”) may cause
the swabbing effect of the cement slurry while pulling out.
ACKNOWLEDGEMENTS
The authors are highly thankful to management of Oil and Natural Gas Corporation, Ltd for permission to
publish this paper.Authors are also thankful to HOI-IDT, for his encouragement. Special thanks are due to
many colleagues for their advice and assistance provided during the study in the laboratory.
REFERENCES
1. Joel OF, Ndubuisi EC, Ikeh L. Effect of cement contamination on some properties of drilling mud. In:
Nigeria Annual International Conference and Exhibition, 6e8 August 2012, Lagos, Nigeria.
DOI: http://dx.doi. org/10.2118/163023-MS.
2. Fakhreldin YE, Sharji H, Aghbari SA, Al-rashdi S. Novel technique to determine cement
contamination. In: SPE/IADC Middle East Drilling Technology Conference and Exhibition, 24e26
October 2011, Muscat, Oman. DOI: http://dx.doi.org/10.2118/148527-MS.
3. Agbasimalo N and Radonjic M (2014) Experimental study of the impact of drilling fluid contamination
on the integrity of cementformation interface. Journal of Energy Resources Technology 136(4):
(042908)1–5.
4. Shadravan A., et al, "Engineering the Mud-Spacer-Cement Rheological Hierarchy Improves Well bore
Integrity", SPE-173534-MS, Presented at SPE E&P Health, Safety, Security and Environmental
Conference, Denver, Colorado, USA, 16-18 March 2015.
5. Chen Z., Chaudhary S. and Shine J., "Intermixi ng of Cementing Fluids: Understanding Mud
Displacement and Cement Placement". SPE 167922, Presented at 2014 IADC/SPE Drilling Conference
& Exhibition, Fort Worth , Texas, USA, 4-6 March 2014.
6. API (American Petroleum Institute) (2013) Recommended Practice for Testing Well Cements, 2nd edn.
API, Washington, DC, USA.
7. Erik B. Nelson and Dominique Guillot.: Well Cementing, second edition, Schlumberger, Texas (2006).

Title: “Application of Solvents for use in different way

-Tilak Singh, Dileep Kumar, JM Karnik and R M Patil, Oil and Natural gas Corporation
Keywords: Solvent, Wax, Asphaltene & SARA
Abstract
Solvents are very important for dissolve paraffin, asphaltene, wax etc. to enhance production and clear the way
to flow the crude. Mumbai off-shore is biggest field of producing Hydrocarbon like MH, NH, B&S Asset and
WOB have multilayered of Reservoir and heterogeneous with varying petro physical properties. It has main
three pay zones A, B and alterations. Problem creates in pipelines and formations due to asphaltene, wax and
Carbonates. These problems cannot dissolve with direct chemicals. Solvents have a useful for clear the
pipelines of wax, asphaltene and solids contents etc. Solvents may be used different types with different doses
for remove or dissolve of wax, asphaltene and solid contents.
The wax, asphaltene and solid contents precipitation and remedial measures to combat the problem by using
solvents. Colloidal Instability Index (CII) calculated on the basis of SARA analysis, indicate maximum
asphaltene problem in offshore and onshore field. SIMDIS analysis shows that carbon atom distribution is
maximum at C11 and C12 which further supports the problem of wax deposition near the well bore appearance
negligible.
Asphaltene solubility studies on the crude oil samples with various combination of chemicals (solvents) with or
without dispersant, diesel,Xyleneor Toluene have carried out practically in field. Substantial improvement in
asphaltene solubility is observed in case of solvent with suitable dose of Chemicals.Solvents may vary with
different doses and different composition of chemicals. Socking time depends upon composition of solvents.
Solvent formulation with combination of aromatic solvent, mutual solvent and surfactant to be right solution
for removal of wax, asphaltene and solids.
Solvent will be combination for xylene, toluene, surfactants, dispersant and naphthalene powder with different
percentage. Solvents will beused for dissolving asphaltene in offshore MH, NH and B&S Asset.
Introduction:
MH, NH and B&S Assets are anoffshore oil filed which has been producing more than 40 years. The current
offshore oil field water cut is around more than 60% and total oil production is around 270000 BPD. The key
challenges in all Asset in Mumbai offshore are high water cut and flow assurance, wax deposition,
Asphaltene& fine sand etc. To overcome these challenges numerous well interventions and work over activities
such as gas lift valve change out for gas lift omission, water shut off, additional perforations for new zone and
well stimulations jobs are planned to maximize oil production.
Solvent jobs were carried out by Mumbai Assets yielded good results in some of wells. However, sustainability
of the gain was limited. The details studies on the asphaltene precipitation and remedial measure to combat the
problem by modifying the formulation.
Crude oil is consider to be in colloidal comprising fractions of Saturates, Aromatic, Resin, and
Asphaltene.Asphaltene fractions are defined as dispersed colloids in the oil phase and are stabilized, to some
extent, by the Resin molecules that acts as protective bodies for Asphaltene particles. Colloidal Asphaltene can
be naturally or artificially precipitated if the Resin protective shield is removed from Asphaltene particles
surfaces. Asphaltene deposition can occur in different parts of the production system, including in the well
tubing, surface flow lines, and even near well bore, reservoir. Asphaltene precipitation and deposition in oil

production system depend on the changes in flow condition, such as pressure, temp and oil composition. The
factor that plays a major role in Asphaltene problems under flow condition in well flow pressure behavior.
Colloidal Instability Index (CII) calculated on the basis of SARA analysis, indicated maximum Asphaltene
problem in South Heera and Main Heera in NH Asset&MH Asset. SIMDIS analysis shows that carbon atom
distribution is maximumat C11 and C12 which further supports the possibility of asphaltene precipitation.
Over View of Asphaltene:

Asphaltene fraction of petroleum crude is defined as the fraction insoluble in low boiling point Paraffin
Hydrocarbons, but soluble in carbon tetrachloride and benzene. Asphaltene is defined as the fraction insoluble
in n-heptane but soluble in toluene.
On heating above 300-400 deg.0C, Asphaltene are not melted but decompose forming carbon and volatile
products. Asphaltene are not crystalized and cannot be separated into components or narrow fractions.
Asphaltene are lyophilic with respect to aromatics in which they form highly scattered colloidal solutions.
Asphaltenes of low molecular weight are lyophobic with respect to Paraffins like pentanes and petroleum
crudes.
One of representative structure for Resin and Asphaltene molecules includes Carbon, Hydrogen, Oxygen,
Nitrogen, Sulphur as well as polar and non-polar groups as it is shown by figure no.1.
Figure: 1

Figure:2
Asphaltene particles can assume various forms when mixed with other molecules depending on the relative
sizes and polarities of the particles present. It has been shown that asphaltene molecules span a wide range of
molecular weights.
Data Interpretation:
Calculate of percentage of Asphaltene = 100-100x (Final wt. - Filter paper wt.)
Initial wt. of sample
Colloidal instability Index (CII):

It is measure of asphaltene precipitation in depleted reservoirs operation near the bubble point pressure.CII
values over 1 indicate possibility of Asphaltene precipitation whenever there is change in flow parameters
pressure, temp and crudecomposition.
1. Appreciable Asphaltene in crude oil

2. CII>1 in areaSIMDIS analysis shows, carbon atom distribution is maximum C11 and C12. Lighter
crude are prone to Asphaltene precipitation than heavier one.
3. Aromatic solvents do solubilize the Asphaltene to some extent.
4. To sustain them in colloidal form an Asphaltene dispersant is essential.
Asphaltene problem is existing in all Assets. Solubility of Asphaltene is limited at almost 55-58% in solvent
without dispersant.Dispersant is required in the formulation to keep Asphaltene in suspension.

Table:1SARA analysis of wells
Sl.No. Well Saturates Aromatic Resins Asphaltene Wax

no.
1 w 82.81 9.58 7.01 0.60 6.67
2 x 70.09 24.24 5.42 0.25 3.6
3 y 67.24 26.70 5.76 0.3 --
4 z 64.36 9.07 9.07 0.61 --
CII Calculation:
CII values can be calculate from the formula
CII = Saturates + Asphaltene / Aromatics +Resins
CII > 1 indicates Precipitation
Table:2 Calculation of CII
Sl. No. CII Remarks

1 5.03 Precipitation
From the above table it is observed that the CII values are very high so that precipitation is possible.
Refractive Index (RI):1.4 saturates+1.5Aromatics+1,6Resin+1.7 Asphaltene greater than or equal 1.48

indicates favorable of Asphaltene precipitation.
Ratio of Resin / Asphaltene, Less than 10 indicates high probability.
Simulation Analysis:
Simulated distillation (SIMDIS) Analysis provide insight to the carbon atom distribution of the crude oil. It
indicates to identify the nature of crude. SIMDIS analysis is carried out using programmed capillary / wide
bore capillary gas Chromatograph. Carbon atom distribution as a function of boiling point is determined and
quantified.

Table: 3
Carbon Wt.% Carbon Wt.%

no. (w/w) no. (w/w)
C6 3.53 C25 0.68
C7 0.63 C26 0.91
C8 3.88 C27 0.85
C9 2.21 C28 0.64
C10 8.16 C29 0.68
C11 17.24 C30 0.66
C12 27.00 C31 0.48
C13 5.86 C32 0.44
C14 7.27 C33 0.01
C15 7.45 C34 0.10
C16 3.60 C35 0.07
C17 0.07 C36 0.06
C18 0.96 C37 0.04
C19 2.33 C38 0.02
C20 1.15 C39 0.02
C21 1.02 C40 0.01
C22 0.87 C41 0.01
C23 0.04 Sum 99.91
C24 0.96
From the above table the C11 and C12 carbon numbered hydrocarbon constitute major portion of the crude.
The problem of asphaltene precipitation is generally expected to occur in the crude with lower content of
molecular weight hydrocarbons.
Problem Identification:
The problem of heavy organics precipitation can be eliminated by modification of the production practices
rather than by chemical or mechanical means cost of production can be reduced appreciably. The main reason
to deposition of asphaltene
1. Reduction of sheer rate.

2. Elimination of incompatible materials from asphaltene crude oil streams.
3. Minimization of pressure drop in production facility.
4. Minimization of mixing of lean feed stock liquid into asphaltic crude steams.

Experimental Procedure:
Table: 1
Based on the performance of the dispersant dose is optimized by varying the concentration
from 1.5 % to 4 % (wt./V).
Sl Formulation Solubility
no.
1 Xylene+ Toluene +Naphthalene+ 2% 58%
Residue -------Blank
2 Xylene+ Toluene +Naphthalene+ 2% Residue+1.5% Alkyl phenol 89%
polyethanoxy ether
3 Xylene+ Toluene +Naphthalene+ 2% Residue+ 2% 90%
Alkyl phenol polyethanoxy ether
There is no significant change in the solubility of Asphaltene with increase in dispersant

concentration from 1.5% to 4%.Dispersant dose of 1.5% is sufficient to achieve over 90%
Solubility.
Table: 2
Sl. Formulation Solubility

No.
1 Xylene+10-30%ethyle Benzene 97
2 Terpeneand Terpenoids, Terpentine oil limonene 96
3 Heavy aromatic petroleum Neptha +10-30% 1,2,4 tri methyle 97
benzene
Any above formulation can be used for 100% solubility. But formulation no 1 of flash point
is 27 not suitable for safety point of view.
Various formulation of solvent are

1. 1.5% of Alkyl phenol polyethanoxy ether is recommended as dispersant to achieve over 90% solubility
of Asphaltene.
2. 40 – 45% diesel + 30 – 33 % Xylene + 20 – 25% toluene + 10 - 11%
a. (wt./v) naphthalene + 1.5 % Dispersant
3. 70% Condensate+24%Xylene+5% EGMBE+1% Surfactant for dissolve 82-83%
4. 30%Xylene +20%Toluene +10% EGMBE+1% Surfactant+2% Naphthalene.
5. 30% Xylene + 20% Toluene + 10% EGMBE + 1% Surfactant + 39% diesel

Flash Point of Xylene: 320C

Flash Point of Toluene:70C
Results & Discussions:

1. Asphaltene problem exists in all the areas of NH, MH and B&S field as per SARA analysis.
2. NH crude is rich in lighter hydrocarbons as is evident from SIMDIS analysis. C11, C12 is major
constituent. Such crudes are prone to asphaltene precipitation.
3. Solubility of asphaltene is limited at almost 58% in solvent without dispersant.
4. Alkyl phenol polyethanoxy ether is most suitable option as dispersant to achieve over 90% solubility.
5. Choose any one formulation from Table no. 2 except formulation no.1because formulation no. is Flash
point is less.
Conclusions:
1. Solvent wash is required for removing the damage induced by Asphaltene precipitation.
2. Solvent formulation is effective with limited sustainability.
3. Dispersant is required to keep Asphaltene in dispersed form.
4. Naphthalene is cryozanic which cannot be used.
5. On mixing with diesel flash point of Xylene and toluene increases.
Acknowledgments:
The authors would like to thanks to Head well service, Location Manager,operation manager of WSS and
support for permission to publish this paper.
References:
1. IPTC-16418, Success application of novel organic-Solvent-Acid –Stimulation Approach for unlocking
productions and optimizing field watercut in the Tamana offshore brown field.
2. Identification of suitable solvent and its implementation in NH&MH Asset.
3. Development and field use of a novel solvent/water emulsion for removal of Asphaltene deposited in
fractured carbonate formation.
4. Implementation of solvent xylene based stimulation jobs in Mumbai offshore.

Title: “Inhibition effect of salts CaCO 3 and MgCO 3 on the kinetics of Methane Hydrates”
-Ekta Chaturvedi, Ajay Mandal, Petroleum Engineering Department, IIT (ISM), Dhanbad
Key Words: Calcium carbonate; kinetics; Magnesium carbonate; artificial seawater.
Abstract
The huge amount of methane hydrate deposits identified in deep marine sediments is considered as the new
resource for future energy. Since carbonates are one of the major components of marine sediments, in the
present study, an investigation has been made to study methane hydrate stability and kinetics in the presence of
CaCO 3 and MgCO 3 . Experiments were performed with 0%, 2%, 4%, 6% and 10% by weight of CaCO 3 and
MgCO 3 in distilled water. It has been observed that in presence of inhibiters, the rate of hydrate formation is
decreased as the solubility of CaCO 3 and MgCO 3 saltsin water is controlled by the presence of simultaneous
chemical equilibriainvolving a high number of species like Ca2+,Mg2+,CO 3 2−. Comparative studies between
CaCO 3 and MgCO 3 have also been done in the presence of artificial seawater at optimized concentration of 6%
by weight to consider the effect of presence of different salts. Mole consumption of methane gas during hydrate
formation in different carbonate samples was measured using real gas equation and found to be minimum in
CaCO 3 inseawater sample due to the combined effect of the presence of CaCO 3 and different salts of seawater.
Also, equilibrium curve is shifted towards the higher pressure and low temperature regions, indicating the
inhibition effect on hydrate formation. Further, an increase in induction time and decrease in hydrate formation
rate confirmed the inhibition effect of carbonates. Inhibition effect of CaCO 3 was observed to be more
prominent than MgCO 3 . Induction time was lowest in the presence of CaCO 3 in artificial sea water.
1. Introduction
Gas hydrates are ice like crystalline solids, first discovered by Sir Humphrey Davy in 1810. Gas hydrates are
formed by the encapsulation of gases like methane, ethane, butane, carbon dioxide, hydrogen etc. into water
cages through hydrogen bonding at low temperature and high-pressure conditions. They look similar to the ice
in appearance but their properties and structures are completely different from ice and can exist at temperatures
far above the ice point [1]. Gas hydrates are found undersea in the polar region or in deep marine sediments of
continental margin with depth ranging from the 150-2000 m from seabed [2,3] .
Gas hydrates occur in different structures i.e. sI, sII and sH based on the size of guest gases and occupying
cages [4]. Gas hydrates were seen as a major threat to the gas industry during the initial period because of their
formation in pipelines leading to the clogging, blowout and other environmental risks. Gas hydrate is formed in
the metastable region, where the hydrate formation and dissociation depend on many factors like the saturation
of the gas, availability of water or salinity of the water and composition of the natural gas [5]. Presence of
different salts in water affects the hydrate formation by decreasing the stability of gas hydrates and lowering the
dissociation temperature by a constant amount compared to a pure water system. Dissolved salts in sea water
also reduce the activity of watertherefore, it is vital to understand the behaviour of gas hydrate formation and
dissociation in the presence of different salts for better understanding of the hydrates [6].
Several authors investigated the formation and dissociation behaviour of gas hydrates in presence of the various
salts. It was observed that salts behaved as inhibitors for hydrate formation resulting in the shift of phase curve
to a higher pressure and lower temperature [7, 8]. Chong et al. investigated methane hydrate formation and
dissociation kinetics in the presence of NaCl. [9] Presence of NaCl kinetically inhibited hydrate formation by
retarding the hydrate growth. A reduction in hydrate formation conditions was reported by Bishnoi and

Dholabhai [10] in presence of NaCl, KCl and CaCl 2 as compared to water. Salts like KNO 3 , MgSO 4 and
CuSO 4 inhibit the hydrate formation process and increase the inhibiting strength with an increase in salt
concentration [8]. Formation and dissociation behaviour of methane hydrate in the presence of MgCl 2 and KCl
was investigated by Chong et al. [11]. Very few literatures are available on hydrate stability and kinetic studies
in presence of carbonates.
In the present work, an emphasis has been given to the stability and kinetic studies of methane hydrate in the
aqueous solution of CaCO 3 and MgCO 3 . Comparative studies have also been done in presence of artificial sea
water. The work is focused on how formation conditions change in the presence of carbonates and different
salts. Gas consumption and hydrate formation rate have also been calculated to examine the effect of the
carbonates.
2. Experimental Section
2.1 Materials
All experiments were performed with the methane gas having 99.99% purity, purchased from Chemtron
Science Laboratory, Navi Mumbai (India). Calcium carbonate and magnesium carbonate were purchased from
Finar Chemicals (India) Private Limited, Ahmedabad, India and Otto Kemi Mumbai, India respectively.
Experiments were also performed in the presence of artificial seawater, which was prepared on the basis of the
composition of Indian standard IS 8770. Samples of different compositions of CaCO 3 and MgCO 3 were
prepared using distilled and artificial sea water for experiments.The composition of the samples used during the
experiments is shown in Table 1 and are identified as S1, S2, S3, S4, and S5.
Table 2: Composition of prepared Samples in water
Sample CaCO 3 Composition MgCO 3 Composition

Water
No. (wt. %) (wt. %)
S1 Distilled Water 0 0
S3 Artificial Sea Water 6 0
S5 Artificial Sea Water 0 6
2.2 Apparatus
High-pressure autoclave cell with a capacity of 250cc was used to study the kinetics of the hydrate formation.
The autoclave was designed by Vinci Technology, France as shown in Figure 1, which is having a pressure
limit of 3000 psi. A thermocouple is used to measure the temperature in the range of -10ºC to 60ºC with an
accuracy of 0.1ºC.

Figure 5: Auto Clave High-Pressure Hydrate Cell Schematics Diagram
2.3 Procedure
Initially, prepared samples were taken into the autoclave cell and then the cell was immersed into the coolant
bath. Then the methane gas was injected into the cell with an initial pressure and temperature conditions of
2000 psi and 20° C respectively. The Cell was then cooled stepwise to reach the hydrate formation conditions.
Hydrate formation point was detected by a sudden drop in pressure. After the formation, the cell was heated at
a constant rate for dissociation until the heating curve meets the cooling curve.Initial temperature and pressure
conditions were kept constant for all experiments.
3. Results& Discussions
3.1 Methane Hydrate Formation and Dissociation
In the present paper, studies have been done on the methane hydrate formation and dissociation in presence of
the calcium carbonate with varying concentrations of 2%, 4%, 6%, and 10% by weight. Methane hydrates
formation can be illustrated by the following Equation (1);
𝐂𝐂𝐂𝐂𝟒𝟒 (𝐠𝐠) + 𝐧𝐧𝐇𝐇𝟐𝟐 𝐎𝐎 (𝐥𝐥) → 𝐂𝐂𝐂𝐂𝟒𝟒 . 𝐧𝐧. 𝐇𝐇𝟐𝟐 𝐎𝐎 (𝐬𝐬)(𝟏𝟏)
The initial conditions of temperature and pressure were set at 293.15 K temperature and 13.789 MPa pressure
for all experiments. Temperature and pressure diagram for 2 wt. % calcium carbonate sample is shown in
Figure 2 (b).A pictorial view of formed hydrate is shown in Figure 2(a).Similar types of plots were obtained for
the composition of 4%, 6% and 10% by weight.An experiment with 6 wt.% calcium carbonate was also
performed in the presence of artificial sea water to observe the effect of salts present in sea water on hydrate
formation and dissociation.The presence of salts shows ion repulsive effect with water ions resulting in lower
water activity and thus decelerating the hydrate formation rate at high salt concentrations.

(a) (b)
Figure 2: (a): Pictorial view of formed hydrate; (b): hydrate formation & dissociation curve of 2 wt.% calcium
carbonate in distilled water
3.2 Nucleation and Induction Time study

Kinetics of hydrate formation started at the thermodynamic equilibrium point where hydrate dissociation was
completed. Since a certain time is required to start the nucleation of hydrates after hydrate forming components
are placed in hydrate cell at initial operating conditions. The difference between the initial
temperature and the thermodynamic equilibrium point (nucleation point at which hydrate formation initiated)
was termed as induction time required to form the first hydrate crystal [12, 13] as shown below by Equation
(2);
𝐭𝐭 𝐢𝐢 = 𝐭𝐭 𝐧𝐧 − 𝐭𝐭 𝐬𝐬 (𝟐𝟐)
Where, t i is induction time, t n is nucleation time and t s is initial time. Nucleation temperature and pressure for
all samples were found to be low as compared to the pure water system. Also, the addition of CaCO 3 and
MgCO 3 increased the time required for the nucleation of hydrates as compared to water. Addition of salts
altered the activity of water and disturbed the lattice structure of gas hydrates and thus increased the barrier of
hydrate nucleation [9]. Induction time for CaCO 3 was found to be higher as compared to MgCO 3 in both pure
water and artificial sea water resulting in higher inhibition as the activity of CaCO 3 towards water is higher as
compared to MgCO 3.

Figure 3: Induction time of different samples of CaCO 3 and MgCO 3
3.3 Gas Consumption during hydrate formation

During hydrate formation, gas uptake was calculated using the real gas equation given by [14]:
Pi V Pf V
Methane Moles Consumption (∆n) = � �− � � (3)
Zi R Ti Zf RTf
Where ∆n is the number of moles of methane consumed during hydrate formation, v is the constant volume of
gas, R is the gas constant, Pi and Pf are the initial pressure and final pressure and Ti &Tf are initial and final
temperature andZ is the compressibility factor. Comparative plots of gas consumption in presence of CaCO 3
and MgCO 3 in distilled water and artificial seawater are shown in Figure 4. . Maximum gas consumption
occurs in pure water system as observed from Figure 4. Addition of CaCO 3 and MgCO 3 resulted in less
consumption of methane gas as compared to the pure distilled water sample.
The percentage of the methane molecules combined with water molecules during hydrate formation is shown in
Figure 5 as calculated by the following equation 4 [15]:
moles of methane gas consumed

Methane to hydrate conversion (%) = � � × 100 (4)
moles of methane gas feed in cell

0.12
Pure Water
6% CaCO3 in DW
6% CaCO3 in ASW
0.10
6% MgCO3 in DW
6% MgCO3 in ASW
Gas consumption (moles)
0.08
0.06
0.04
0.02
0.00
0 100 200 300 400 500 600
Time (min)
Figure 4: Comparative Plot of Gas consumption for all samples
Figure 5: Methane to hydrate conversion for all samples

4. Conclusions
Kinetics studies of methane hydrate were performed in the aqueous solutions of CaCO 3 and MgCO 3 and in
artificial sea water with different salts composition. Both CaCO 3 and MgCO 3 significantly inhibited the
formation of hydrates. Low solubility and pressure drop were observed in the presence of the salts. Gas
consumption was found to be less in the presence of CaCO 3 and MgCO 3 as compared to the pure water system.
Induction time increased in the presence of CaCO 3 and MgCO 3 indicating the delay in hydrate formation as
compared to the pure water system.
References
[1] A. Demirbas, Green Energy And Technology: Methane Gas Hydrate, 2010.
[2] G. Bohrmann, J. Greinert, E. Suess, M. Torres, Authigenic carbonates from the Cascadia subduction zone
and their relation to gas hydrate stability, Geology. 26 (1998) 647–650.
[3] Kvenvolden, K. A., Lorenson, T. D., 2001. The global occurrence of natural gas hydrate. Natural gas
hydrates: occurrence, distribution, and detection, 3-18.
[4] Sloan ED, Koh CA. Clatherate Hydrate of Natural Gases. third. CRC Press, Taylor & Francis Group; 2008.
[5] Makogon, Y. F., 2010. Natural gas hydrates–A promising source of energy. J. Nat. Gas Sci. Eng., 2(1), 49-
59.
[6] Dickens, G. R., Quinby‐Hunt, M. S., 1994. Methane hydrates stability in seawater. Geophys. Res. Lett.,
21(19), 2115-2118.
[7] Clarke, M. A., Bishnoi, P. R., 2004. Development of a new equation of state for mixed salt and mixed
solvent systems, and application to vapour–liquid and solid (hydrate)–vapour–liquid equilibrium calculations.
Fluid Phase Equilib., 220(1), 21-35.
[8] Porz, L. O., Clarke, M. A., Oellrich, L. R., 2009. Experimental investigation of methane hydrates
equilibrium condition in the presence of KNO 3 , MgSO 4 , and CuSO 4 . J. Chem. Eng. Data, 55(1), 262-266.
[9] Chong, Z. R., Chan, A. H. M., Babu, P., Yang, M., Linga, P., 2015. Effect of NaCl on methane hydrate
formation and dissociation in porous media. J. Nat. Gas Sci. Eng., 27, 178-189.
[10] Bishnoi, P. R., Dholabhai, P. D., 1993. Experimental study on propane hydrate equilibrium conditions in
aqueous electrolyte solutions. Fluid Phase Equilib. 83, 455-462.
[11] Chong, Z. R., Koh, J. W., Linga, P., 2017. Effect of KCl and MgCl 2 on the kinetics of methane hydrate
formation and dissociation in sandy sediments. Energy.
[12] S. Tantciura, Hydrate nucleation kinetics and statistical analysis of experimental data. MS thesis.
University of Stavanger, Norway, (2014).
[13]V. K. Saw, Gudala, M., Udayabhanu, G., Mandal, A., & Laik, S. Kinetics of methane hydrate formation
and its dissociation in presence of non-ionic surfactant Tergitol. Journal of Unconventional Oil and Gas
Resources, 6 (2014) 54-59.
[14] Abay, H. K., Svartaas, T. M., 2011. On the kinetics of methane hydrate formation: A time-dependent
kinetic rate model. In Proceedings of the 7th International Conference on Gas Hydrates, Edinburgh, Scotland,
United Kingdom.
[15] Kono, H. O., Narasimhan, S., Song, F., Smith, D. H., 2002. Synthesis of methane gas hydrates in porous
sediments and its dissociation by depressurizing. Powder Technol., 122(2), 239-246.

Title: “Delaying the Onset of Asphaltene Flocculation Using Asphaltene Inhibitors”

-Min Wang, Helen Sarginson, Bethan Warren, Craig Davies, Croda
Keywords: asphaltene, inhibitor, precipitation, dispersant, flocculation titrimeter
Abstract
Asphaltenes are the heaviest and most polar fraction of crude oil and are known to be one of the largest causes
of production problems due to their tendency to precipitate and form deposits. Chemical additives used to treat
asphaltene problems can be either asphaltene inhibitors or asphaltene dispersants. Asphaltene inhibitors are
typically polymeric surfactants injected downhole before the crude oil has been produced and their purpose is
to change the onset point at which the asphaltenes start to flocculate. In contrast, asphaltene dispersants are
normally nonpolymeric surfactants which are deployed after the crude oil has been produced and treat the
already flocculated asphaltenes by suspending them in the fluid.
Using a Flocculation Titrimeter FT5 (PSL Systemtechnik), a method has been developed and validated to study
the effects of asphaltene inhibitors. Using this instrument, a sample of crude oil is titrated with an n-alkane or a
light crude oil until asphaltenes begin to precipitate. An effective asphaltene inhibitor will delay the onset of
asphaltene precipitation. A slow titration rate is required to ensure equilibration of the system and for a realistic
onset point to be obtained.
Asphaltene inhibition has been studied with a range of asphaltene inhibitors in crude oils produced in Latin
America, the Middle East and the North Sea. It has been found that asphaltene inhibitor performance is crude
oil and dosage specific. Polyolefin esters can be used as asphaltene inhibitors at 1000 ppm. In contrast,
dodecylbenzenesulfonic acid (DDBSA) promoted asphaltene deposition rather than providing inhibition for
certain crude.
This methodology will assist the scientific understanding of asphaltene flocculation, enabling chemical
suppliers to design efficient asphaltene inhibitors.
Introduction
Asphaltenes are molecular substances that are found in crude oil along with resins, aromatic hydrocarbons, and
saturates. Asphaltenes consist primarily of carbon, hydrogen, nitrogen, oxygen and sulphur as well as trace
amounts of vanadium and nickel. Asphaltenes are defined operationally as the n-heptane insoluble and toluene
soluble component of a carbonaceous material such as crude oil, bitumen or coal [1].Asphaltenes impart high
viscosity to crude oils negatively impacting production and asphaltenes are known to be one of the largest
causes of fouling [1]. Asphaltenes are present within micelles in crude oil and once this protective micelle has
been removed, polar asphaltenes agglomerate and are transported to metal surfaces where they can stick and
form a foulant layer.
Asphaltene inhibitors are polymeric additives that delay the onset of asphaltene destabilisation including
alkylphenol formaldehyde resin, polyolefin esters and amides, styrene acrylate copolymers etc [2]. The
flocculation could be modified and slowed down by the π–π, hydrogen bonds and acid-base interactions
between asphaltenes and asphaltene inhibitors [3] [4]. The aims of this study are to develop and validate a test

method using a FT5 Asphaltene Flocculation Titrimeter [5] and study how different asphaltene inhibitors affect
the onset flocculation of asphaltenes in different crude oils.
Experimental Procedure
An FT5 Asphaltene Flocculation Titrimeter (PSL Systemtechnik) was used. The principle of the equipment is
equivalent to ASTM D6703 (Automated HeithausTitrimetry) and involves the measurement of translucency of
crude oil via a light source. Pictorially, the measurement principle is described in Figure 1.
Figure 1. Measurement principle of the FT5 Asphaltene Flocculation Titrimeter

(courtesy of PSL Systemtechnik, Germany).
At the start of the test, the translucency of the crude oil is measured and normalised to 100% transmission.
During the test, a sample of asphaltenic crude oil is titrated with a flocculant (e.g. heptane) until the asphaltenes
begin to flocculate. Until the point of flocculation, the crude oil sample is simply diluted which can be
observed by a linear increase in the relative transmittance. Asphaltene flocculation starts slowly, and as soon as
this happens, transmittance is decreased. The asphaltene flocculation onset point is the point where the increase
in transmittance starts to slow down (e.g. the initial gradient of the curve decreases slightly). However, this is
sometimes difficult to see, so a nominal asphaltene flocculation onset point can be identified at the maximum
of the transmittance curve as shown in Figure 2. Comparison of the nominal asphaltene flocculation onset
points can be used to determine relative asphaltene inhibition.

Figure 2. Example titration plot from the FT5 flocculation titrimeter showing the nominalonset of
destabilisation of asphaltenes in crude oil.
A decrease in transmittance follows the maximum, which indicates that asphaltenes are now readily
destabilising and flocculating in the fluid. All asphaltenes have been flocculated once the curve finally plateaus.
Further titration after this point only leads to further dilution of the sample, not to more flocculation. This can
be seen in some cases by a fresh increase in transmittance at the end of the plot.
The amount of flocculation solvent required for determining the onset point of flocculation depends on the type
of crude oil and the amount of resin within the crude.
The instrument can detect particle sizes of 1-2 nm. Based on this information, it is assumed that the FT5
method will detect destabilised asphaltenes at the nanoaggregate level, before they agglomerate into deposits,
therefore truly measuring inhibition rather than dispersion.
In this study, a sample of crude oil containing asphaltenes was mixed with toluene (10:20 mL) and where
appropriate asphaltene control additives were added from a 1% (w/v) stock solution in toluene. This was
titrated with n-heptane at 0.5 mL / min until the asphaltenes begin to flocculate/precipitate.
Other experimental parameters were:

• Temperature = 30°C
• Stirrer speed = 300 rpm
• Light intensity = 10%
• Mirror cap gap length = 1 mm
• Titration rate = 0.5 mL/min
Crude oils produced in Middle East, LATAM and North Sea were tested. They contained different amount of
asphaltenes.Threeester basedasphaltene control agents(Ester 1, Ester 2 and Ester 3)were evaluated and
compared withDodecylbenzenesulfonic Acid (DDBSA) to check how they may prevent the asphaltenes from
flocculation in the three crudes.Ester 1 and Ester 2 were non-ionic polyolefin esters with different polarity and
different molecular weight (>2500 Dalton). Ester 3 was non-ionic 100% biobased fatty ester.

Results & Discussions
Method development work was carried out on the Middle East crude due to its large volume. Toluene was
chosen as the diluent since asphaltenes are soluble in it and its addition should not change the stabilization
properties.The diluted crude oil produced a lower transmittance change over the course of the titration due to
less crude oil being present, therefore there are less asphaltenes in the test solution to destabilise and detect.
The diluted crude oil also produced a later asphaltene onset point, meaning that it is taking longer for the
heptane to destabilise the asphaltenes. This could be due to the toluene having an improved solvency effect on
the asphaltenes.A dilution rate of 10 mL crude oil to 20 mL toluene was chosen and used for most experiments
unless otherwise stated.
The rate at which heptane was titrated into the FT5 instrument measuring cell (autoclave) is controlled by a
dosing pump. It was found if heptane is titrated too fast the onset of asphaltene destabilisation and flocculation
may be missed whereas if titrated too slowly, the asphaltenes may destabilise and re-stabilise in the crude oil.
An ideal curve profile should show the translucency increasing as the sample is diluted and then as the
asphaltenes are destabilised and flocculate, the translucency should decrease. It is concluded that a slow
titration rate is required, to ensure that the onset point is correctly detected, particularly in oils where the
asphaltenes take time to destabilise on the addition of the n-alkane solvent.At the 0.5 mL / min titration rate
also gave an ideal curve profile, this was chosen as the titration rate moving forward.
Middle Eastern Crude
The three ester products were dosed at 100 ppm in a Middle Eastern crude oil (1:2 dilution in toluene) and the
results shown in Figure 3. In this plot, and all future plots, the asphaltene flocculation onset region for the blank
is highlighted in a grey box. This relates to the maximum blank transmittance value ± the estimated error
identified during the repeatability test. Any maxima to the left of this onset region will indicate promotion of
asphaltene destabilisation, and any maxima to the right of this region will indicate inhibition of asphaltene
destabilisation.
Figure 3. Asphaltene destabilisation transmittance curves for asphaltene inhibitor candidates dosed at 100 ppm in a
Middle Eastern crude.

In this crude oil, none of the candidates have functioned as an asphaltene inhibitor as there is no delay in the
asphaltene flocculation point. In the case of DDBSA, it appears that asphaltene flocculation has been promoted,
as the DDBSA onset point is significantly earlier than the onset point of the blank.
Latin American Crude
The three ester products were dosed at 100 ppm first and Ester 1 showed some change in the on-set point
(Figure 4). Then the dosage was increased to 1000 ppm in a Latin American crude and the result shown in
Figure 5.
At 100 ppm dosage, none of the candidates functions as an asphaltene inhibitor as shown by the little difference
in the flocculation onset points when compared to the blank. However, at 1000 ppm dosage, there is a clear
delay (beyond the error of the test) in the asphaltene flocculation onset point for Ester 1, Ester 2 and Ester 3,
with Ester 3 providing the better effect. Ester 1, Ester 2 and Ester 3 are behaving as asphaltene inhibitors at this
higher dosage in this oil. DDBSA has not affected asphaltene flocculation at either dosage in this crude oil.
Figure 4. Asphaltene destabilisation transmittance curves for asphaltene inhibitor candidates dosed at 100 ppm
in a Latin American crude.

in a Latin American crude.
North Sea Crude

Similar results were found for the three ester products for a North Sea crude as LATAM crude. They were
dosed at 100 ppm and 1000 ppm in a North Sea crude and the results shown in Figures 6 and 7 respectively.
in a North Sea crude.

in a North Sea crude.
Again, there is a difference in performance depending on the dosage of additive used. At 100 ppm, Ester 2 and
Ester 3 have promoted the onset of asphaltene precipitation slightly. However, for these same two esters at
1000 ppm dosage, the transmittance curves have not reached their maximum during the course of the test,
indicating that a delay in asphaltene onset could have occurred.
DDBSA has promoted asphaltene flocculation when treated at both 100 ppm and 1000 ppm indicated by an
earlier onset point.
Conclusions
A method has been developed and validated for the determination of asphaltene inhibition in crude oil, by
measuring the onset of asphaltene flocculation resulting from the slow titration of a flocculant (heptane). It has
been found that a slow titration rate is important to ensure the system equilibrates in real time and generates a
realistic onset point.
There are two important factors for stabilising asphaltenes using an inhibitor. Firstly, the inhibitor is polymeric
with multiple anchoring points to strongly adsorb onto the surface of the asphaltene molecule and secondly it
needs to create a stable alkyl layer around the asphaltene molecule. Surfactants with short hydrophobic chains
cannot stabilise asphaltene particles because they cannot form a strong/thick steric stable layer. Instead, these
surfactants will be surrounded by asphaltenes themselves and both will then precipitate out. This has been seen
when using DDBSA. In two crude oils, DDBSA had a negative effect on asphaltene precipitation by promoting
the onset of destabilisation. Although DDBSA has a highly polar sulphonic acid head group and some
aromaticity to provide π-π interactions with the asphaltenes, it is failing as an asphaltene inhibitor because of its
short hydrophobic tail and the fact it is not polymeric.

The non-ionic polyester chemistries provide positive results in some crude oils in terms of asphaltene
inhibition. However, this performance is crude oil and dosage specific. Generally, a higher dosage (1000 ppm)
is required for the polyester chemistries to function as asphaltene inhibitors.
Acknowledgements
The authors thank companies for providing crude oil samples, Croda management team for permission and
support for publishing this work, and PSL Systemtechnik GmbH for technical support using the FT5
Asphaltene Flocculation Titrimeter.
References
[1]KellandM.A.Production Chemicals for the Oil and Gas Industry. 2nd ed. Florida:CRC Press; 2009.
[2] Rogel E, Effect of inhibitors on asphaltene aggregation: A theoretical framework, Energy and Fuels2011;
25: 472–481.
[3] Mohamadshahi N,NazarA.R.S, Experimental Evaluation of the Additive Compounds Performance on

Asphaltene Precipitation Using Automatic Titration Method, J. Dispers. Sci. Technol. 2012; 33: 821–826.
[4] Gharbi K, Benyounes K, Khodja M, Removal and prevention of asphaltene deposition during oil
production: A literature review, J. Pet. Sci. Eng.2017; 158: 351–360.
[5] Pfeiffer J, Hase A, Another insight view on HP/HT asphaltene stability measurement in the presence of
asphaltene inhibitors, Petrophase 2018, Park City, US.

Title: “Influence Of Guar Gum And BN Nanoparticles On Rheology Of Drilling Fluid For Hydrate
Bearing Sediments”
-Moumita Maiti, Ajoy Kumar Bhaumik, Ajay Mandal, Indian Institute of Technology (ISM)
Keywords: Drilling Fluids, good low temperature performance, gas hydrate, inhibitors
Abstract:
The term “Natural Gas Hydrate” or “NGH” is generally used to signify a clathrate or hydrates of methane
dominated natural gas which has no particular crystal structure or composition. In the past few decades, from
some widespread exploration through boreholes it has been proved that NGHs are widely distributed. However,
the drilling operation through such hydrate-bearing formation is quite risky because of unconsolidated
formation, fragile nature of formation and uncontrolled formation of hydrate in the drilling fluid. In this study,
an attempt was made to overcome the issues by a specially designed nanoparticle-enhanced water-based
drilling fluid for its potential application in hydrate reservoirs. In this study, the effect of boron nitride (BN)
and guar gum on drilling fluid rheology and fluid loss were investigated. BN nanoparticles were dispersed in
calcium carbonate (CaCO 3 ), polyvinyl pyrrolidone (PVP K-90) and guar gum solution in water. This fluid was
treated with NaCl and bentonite to maintain to laboratory drilling fluid systems. The rheological properties of
these drilling fluid with varying concentration of BN nanoparticles and guar gum have been investigated both
at high pressure and low temperature condition. Drilling fluids with varying concentration of guar gum and BN
have been prepared according to the American Petroleum Institute process and their rheological characteristics
have been investigated using a rotational viscometer. High pressure and low temperature rheology of drilling
fluid was measured by Bohlin Gemini 2, (Malvern Instruments U.K Ltd.). The results showed that, the addition
of BN nanoparticles reduces the filtration loss of drilling fluid which is required to inhibit formation damage.
With addition of very little concentration of guar gum, drilling fluid shows very high viscosity. Plastic viscosity
and yield point increases with addition of guar gum. With decreasing temperature, the rheological properties of
guar gum with bentonite increases. When temperature reduces, the bond strength between particles becomes
stronger, thus rheological properties increases. From different rheological model, these drilling fluid were best
fitted to Herschel-Bulkley model. Under both static and dynamic condition, the designed drilling fluid shows
excellent inhibition effects on hydrate formation. Therefore, the experimental results reveals that this drilling
fluid has optimal density, good rheology at low temperature and high pressure, and it has the ability to inhibit
hydrate formation in the drilling fluid circulation system.
1 Introduction: The term “Natural Gas Hydrate” or “NGH” is generally used to signify a clathrate or hydrates
of methane dominated natural gas which has no particular crystal structure or composition [1]. In the past few
decades, from some widespread exploration through boreholes it has been proved that NGHs are widely
distributed [2]. Gas hydrates are white, ice-like crystalline solid structure consisting of water and natural gas
(methane, ethane) where methane molecules are enclosed within microscopic cages of water molecules.
Methane hydrates are only stable under pressures in excess of 35 bar and at low temperatures. So, seafloor is a
favourable place for their formation, the temperature of the oceans bottom water and seabed are more or less
same varying from 273.15 K to 277.15 K. But, temperature started increasing with sediment depth below the
seafloor because of the closeness of the earth’s interior. At depth greater than 1km below the seafloor, the
temperature rises to about 303.15 K. At this temperature methane hydrates cannot be deposited.
There are three possible types of crystal structures of gas hydrates such as structure I and II, structure H and a

new unspecified structure [3]. Structure I hydrates are generally originate from nature and they have a body-
centered cubic structure. Structure II hydrates have a diamond shaped network which is surrounded by cubic
structure framework and they are commonly found in artificial systems like oil and gas pipelines. Structure H
hydrate shows a hexagonal crystal structure [4]. The guest molecules size affects the types of crystal structures
such as methane and ethane guest molecules form structure I hydrates, propane form structure II hydrates and
the combination of methane and other relatively larger guest molecules e.g., cyclopentane form structure H
hydrates [5].
In the past few decades, there are numerous amount of deep water drilling operations are going on and this
should keep going in near future also, especially in gulf of Mexico or gulf of Guinea where numerous
exploitation license have been taken up to extreme depth [6]. Natural gas hydrates have a lots of potentially to
produce natural gas. It can change the petrophysical properties of the formation rock and below the seafloor,
decomposition of gas hydrate can cause landslide, thus methane can release from the formation and resulting
affect global climate. Besides deep water gas hydrate can cause a serious hazard when drilling through the
hydrate formation to recover oil and gas.
There are different types of drilling fluids are present such as water based drilling fluid, oil based drilling fluid
and pneumatic drilling fluids and they are used with different appropriate polymers and some clay additives
[7]. Some gas hydrates are generally formed in association with shale formation. They even failed to make a
proper filter cake which could reduce fluid penetration[8]. Generally, oil based drilling fluids are better to
prevent shale instability as oil can not react with the shale [9].
In this study, different drilling fluids with varied composition including nanoparticles are prepared and their
rheological properties such as plastic viscosity, apparent viscosity, filtration loss were examined before and
after the addition of the nanoparticles.
2 Materials and Methods

In thelaboratory, the formulation of some drilling fluids was developed for deep water offshore drilling. The
gas mixture, Methane (90 mol%), ethane (7 mol%) and propane (3 mol%) used in this study was supplied by
Chemtron Science Laboratory, Navi Mumbai (India).The bentonite used in this experiment, was purchased
from LobaChemiePvt. Ltd. where, sodium chlorite was from Finer Chemicals Limited., Ahmedabad. Calcium
Carbonate and Boron Nitride both the materials are supplied from Sisco Research Laboratories Pvt. Ltd. Guar
gum and Polyvinylpyrrolidone K-90 were obtained from Sigma-Aldrich Chemie GmbH and Central Drug
House (P) Ltd. respectively.
To achieve dispersions of bentonite, a definite amount of bentonite was added to 500ml distilled water and then
mix it with Hamilton Beach Spinner for 20 minutes. After that, specific amount of NaCl is added to get
simulated sea water. Then CaCO3, PVP K-90 and Guar gum finally were added to the base fluid gradually to
form drilling fluid sample.
3 Apparatus and procedure for gas hydrate study

In this study, the experiments to check the inhibition effects of drilling fluids on hydrate formation have been
conducted with PMI gas hydrate autoclave system with a capacity of 500 cc, as shown in Fig. 1. The set-up is
capable of controlling the temperature upto 523.15 K and raises the pressure up to 20.68 MPa. Inlet line of the
autoclave was connected with a pressure sensor. The pressure and temperature of the system can be controlled
by inbuilt software installed in a computer and pressure-temperature variation during the experiment can be
observed in the computer interface. Within the autoclave cell, a mechanical stirrer is equipped with an
adjustable rotation speed ranging from 0 to 1000 RPM to agitate the test fluid.
For the kinetic hydrate studies, a 200cc volume of test fluid was prepared by diluting the drilling fluid sample
(FS 5) with distilled water in the ratio of 1:1. Then the sample was taken into the hydrate cell and the unit was

then sealed. Temperature was controlled by apcon technology chiller which is connected with the cell and was
maintained at the required temperature. After that, the cell was pressurized by methane gas to the desired level.
Initially, the test fluid was stirred at a constant of 500 RPM by the mechanical stirrer. The pressure and
temperature of the system were recorded with 5 minutes’ interval by algorithm based interface. Till the pre-
estimate time the experiment was continued and for hydrate formation, the sudden drop in pressure was
recorded for experimental analysis.
Fig. 1: Sketch of an experimental system for Gas Hydrate formation studies
4 Rheological Results and Discussion
The compositions of different drilling fluids are reported in Table 1.Effect of bentonite on drilling fluid is
shown in Fig. 2. As the concentration of bentonite increases, the PV and YP value also increases. With
increasing amount of bentonite, shear stress of the fluid increases with shear rate.
Table 1: Different drilling fluids with different concentration of additives
Fluids Distilled Bentonite NaCl CaCO 3 Guar Boron PVPK-

Water (wt%) (wt%) (wt%) gum nitride 90
(ml) (wt%) (wt%) (wt%)
FS 1 500 4 3.5 8 0.4 0.0095 0.7
FS 2 500 5 3.5 8 0.4 0.0095 0.7
FS 3 500 5 3.5 8 0.5 0.0095 0.7
FS 4 500 5 3.5 8 0.4 0.02 0.7
FS 5 500 5 3.5 8 0.4 0.1 0.7
FS 6 500 5 3.5 8 0.4 0.2 0.7

1000
FS 1
FS 2
100
Shear stress (Pa)

10
0.1
0.01
0.01 0.1 1 10 100 1000
Shear rate (1/s)
Fig. 2: Effect of bentonite on shear rate - shear stress
4.1 Effect of Guar gum and boron nitride concentration on drilling fluid rheology:
With addition of very little concentration of guar gum, drilling fluid shows very high viscosity. As shown in
table 2, viscosity of the drilling fluid increases with increasing concentration of guar gum. Interaction of
intermolecular chain enhanced with increasing guar gum concentration, thus viscosity increases [10]. Guar gum
has a significant effect on filtration loss properties. Fluid loss of the drilling fluid reduces with increasing
concentration of guar gum. Boron nitride nanoparticles has a greater effect on filtration loss. Filtrate loss
decrease significantly with increasing boron nitride. Rheology of different drilling fluids with different
concentration of guar gum and boron nitride are shown in Fig. 3. Shear thinning behaviour at 303.15 K
temperature, which means that at constant temperature, the viscosity of these drilling fluids decrease with
increasing shear rate. Shear thinning behaviour of these drilling fluid increase with polymer concentration. As
shown in Fig. 2 and 3, the flow curves of drilling fluids measures from rheometer is behaving like a power law
fluid because it has no yield stress. Amongst all the sample fluids, FS 5 is showing a desirable median value of
PV (15 mPa.s), AV (22.5 mPa.s) and YP (15 Pa), thus FS 5 is showing optimized rheological values. So, for
further studies, FS 5 fluid has been used.
1000 FS 4
FS 3
FS 5
100 FS 6
Shear stress (Pa)
10
0.1
0.01
0.01 0.1 1 10 100 1000
Shear rate (1/s)
Fig. 3: Effect of guar gum and BN nanoparticles on shear stress-shear rate

Table 2: Rheological properties of sample fluids at 303.15 K.
Drilling Plastic Yield Apparent Gel strength YP/PV FL Flow Consistency Density
Fluid Viscosity Point Viscosity (10sec/10min) (ml) index index (lb/gal)
(mPa.s) (Pa) (mPa.s) (Pa/Pa) (n) (K)
(Pa.sn)
SF 1 10 18 19 1/1.5 1.8 10.8 0.46 0.91 9.14

SF 2 12 18 21 2.5/3 1.5 10.6 0.38 2.13 9.27
SF 3 14 12 20 3/4.5 0.86 8.9 0.45 1.96 10.7
SF 4 15 16 23 5/6 1.07 8.8 0.54 0.66 10.21
SF 5 15 15 22.5 7/8 1 8.0 0.42 5.12 11.68
SF 6 17 18 26 6/8 1.05 7.4 0.44 3.17 12.13
4.2 Effect of temperature on drilling fluid rheology:

The effect of temperature on rheological characteristics such as plastic viscosity, yield point and apparent
viscosity is shown in Fig. 4.From this figure it is clear that plastic viscosity ofFS 5 sample increases with
decreasing temperature. It can be responsible for the decrease in Brownian motion and accelerate in dispersion
with decreasing temperature. For most of the bentonite, the rate at which flakes get separated is directly related
to the energy introduced during hydration [11]. Therefore, as temperature decreases, each single platelets in
bentonite dispersion decreases which attributes to an increase in plastic viscosity. Temperature also has a
greater effect on bentonite based drilling fluid in the presence of guar gum and BN nanoparticles. With
decreasing temperature, rheological properties like plastic viscosity, yield point and apparent viscosity of these
drilling fluid increases. When temperature reduces, the bond strength between particles becomes stronger, thus
rheological properties increases.
100
286.15 K (b)
1000 (a)
286.15 K 278.15 K
278.15 K 271.15 K
271.15 K
100 10
Viscosity (Pas)
Shear stress (Pa)
10
1
0.1
0.1
0.01 0.01
0.01 0.1 1 10 100 1000 0.01 0.1 1 10 100 1000
Shear rate (1/s) Shear rate (1/s)
Fig. 4:(a) Flow curve and (b) Shearrate- viscosity plot of FS 5 at low temperatures
Table 3: Rheological characteristics of FS 5 at low temperature
Temperature (K) PV (mPa.s) YP (Pa) AV (mPa.s) YP/PV

271.15 K 35.65 52.45 61.95 1.47
278.15 K 27.84 38.86 65.94 1.39
286.15 K 22.65 28.58 42.73 1.26

4.3 Effect of pressure on drilling fluid rheology:

High pressure has a greater effect on bentonite based drilling fluid withaddition of guar gum and BN
nanoparticles. Rheological properties of drilling fluid with addition of guar gum and BN nanoparticles
enhanced with increasing pressure. Plastic viscosity, apparent viscosity and yield point increases with pressure.
Apparent viscosity of FS 5 fluid increases with increasing pressure as shown in Fig 5 (a). Viscosity of the
drilling fluid decreases with increasing shear rate, thus following shear thinning behaviour which is shown in
Fig. 5 (b). Rheological properties of FS 5 at high pressure is mentioned below in Table 4.
1000
(b) 7.8 MPa
1000 7.8 MPa (a) 8.8 MPa
8.8 MPa 11 MPa
11 MPa 100
Viscosity (Pa.s)
Shear stress (Pa)
100 10
10
0.1
1 0.01
0.01 0.1 1 10 100 1000 0.01 0.1 1 10 100 1000
Shear rate (1/s) Shear rate (1/s)
Fig. 5: (a) Flow curve and (b) Shearrate- viscosity plot of FS 5 at high pressure
Table 4: Rheological characteristic of FS 5 at high pressure
Pressure PV YP AV YP/PV
(MPa) (mPa.s) (Pa) (mPa.s)
7.8 27.89 40.25 47.59 1.44
8.8 45.58 68.98 77.68 1.51
11 55.29 87.75 97.54 1.58
5 Hydrate inhibition studies of drilling fluid:
Formation and dissociation behaviour of hydrates:

Fig. 6 (a) and (b) shows the variation of pressure with temperature during hydrate formation and dissociation
for pure water and drilling fluid (SF3) systems. In case of pure water, an experiment was performed with
starting temperature of 289.65 K and pressure of 10.72 MPa. Formation of hydrate is started at 283.65 K when
sudden drop of pressure was observed. A sudden rise in temperature was also observed with pressure drop due
to the exothermic reaction of hydrate formation. Under the similar condition of temperature (289.75 K) and
pressure (10.92 MPa), an experiment was carried out with FS 5 drilling fluid. In this case, hydrate formation
occured at temperature of 274.45 K, which is 9.2 K lower than pure water’s hydrate formation temperature.
Higher subcooling is needed (9.2 K) to initiate hydrate formation in presence of PVP K-90 than pure water as it
inhibits hydrate formation.
12
12 FS 5 Sample (b)
Pure Water (a)
11 11 Start cooling
Nucleation Start cooling
Nucleation
10 10
Pressure (MPa)
Pressure (MPa)
9
9
8
8
7
7
6
Dissociation begins 6
5 Start heating Dissociation begins
Start heating
276 278 280 282 284 286 288 290 292 274 276 278 280 282 284 286 288 290
Temperature (K) Temperature (K)
Fig. 6: Pressure-temperature profile of methane hydrate formation and dissociation in (a) pure water and (b) FS
5 sample
Conclusions:
1. The prepared sample fluid (FS 5) has good rheological properties, suitable fluid loss, and moderate
density. With an increase in pressure, FS 5 was showing an increasing trend in plastic viscosity, yield
point, apparent viscosity.On the other hand, plastic viscosity, apparent viscosity, yield point increases
with decreasing temperature.
2. Fluid loss reduction takes place as BN and guar gum are added to the drilling fluid.
3. From the experimental results, it can also be said that selected FS 5 has a good capability of inhibiting
hydrate formation at high pressure and low temperature.
4. From the experimental results, it is clear that FS 5 sample has a good capability of inhibiting hydrate
formation.
References:
[1] Max, M.D., Johnson, A.H., 2016. Exploration and Production of Oceanic Natural Gas
Hydrate. https://doi.org/10.1007/978-3-319-43385-1
[2] Zhang, H., Cheng, Y., Shi, J., Li, L., Li, M., Han, X., Yan, C., 2017. SC. J. Nat. Gas Sci. Eng.
https://doi.org/10.1016/j.jngse.2017.08.029.
[3] Udachin, K.A., Ripmeester, J.A., 1999. Udachin1999 397, 4–7.
[4] Jensen, L., Thomsen, K., Von Solms, N., 2011. Inhibition of structure I and II gas hydrates using synthetic
and biological kinetic inhibitors. Energy and Fuels 25, 17–23. https://doi.org/10.1021/ef100833n
[5] Shahzad, M., Hussein, I.A., Sultan, A.S., Solms, N. Von, 2016. Application of various water soluble
polymers in gas hydrate inhibition. Renew. Sustain. Energy Rev. 60, 206–
225. https://doi.org/10.1016/j.rser.2016.01.092
[6] Dalmazzone, C., Dalmazzone, D., Herzhaft, B., 2000. SPE 62962 Differential Scanning Calorimetry : A
New Technique to Characterize Hydrate Formation in Drilling Muds.
[7] Ozbayoglu, E.M., 2008. Effect of Pipe Rotation on Hole Cleaning for Water-Based Drilling Fluids in

Horizontal and Deviated Wells IADC / SPE 114965 Effect of Pipe Rotation on Hole Cleaning for Water-Based
Drilling Fluids in Horizontal and Deviated Wells. https://doi.org/10.2118/114965-MS.
[8] Cai, J., Chenevert, M.E., Sharma, M.M., 2012. Decreasing Water Invasion Into Atoka Shale Using
Nonmodified Silica Nanoparticles 103–112.
[9] Chenevert, M.E., Production, E., 1970. Shale Control with Balanced-Activity Oil-Continuous Muds.
[10] Mudgil, D., Barak, S., 2011. Guar gum : processing , properties and food applications — A Review.
https://doi.org/10.1007/s13197-011-0522-x
[11] Razi, M.M., Ghiass, M., Razi, F.M., 2013. Effect of Guar Gum Polymer and Lime Powder Addition on the
Fluid Loss and Rheological Properties of the Bentonite Dispersions. J. Dispers. Sci. Technol. 34, 731–736.
https://doi.org/10.1080/01932691.2012.683985

Title: “Sustainable Model for The Future Oil And Gas Industry”
-Rathnabai B, Sivashankari S, Department Of Petroleum Engineering, Dhaanish Ahmed College of
Engineering
Keywords: sustainability, policies, challenges, innovation, smart solutions, oil and gas industry
Abstract.
The oil and gas industries remain an important drive for the world economy. On one hand, global demand for
fossil fuels is still rising, and on the other hand, companies face complex investment challenges due to the
harsh operational environment of exploration and production activities. Workforce regulations aim to provide a
safe and secured working environment. However, exploration and production activities still cause local and
global environmental risks such as groundwater contamination, or climate change in broader scale. Analyzing
and reporting mechanisms are key performance indicators of sustainable development at the level of oil and gas
companies. Obtaining and analyzing required data, nevertheless, seem to be a persistent challenge as to what
degree these findings can affect the routine and strategic decisions of the oil and gas companies. In order to
enable oil and gas companies to measure and control risks and manage incidents, artificial intelligent
technologies in extended monitoring and supervising E&P operations is known to be an efficient prevention
strategy. Such tools not only aid in profitability of the oil and gas companies, but also increase awareness of
environment and climate change to act more responsibly. This paper provides a comprehensive review of
emerging technologies in addressing existing and foreseen challenges in sustainable development in oil and gas
industries, with the aim of suggesting prime solutions for strategic planning attempts.
Introduction
The oil and gas industry continues to be the main source of energy in the world, and is one of the most
important parameters that have left an impact on the growth of the global economy. Oil and Gas industries
supply more than 50% of global fuel consumption, and hydrocarbons are expected to remain the superior
source of energy in 2035. Daily production of oil was around 96.3 million barrels in 2016 which yields 2 litres
per day per each person in the world. Continued research of BP shows that till 2035, natural gas will become
the second largest fuel source, so fossil fuel demand is rising. Hence, continuous exploration and production
activities in the world. The expected needs of investment in the upstream section will be 700 USD billion
yearly till 2040 to meet the global energy needs as International Energy Agency (IEA) stated. On the other
hand, the financial markets of the world now have billions of dollars in turnover from the daily production of
more than 96 million barrels of oil (IEA, 2016b), which has left economic impacts on the regional markets of
the countries that are either exporters of oil and gas or importers of fossil fuels. Apparently, there has been no
precise forecast for changing the principles of energy market neither on demand nor the supply side. But it is
obvious that from each barrel of oil however, there are many more barrels of waste generated.
Overview of the O&G industry
To be able to properly understand the role of oil and gas industry with respect to sustainable development, and
to properly assess the challenges and the roles of each component of the oil business chain, there is need for a
proper understanding of the structure of this industry. The oil and gas industries are usually divided into three
major sectors: Upstream, Midstream and Downstream - Upstream sector is known as “E&P”, where “E” stands
for exploration and “P” for production that each of them may be divided to other categories depending on the
characteristics of the reservoir and circumstances of the field. In upstream, searching of potential on-shore or
off-shore crude oil and natural gas is performed, then exploratory and appraisal wells are drilled. Commercial

production then starts after drilling a number of development wells and connecting them to the surface
production unit and transportation facilities. - Downstream and Midstream sectors are supplements of the
upstream section to deliver the products to consumers. Midstream is mainly comprised of transportation means
from the well to the processing facilities, and then to refineries. - The main component of the downstream
sector however is refining of crude oil and processing of natural gas. This process provides gasoline or petrol,
kerosene, diesel, fuel or jet oil, lubricant waxes, asphalt, NLG or LPG besides petrochemicals. Delivery to the
end user is also a part of downstream sector.
The major developers of the petroleum industry can be grouped as national oil companies (NOC) and
international oil companies (IOC). These companies often operate in an integrated manner, encompassing both
upstream and downstream (Whitson, 2009), forming the basic structure of this industry. There are plenty of
smaller size businesses that contribute to the main activities of the oil and gas industry (i.e. E&P and refining),
or supply services to NOC’s, IOC’s and other type of companies involved in this industry.
Oil and Gas Industry and Sustainability

In recent years, the oil and gas industry has also been called to deliberate over environmental protection. The
severity of environmental crises and climatic change emanated from the production of oil and gas has left grave
repercussions for many societies. Major oil companies have been accused of creating disorder in global
environmental issues and they face reliability issues by policy-makers and the public from around the world.
People of the world are re-examining how fossil fuels are used in their lives. This negative mentality is based
on several evidences, issues like the Santa Barbara oil spill in 1969 in California and Deep water Horizon
disaster in the Gulf of Mexico in 2010 .These environmental disasters have prompted the public into seeking
both measurable improvement in performance and greater transparency and operation in oil and gas industries,
pertaining to sustainability. Consequently, the oil and gas industries, like other industries, have redefined their
business development strategy on the basis of sustainable development while some of them have become
responsive toward some of the operational criticisms. The oil companies adopting supportive policies for
protecting the environment to ensure safety measures in exploration and production activities. This is how the
concept of sustainable development has entered into the oil and gas industry literature, and terms such as Green
Economy, Sustainable Development, Social Responsibility and Risk Management have become commonplace
in lectures and seminars presented by oil companies. In the same vein,Oil Company’s top management are now
in favour of smart solution implementations and innovations such as Performance Assurance and Operation
Risk Management, Contaminated Site Management and Air Quality and Climate Change. However there is
always a difference between what oil companies declare about sustainability and how they perform. For this
reason, considerable studies have been conducted and the overall conclusion conveys that sustainable
development has seriously gained entrance into the decision-making levels of major oil and gas producing
companies, although in reality, the oil industry still remains one of the main causes of environmental
degradation and climate change. For this reason, organizations such as IPIECA, API and OGP are very active
in organizing sustainable development management standards in the oil and gas sector, and encouraging oil and
gas companies and their shareholders to provide voluntary reports as one of their priorities, thereby
consolidating with, and adhering to sustainable development strategies. The study conducted herewith, reveals
that in spite of the very simple and effective definitions about sustainability provided in the past decades, there
are still many ambiguities around this concept and in practice, this concept has exhibited contradictory
interpretations.
Challenges of sustainability in oil and gas industry

Over the past years, the petroleum industry has faced several complex challenges. The oil industry should
invest pro rata to the increasing demand for energy in the world, and on the other hand, in view of the more

competitive activities in these sectors, this industry should reduce the total cost of production of hydrocarbon
resources, while simultaneously adhering to the environmental laws and social responsibilities. Some
significant challenges for oil and gas industry include:
• Price fluctuation
• Increasing pressure on managers by shareholders focusing on value creation instead of output because
of low returns on investments
• Complexity of drilling and production process
• Increasing demand for oil and gas in most regions
• HSE compliance remaining critical - especially in the current environment of volatile prices and cost
savings
• Protection of the social license of operation and corporate social responsibilities
• Fluctuation of fiscal regimes;
• R&D and innovation;
• Handling growing size of data and knowledge management and
• Unstable partnership of NOC-IOC:
The challenges mentioned above are a set of effective factors that have hit major oil and gas producing
companies in the process of implementing sustainable development policies. As mentioned earlier, the
production of every barrel of crude oil, refining and transportation of petroleum products to the customer, due
to the high pressure- high temperature conditions of underground reservoirs, and the use of a variety of
chemicals to safely drill and produce hydrocarbons, is an industry that causes contamination and pollution.
In general, the challenges of sustainable development in the oil and gas sector can be categorized as follows.
• Flaring and venting;
• Decommissioning of oil and gas installations;
• Oil storage tank disposal;
• Managing drill cuttings;
• Produced water disposal/treatment;
• Managing drilling muds and fluids;
• Estimating and validating greenhouse gas emissions;
• Subsidence;
• Spills;
• Safety; and
•Enhanced profitability.
Each of the abovementioned challenges has created many environmental concerns and occasionally
environmental crises in the past. Of course, some major oil companies have made decisions about each of these
challenges, and billions of dollars have been spent annually on improving methods and technologies, and
dealing with indigenous communities around oil and gas facilities. Also, over the past years, national oil
companies under the pressure of governments, and international oil and gas companies under pressure from
public and lawmakers, have taken a number of measures to address the challenges of sustainable development
in the petroleum industry.

And also, lobbying continues to take place among some oil company executives and local governments and
worries about the repetition of bitter memories such as the fire of the Alpha Piper oil rig in 1988 causing the
death of 167 people and so on, is still in the minds of environmental activists. Meanwhile, a number of oil and
gas companies have also made significant strides in the social corporate responsibility (SCR) sector, and they
most effectively support the achievement of the SDGs and the 2030 Agenda. Such companies do not guarantee
a world free of any environmental crises, but have demonstrated some significant efforts to avoid such
incidents. However, the existed conditions proved that they can do much more than what they claim.
Sustainable drivers
The world's population is steadily increasing, ensuing the need for more affordable and accessible energy. The
fluctuation in pricing has led to staggering competition in the energy supply market incurring reduction of
prices. Over the past decades, regional, cultural and security disputes have steadily increased reaching their
peaks in recent times. Under such critical circumstances, the provision of sustainable energy has greatly
increased the risk prospects in corporate activities, leading to higher investment costs. Climate change is
steadily exacerbated every year. The world is facing devastating consequences of global climate change. There
is danger of raising sea level, and more villages and towns are at risk of floods and storms. This is one aspect of
challenges of which addressing requires long term efforts. Meanwhile, with the steady rise in production costs,
the expectations of shareholders and owners of enterprises have also increased. The shareholders consider
economic gain as the priority of their activities, and expect a steady increase in the profitability through
executives of business entities. All of the several factors, such as increasing population, escalating competition,
global climate change, and shareholder expectations, regional trade patterns are Sustainable Drivers that have
instigated the business environment with risks and tension. Identifying challenges and addressing each
challenge is an ongoing battle for oil and gas companies and they are constantly improving their business plan
to be as comprehensive and consistent as possible. This paper provides insights into some of the existing
challenges, and discusses statistical results of a survey over some of the sustainability indicators.
Conclusion
The use of information technology, intelligent control tools, intelligent maintenance programs as well as
organizational reform and targeted investment in the R & D sector to fulfill the goals of sustainable
development, includes a series of measures that will restore public confidence in the oil industry, and in fact, in
this research, it became clear that the implementation of sustainable development requires a change in the
minds and policies of oil and gas producing companies. According to this study, private sector seemed better
able to respond to the price fluctuations due to their structural constitution and values. Skills development and
job creation during the industry downturn were a priority within the private sector while the governmental
entities tended to freeze the employment, and therefore, their contribution to the job market was minimized. In
terms of benefiting from customer intimacy, larger sized companies were doing better off, which reflects
efficiency of the customer relation policies they might have adopted in their organizations. Profitability and
efficiency were the main performance indicators among state owned and private companies respectively.
Should a company have to improve the strategic plan in order to boost the sustainability, all of these findings
must be utilized. One of the most effective tools is using smart and intelligent tools to continuously monitor the
activities and services to customers, especially where the number and type of customers are large, then
adopting dynamic and more responsive policies that can maximize values of the entire industry. Maintaining a
biodiversity policy is also another emerging requirement within the petroleum industry, which needs a lot of
work. Companies in the Middle East region are not fully aware of significances of environmental protection
policies, and thus, unintentionally risk the environment by further exploration and production activities. Given
the fact that almost half of the respondents to this survey indicated that there is no specific department

responsible for sustainability in their organization, a comprehensive approach must be taken to educate
managers and employees to improve the quality of services to the industry and relevant customers now, and in
coming future.
References
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responsibility.
• Human Relations, 0018726717726586.BP. (2017a).
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economics/energy-outlook2017/bp-energy-outlook-2017.pdf BP. (2017b).
• Statistical Review of World Energy.Retrieved from
https://www.bp.com/content/dam/bp/en/corporate/pdf/energy-economics/ statistical-review-2017/bp-
statistical-review-of-world-energy-2017-full-report.pdf Bratianu, C., &Bolisani, E. (2015).
• Knowledge strategy: an integrated approach for managing uncertainty. Paper presented at the 16th
European Conference on Knowledge Management, University of Udine, Italy. Dima, A. M., Hadad, S.,
&Luchian, I. (2017, July).
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Conference on Business Excellence (Vol. 11, No. 1, pp. 64-73).
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Engineering, 18(1), 3-33. Hall, J., &Vredenburg, H. (2003).The challenge of innovating for sustainable
development.
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https://www.iea.org/about/faqs/oil/ IEA. (2016b).
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&Petters, S. W. (2013).
• Petroleum exploration and production: past and present environmental issues in the Nigeria’s Niger
Delta.
• American Journal of Environmental Protection, 1(4), 78-90.
• Miron, D., Dima, A.M. and Vasilache, S. (2010).
• Models of the Intra-regional Trade Influence on Economic Sustainable Development in
Romania.Amfiteatru Economic, XI (27)

Title: “Enhanced Oil Recovery (EOR): From Lab Screening to Field Implementation – Connecting the
Dots”
-Neeraj Rohilla, Christopher W. Nelson, Pete Rozowski, the Dow Chemical Company
Keywords: Enhanced Oil Recovery, Wettability Alteration, Surfactants for EOR
Abstract:
Chemical flooding technologies involving surfactant (Surfactant-Polymer (SP)/Alkali-Surfactant-Polymer
(ASP)) are critical to recovering additional oil from matured reservoirs close to residual oil saturation. One of
the critical risk factors is the formation of highly viscous unfavorable phases during chemical injection and
propagation through the reservoir. Co-surfactants and co-solvents are shown to prevent formation of such high
viscosity phases. Moreover, a formulation optimized by co-surfactants/co-solvents also helps in reducing phase
trapping of the surfactant. This approach is beneficial to reduce the surfactant retention,allowing the chemical
flooding process to be more economical. Current work utilizes automated high throughput screening methods
to generate structure property relationships of optimal salinity and type III micro-emulsion occurrence.
Furthermore, the ability of various co-solvents to reduce viscous emulsions is also investigated.
Finally, we present a case study for wettability alteration in carbonates involving a comprehensive process from
lab screening to field scale implementation. The unique functionality of Dow ELEVATETM1surfactants alters
reservoir surface wettability to more water wet with low adsorption on the rock surface, yielding a negligible
change in interfacial tension. Core flood experiments demonstrated significant oil recovery and field trial show
injectivity improvements, indicating wettability alteration to a more water wet state.
Introduction:
Conventional water flood methods leave behind more than 50% of original oil in place (OOIP) in the form of
discontinuous oil ganglia trapped due to capillary forces.[11, 16, 17, 19, 20, Figure 6A]. Capillary number
governs the mobilization of the residual oil post waterflood,Nc = (µ w v/σ ow ); where, µ w is viscosity of water, v
is the displacement rate and σ ow is the interfacial tension between oil and water phase. A surfactant formulation
that recovers significant amounts of residual oil post waterfloodneeds to enhance the Capillary number by at
least three orders of magnitude as shown in Figure 6[11, 20]. Lowering the interfacial tension (IFT) between
the aqueous and oil phases to an ultra-low value (10-3 dynes/cm or lower) is critical to mobilizing trapped
residual oil in the reservoir [3, 5, 7].
1
™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow

Figure 6(A) Various recovery stages in the life of a typical conventional oil reservoir (B) Capillary number and
Residual oil recovery relationship post waterflood.
Blends of primary surfactants, secondary surfactants, and solvents are used in chemical enhanced oil recovery
(CEOR) due to their ability to form Windsor Type III microemulsions. Type III microemulsions have low
viscosity and ultra-low interfacial tension (ULIFT), which facilitates the removal of oil trapped in reservoir
formations. Figure 7 shows three distinct types of microemulsion phases observed during phase behavior tests
when salinity is systematically increased. At low salinity, surfactant molecules self-assemble in the form of a
micelle and small amounts of oil are solubilized in the core of the micelle, creating a type I microemulsion. At
intermediate salinity, a third phase or type III microemulsioncomprising of surfactant/water/oil co-exists with
excess water and oil phases. A type III microemulsion is characterized by close to zero curvature which results
in ULIFT between oil and water as shown in Figure 7[8]. Finally, at high salinity, reverse micelles are formed
that solubilize water in the core of the micelles. This phase is referred to as a type II microemulsion or water/oil
microemulsion.
Figure 7(A) Typical trend of interfacial tension observed with increasing salinity. (B) Ultra-low IFT is
achieved when a type III/middle phase microemulsion is present [3, 8, 16]
Surfactant constituents of either a SP or ASP formulation typically contain two or more surfactants and
sometimes a co-solvent. In this work, we describe a method to perform automated high throughput screening
that can be used to map out the phase behavior space of microemulsions as a function of brine salt content, co-

surfactant type, primary to secondary surfactant ratio, and solvent type. The objective is to perform a proof of
concept experiment that can be used to create a comprehensive library of formulation compositions that yield
Winsor type III microemulsions for enhanced oil recovery.
Materials:Formulations composed of water, salt, oil, one or two surfactants, with or without solvent, are
prepared by hand and stored at elevated temperature for 14 days. De-ionized water is obtained from the
laboratory building supply. Sodium chloride is obtained from Fisher Scientific, and dodecane(model oil) is
obtained from Sigma Aldrich. All materials are used as received. The surfactants selected for study included
three ELEVATETM anionic sulfonated surfactants and one Shell Enordet™ internal olefin sulfonate.
Phase Identification and Image Capture: Formulated libraries are placed in the “Phase Identification and
Characterization Apparatus - Large Volume (PICA LV)” pre-heated to 65 °C. The libraries are left in the
machine for 15 minutes to thermally equilibrate prior to image capture. Images are captured at various time
points over the course of 2 weeks. Between image collection points, samples are stored in an oven at 65 °C to
maintain their temperature. The vials are gently inverted on Day 3 and Day 5 to ensure good contact between
the two phases. Once images are obtained for each library, PICA tools are used to stitch together images into
strips as a function of composition (Figure 8).Each row, as indicated at the left, corresponds to a different ratio
of primary surfactant to secondary surfactant. The percentage indicates the ratio of primary to secondary
surfactant, with the total surfactant concentration always fixed at 2 % w/w of the total aqueous phase. Each
column in the image corresponds do a different salinity, indicated along the top by the percentages (by mass) of
sodium chloride present in each solution.
Figure 8 An example of a full image montage from the experimental design.

Figure 9 Tilt test for microemulsion viscosity characterization
Viscosity Characterization of the Middle Phase Microemulsion: In order to qualify the overall viscosity of
the microemulsion systems, simple bench-top ‘tilt tests’ are performed. In these experiments, the
motion/deformation of the menisci in each vial is observed in response to a tilting motion (30-45 degrees).
Figure 9 illustrates the tilt-test process. A lack of deformation of the middle-phase fluid interface in response to
a tilt would indicate a highly viscous or gel-like phase. In addition to images, the operator notes any
formulations which appear highly viscous based on their observations while handling the vials.
Interfacial Tension ‘Shake-Tests’: Shake tests are performed to qualify the interfacial tension (IFT) of the
microemulsions and aid in more accurately identifying potential Windsor type-III systems. Using the PICA LV,
a picture-shake-picture protocol is employed to take images of the vials after 2 weeks of incubation at 65 °C
just before, and then immediately after vigorous wrist shaking using the PICA’s automated wrist shaker.
Shown below inFigure 10are the results of a typical picture-shake-picture experiment for five
differentmicroemulsion formulations.
Figure 10Distinction between type I and type III microemulsions by using the ‘Shake-Test’. (A) Vials at
equilibrium and (B) Vials immediately after the ‘Shake-Test’

Figure 11Inversion test determines that the presence of co-solvent to a fixed formulation may increase the
salinity range for observing type III microemulsion and ultra-low-IFT
Figure 11 (top-row) shows the salinity scan of a finalized formulation that yields type III microemulsion
between the salinity ranges of 8-11% with 7.25% being border-line type III microemulsion. Using a
functionalized co-solvent the salinity range for type III microemulsion was enhanced to 5-11% as shown in
Figure 11 (bottom-row). Enhanced salinity range for ultra-low-IFT adds robustness to the existing formulation
making it less prone to variations of salinity in the reservoir.
Wettability Alteration Formulations:

More than 60% of the world’s oil reserves are held within naturally fractured carbonate reservoirs. Carbonate
reservoirs present several characteristics that lead to low oil production during secondary oil recovery by
waterflooding, including heterogeneous reservoir rock properties, such as porosity and permeability, and
heterogeneous wettability [18]. Wettability has been widely recognized as a reservoir property that can have a
significant impact on the fraction of oil that is ultimately recoverable [1, 13]. Several laboratory investigations
have shown that changing the rock surface wettability to a more water-wet state can lead to significantly higher
oil recovery during the waterflooding process. It is generally accepted that water-wet conditions create positive
capillary pressure which drive the imbibition of water into the tight rock pores [4, 6, 9]. In particular, the
addition of wettability altering surfactants can enhance water imbibition into the low permeability matrix and
enhance water spreading on the carbonate rock to release trapped oil and hence increase cumulative oil
recovery.
The mechanism of wettability alteration using non-ionic surfactants has been proposed to involve micellar
solubilization of adsorbed hydrophobic material on the carbonate surface into the aqueous solution. Non-ionic
surfactants present several advantages as compared to anionic surfactants, including: 1) brine compatibility and
aqueous stability 2) phase behavior (i.e., minimal formation of viscous macroemulsions that create fluid flow
issues); 3) low adsorption; 4) the ability to improve oil recovery while maintaining a relatively high oil-water
interfacial tension, using capillary pressure as a driving force to expel oil out of the tight matrix pores, which
facilitates transport through the reservoir without the need of a mobility control agent [2, 12].

High Temperature and high Salinity Formulation development: Mechanism

The primary surfactant in this case is a non-ionic surfactant as a wettability altering agent. Typically non-ionic
surfactants have cloud point temperature above which surfactant become insoluble in the water phase and phase
separates. The cloud point temperature of surfactant is inversely proposal to the brine salinity. Some organic
solvent may influence the micellar properties of non-ionic surfactant in solution. The presence of solvent in the
solution leads to an increase in the critical micelle concentration (CMC) of non-ionic surfactants, which is
attributed to an increase of the solubility of the surfactant monomer [14].
A hydrotrope or co-surfactant is an organic compound, commonly amphiphilic with a small polar group
(anionic) and a bulky non-polar group (short-chain or aromatic), which solubilizes hydrophobic compounds in
aqueous solutions [10]. Hydrotropes or co-surfactants are known to increase solubility of non-ionic surfactants.
Molecular structure dictates the mechanism by which co-surfactant enhance solubility of primary surfactant.
There can be two ways by which surfactant solubility and salt tolerance can be enhanced: 1) by increasing the
solubility of primary surfactant by solvency enhanced by a hydrotrope and 2) by increasing the solubility of
primary surfactant by creating mixed micelles between primary and co-surfactant.
Figure 12 shows the picture of co-micellization between primary and co-surfactant to enhance the solubility of
primary surfactant. One can perform various analytical measurements to confirm the mechanism of primary
surfactant solubility by either solvency or mixed micelle formation.
Figure 12 Mixed micelle formation between primary and co-surfactant to enhance the salt tolerance and high
temperature stability.
The first step in our experimental design was to perform cloud point measurements to test aqueous stability of
surfactant and formulations (consisting of surfactants and additives) at high salinity conditions (total dissolved
solids (TDS) at 22% w/w). The brines used in the experiments reported in this paper consisted of sodium
chloride, calcium chloride and other salts.Through these initial experiments, we identified a surfactant that is
soluble in brine at 10% TDS up to a temperature of approximately 80°C (Surfactant “1”). We also identified a
surfactant formulation that is soluble in brine at 22% TDS up to a temperature of 80°C (Formulation “1”). Our
next set of experiments consisted of cloud point measurements to determine the maximum temperature at
which Surfactant “1” and Formulation “1” are soluble in brine at various salinity levels, from 10% to 22%
TDS. Additional phase behavior studies included aqueous stability in brine for up to 96 hours, oil-water IFT
measurements, and oil emulsion forming tendency. Carbonate rock adsorption and chromatographic separation
was also evaluated. Finally, studies to assess the potential of the developed surfactant and formulation as
wettability altering agents to improve cumulative oil recovery were performed. Details on the experiments and
results are discussed below.
Surfactant Phase Behavior Studies: Cloud Point
Cloud point measurements were performed to determine the maximum temperature at which Surfactant “1” and
Formulation “1” are soluble in various reservoir brine compositions. Reservoir brine “1” has very high salinity
with total dissolved salts (TDS) of 215,463 ppm with divalent (calcium + magnesium) ions of 20,552 ppm.
Reservoir brine “2” has salinity of 100,977 ppm with divalent ions of 11,390 ppm. Reservoir brine “3” total
TDS of 51,865 ppm with divalent ions concentration of 6,195 ppm. Cloud point is measured using a high
pressure high temperature stainless steel cell with a Sapphire glass window. This method is particularly useful
when the cloud point temperature is above 100 °C. This experiment is performed by visual observation of the
surfactant solution through sapphire window. The temperature at or above which solution clouds out is
measured as cloud point temperature. Image analysis was performed using the brightness of the pixel point as
shown in Error! Reference source not found..
Contact Angle Measurements with Model Rock Surfaces

Clean calcite plates were polished and soaked in reservoir crude oil at 50 ˚C for about three week period to
bring the surface to reservoir wettability state. Kruss DSA 100 instrument was used to measure contact angle of
1) Reservoir brines and 2) Surfactant/formulation solution on aged calcite plates. Figure 14 shows the measured
contact angles at various brine compositions. Both “Surfactant 1” and “Formulation 1” are able to alter the
wettability of the calcite plate from oil-wet to water-wet.
Figure 13Surfactant cloud point measurement in reservoir brine “3” using formulation “1”. The cloud point of
the formulation “1” is in the range of 115 – 120 oC.
Figure 14Contact angle measurement test for various brines with and without surfactant present

Conclusions:
Experimental work performed with various surfactants and co-solvents with dodecane oil show that the current
gaps in the chemical flooding technology area may be filled with Dow’s portfolio of co-surfactants and co-
solvents. An automated high-throughput screening approach provides accurate mapping of various
formulations for SP/ASP applications such as:
1. Aqueous stability map of salinity and surfactant formulations

2. Regions of salinity where type III microemulsion is formed
3. Qualitatively characterization ofmicroemulsion viscosity and the effect of co-solvents on
viscous phases
For wettability alteration, we have proposed a novel surfactant formulation which is table up to 5.2% brine
salinity and temperature up to 120 °C. We have successfully proposed formulations that are efficient
wettability modifiers and can be potentially applied under a wider range of temperature and salinity conditions
during waterflooding of tight carbonate reservoirs. The formulations proposed were evaluated for aqueous
stability, emulsion tendency, and oil recovery experiments. Formulation “1” was tested by measuring contact
angle alteration, surfactant adsorption on dolomite, and chromatographic separation of the components of the
formulation. Formulation “1” was also tested in core flood experiments which show a significant incremental
oil recovery.
Novel formulations proposed in this study can be utilized in changing wettability of tight fractured reservoir
rocks. Similar surfactants have been utilized in a field case study where water injectivity improvement during
the surfactant treatment was observed. These surfactantscan also be leveraged to the unconventional tight
reservoir to improve oil recovery from oil wet shale rocks.
References
1) Abdallah, W., Buckley, J.S., Carnegie, A., Edwards, J., Herold, B., Fordham, E., Graue, A., Habashy,
T., Seleznev, N., Signer, C., Hussain, H., Montaron, B., Ziauddin, M. 2007. Fundamentals of
Wettability. Oilfield Review19 (2): 44–61.
2) Bennetzen, M.V., Mogensen, K., Frank, S. and Mohanty, K. 2014. January. Dilute Surfactant Flooding
Studies in a Low-Permeability Oil-Wet Middle East Carbonate. In IPTC 2014: International Petroleum
Technology Conference.
3) Bourrel, M., & Schechter, R. S. 2010. Microemulsions and related systems: formulation, solvency, and
physical properties. Editions OPHRYS
4) Gupta, R., Mohan, K., & Mohanty, K. K. 2009. Surfactant Screening for Wettability Alteration in Oil-
Wet Fractured Carbonates. Society of Petroleum Engineers.
5) Healy, R. N., & Reed, R. L. 1974. Physsicochemical Aspects of Microemulsion Flooding. Society of
Petroleum Engineers.
6) Hirasaki, G., & Zhang, D. L. 2004. Surface Chemistry of Oil Recovery From Fractured, Oil-Wet,
Carbonate Formations. Society of Petroleum Engineers.
7) Hirasaki, G. J., van Domselaar, H. R., & Nelson, R. C. 1983. Evaluation of the Salinity Gradient
Concept in Surfactant Flooding. Society of Petroleum Engineers.

8) Huh, C. 1979. Interfacial tensions and solubilizing ability of a microemulsion phase that coexists with
oil and brine. Journal of Colloid and Interface Science, 71(2), 408-426
9) Jadhunandan, P.P., Morrow, N.R. 1991. Spontaneous Imbibition of Water by Crude Oil/Brine/Rock
Systems. In Situ 15(4): 319–345.
10) Matero, A. (2001). Hydrotropes. In Holmberg, K. (Ed.), Handbook of Applied Surface and
ColloidChemistry (407-420). England: John Wiley&Sons, Ltd.
11) Melrose, J. C. &Brandner, C.F. 1974. Role of capillary forces in determining microscopic displacement
efficiency for oil recovery by waterflooding. Journal of Canadian Petroleum Technology, 13(04)
12) Mohan. K. Gupta, R. Mohanty, K.K. 2011. Wettability Altering Secondary Oil Recovery in Carbonate
Rocks. Energy & Fuels25 (9): 3966–3963.
13) Morrow, N. R. 1990. Wettability and Its Effect on Oil Recovery. Journal of Petroleum Technology 42
(12): 1476 –1484.
14) Schick, M.J. (Ed.). Nonionic SurfactantsPhysicalChemistry. Marcel Dekker, New York (1987), p.p.
150-157
15) Sharma, G., Mohanty, K. 2013. Wettability Alteration in High-Temperature and High-Salinity
Carbonate Reservoirs. SPE Journal18(4): 646–655.
16) Sheng, J. 2010a. Modern chemical enhanced oil recovery: theory and practice. Gulf Professional
Publishing
17) Sheng, J. J. 2013. A Comprehensive Review of Alkaline-Surfactant-Polymer (ASP) Flooding. Society
of Petroleum Engineers.
18) Sheng, J.J. 2013. Review of Surfactant Enhanced Oil Recovery in Carbonate Reservoirs. Advances in
Petroleum Exploration and Development6 (1): 1–10.
19) Stegemeier, G. L. 1974. Relationship of Trapped Oil Saturation to Petrophysical Properties of Porous
Media. Society of Petroleum Engineers.
20) Taber, J. J. 1969. Dynamic and Static Forces Required To Remove a Discontinuous Oil Phase from
Porous Media Containing Both Oil and Water. Society of Petroleum Engineers.

Title: “Drilling Fluid Design As A Relacement Of Kcl”

-Bishwjeet Binwal, Noida Institute of Engineering and Technology
Keywords: LSM, Potassium sulphate, Replacement, Bentonite clay.
Abstract:
During the study various formations were prepared to replace KCl from drilling fluid system. KCl should be
replaced from drilling fluid due to its environmental impact on the area around the rig, where the well is
digged. Potassium chloride is non indigenous and imported at high cost. It interfaces with ion exchange
mechanism of plants around drilling areas and a decrease the fertility and yield of agricultural plants when
reaches fields. The various formations used to replace KCl were tested on Bentonite pellet. Bentonite clay was
used to check the inhibition of various formations because it is the worst case. If Bentonite gives the better
inhibition in these formations less than KCl then these formations can easily give better inhibition on the
cuttings of the oil well. If KCl is replaced from drilling fluid system during the well drilling than the area
around the rig will not affected due to KCl and right now in India KCl is being imported from countries like
China. So it will also reduce cost of well drilling. In this study sodium formate (HCOONa), CHS (polyamine),
potassium sulphate, potassium formate (HCOOK), sodium chloride (NACL) these samples were tested on LSM
(Linear Swell Meter) with Bentonite pellet for 4 hours. Here, KCl was also tested with Bentonite pellet on LSM
for 4 hrs so that we can compare swelling percentage of these samples. Few samples were combinations also
like combination of CHS and HCOONa, CHS and potassium sulphate. In these samples who gave better
inhibition with Bentonite pellet then drilling fluid was designed with other formations. The formulation of
drilling fluid is further discussed in paper. Combination of 3% potassium sulphate with 2.5% CHS gave better
inhibition in these samples which were tested on LSM.
Introduction:
The drilling-fluid system commonly known as the “mud system” is the single component of the well-drilling
process that remains in contact with the wellbore throughout the entire drilling operation. “Drilling fluid is as
important to a drilling well as blood is to a human body.” Mainly drilling fluid system is of oil, water and
pneumatic based. In most of the wells water based drilling fluid is used. Water-based fluids (WBFs) are used to
drill approximately 80% of all wells. The base fluid may be fresh water, seawater, brine, saturated brine, or a
formatebrine. The active drilling-fluid system comprises a volume of fluid that is pumped with specially
designed mud pumps from the surface pits, through the drill string exiting at the bit, up the annular space in the
wellbore, and back to the surface for solids removal and maintenance treatment as needed. The capacity of the
surface system usually is determined by the rig size, and rig selection is determined by the well design. In
drilling fluid KCl and other salts are used to make mud formations. Due to these formations the cuttings are
transported from the bottom of the rig to the surface of well. [1, 2]
Potassium chloride (KCl) is used for shale inhibition in KCl drilling fluid systems and as a brine in Mixed Salt
Systems. Potassium chloride (KCl) is a soluble salt that is an extremely efficient shale stabilizer when drilling
hydro sensitive clays and shales. Inhibition is provided through ion exchange; the potassium ion enters between
the individual clay platelets in the shale so that they are held together, thus eliminating entry of water from the
drilling fluid. Potassium chloride is used at concentrations of 10 to 37 lb/bbl (28.5 to 105.6 kg/m3) for shale-
inhibition purposes. Actual level is based on shale testing and knowledge of the formation. Therefore, some

operators use as much as 80.5 lb/bbl (230 kg/m3) as determined by wellbore stability modeling. But KCl has a
vast impact environment: [3]
• KCl cause damage to germinating seedlings, inhibits the uptake of other minerals and reduces the
quality of the crop
• Potassium chloride is non indigenous and imported at high cost
• It interfaces with ion exchange mechanism of plants around drilling areas
• It decreases the fertility and yield of agricultural plants when reaches fields
Due to these and many other environmental problems KCl shouldn’t be used in rigs during well construction.
Below are the functions of the substitutes which can be used to replace KCl from drilling fluid. [4]
Table 1. Functions of chemicals
SUBSTITUTES FORMULAE MOLAR MELTING SOLUBILITY DENSITY

CAN BE USED MASS POINT
SODIUM HCOONa 68.01 2530C Soluble in 1.92 g/cm3
FORMATE g/mol glycerol, alcohol, (200)
formic acid
POTASSIUM HCOOK, 84.12 167.50C Soluble in 1.91 g/cm3
FORMATE HCO 2 K g/mol alcohol
SODIUM NaCl 58.44 8010C Soluble in water, 2.16 g/cm3
CHLORIDE g/mol ammonia,
methanol,
glycerol, etc.
POTASSIUM K 2 SO 4 174.259 1,0690C Slightly soluble 2.66 g/cm3
SULHATE g/mol in glycerol
EQUIPMENTS AND SOFTWARE USED

To study the inhibition capacity of samples (HCOONa, CHS, K 2 SO 4 , etc) with Bentonite pellet LSM (Linear
Swell Meter) was used. It helps to determine shale hydration or dehydration. Drilling problems such as stuck
pipe, tight hole, washout, and sloughing can be related to shale stability. The Linear Swell Meter Model (LSM)
helps determine shale hydration or dehydration by measuring the increase or decrease in length over time of
reconstituted or intact shale core.
Together the LSM and Capillary Suction Time (CST) tests determine the recommended mud system for
drilling through a specific shale formation. First, a CST test is conducted to determine the correct inhibitor for
the shale. Then, a variety of fluids are tested. Test results are graphed to show the percent of swelling versus
swelling time in minutes. The LSM test demonstrates the inhibitive effects of these various fluids on shale
swelling. [5]
The equipments used in study were Fann Viscometer, Compactor for LSM, Hamilton Beach Model
HMD400, Hot Roll Oven, HTHP (High Temperature High Pressure) Filter Press, API (American
Petroleum Institute) Filter press.
Viscometer was used to check the Plastic viscosity (PV), Gelation (gel 0 , gel 10 ), apparent viscosity (AV) and
Yield point (YP). With the help of these we will get the thixotropic property of the drilling fluid. Compactor

was to use to make pellet of Bentonite clay explained further. The HTHP fluid loss test indicates information
on drilling mud filtration into the formation under a static condition over a certain period of time.
The series 300 API Low Pressure Low Temperature (LPLT) Filter Press consists of a mud reservoir mounted in
a frame, a pressure source, a filtering medium, and a graduate cylinder for receiving and measuring filtrate. The
basic unit has a cell assembly constructed of stainless steel and includes the required screen and gaskets. [6]
EXPERIMENTAL PROCEDURE
3.1. Chemicals
The chemicals used here were imported from CDH (Central Drug House (P) Ltd.), Daryaganj, New Delhi-
110002 (India); Molychem, 78/80 Babu Genu road, Mumbai 400002, India and few were imported from M-I
Overseas Ltd., Navi Mumbai 400710, India. All these chemicals were available in R&D lab at IDT-Dehradun
3.2. Procedure
To replace KCl first some samples are required which we can use to replace KCl. So samples of sodium
formate, potassium formate, potassium sulphate, CHS (polyamine), sodium chloride were prepared. The
samples used in this study were 2.5% CHS, 5% HCOONa + 2.5% CHS, 10% HCOONa + 2.5% CHS, 4%
potassium sulphate and 3% potassium sulphate + 2.5% CHS, and 4% potassium sulphate.
Bentonite clay was first dried in hot roll oven for 16 hrs than 20 gm of Bentonite was measured to prepare
Bentonite pellet. These pellets were prepared at a pressure around 10,000 psi for half hr in a compactor. 2
pellets are prepared at a time in a compactor. Once the pellets are prepared then it should be kept in decicator to
avoid swelling. Below is the figure showing swelling in Bentonite pellet using these samples.
Fig1. Linear and gradual swelling of Bentonite pellet

At a time 4 samples can be tested in LSM. 4 cells are presented in LSM which can be increased to 8, if there
are 8 cells then at a time inhibition of 8 samples can be tested. For better results water should be used as a
sample in one cell so that comparison of swelling with Bentonite can be easily done. If swelling of Bentonite is
more in water in comparison with other then its inhibition is better and if swelling of samples is more than
water then that sample has worst inhibition. In LSM swelling is checked w.r.t. time for 4 hrs. Time can be
increased but in these samples 4 hrs is the optimum time which was taken. The swelling of Bentonite pellet
with water is around 22% while with cuttings from drilling is 16%. So if the swelling is less than 22% of these
samples than they are good inhibitors.
Fig2. Working of LSM with 3 samples
Once the swelling of these samples with Bentonite pellet was obtained then its comparison was held as shown
in results table. The inhibition of 3% potassium sulphate + 2.5% CHS was better as compared to other samples,
which means that this combinations formation can be used in drilling fluid as a substitute for KCl. But it has its
merits and demerits which are further discussed.
After getting the better inhibition in this sample we prepare the drilling mud with this combination of
potassium sulphate and CHS taking the same percentage used in LSM. Two rheologies were taken of this mud
one before putting the mud in hot roll and other was taken after putting the mud for 16 hrs in hot roll oven. The
weight of mud was taken after hot roll in instrument named Mud Balance. Once the Rheology was taken after
hot roll then its HTHP and API was taken.
Formulation of the drilling fluid prepared with 3% K 2 SO 4 + 2.5% CHS;

3.3. FORMULATION OF DRILLING FLUID

T/W + 0.1% Biocide + 0.1% Soda ash + 3% Potassium sulphate + 2.5% CHS + 0.3% XCP + 0.3%
PHPA + 1.5% PAC (LVG) + 0.1% SS + 2% SA + 5% Polyol Gd. II + 6% MCC + Barite (1.40)
Table 2. Rheology of mud formulation
Parameter BHR (Before hot roll) AHR (After hot roll)

0
(140 C for 16 hrs)
Specific Gravity 1.40 1.40
Ph 8.9 8.3
Rheology Temp Temp
(24±2) °C (46±2) °C
θ 600 150 110
θ 300 90 68
AV 75 55
PV 60 42
YP 30 26
θ 200 70 56
θ 100 45 38
θ6 15 12
θ3 10 07
Gel 0 10 08
Gel 10 12 10
API (ml) 2.3 ml 3.2 ml
HTHP (ml) - 19 ml
RESULTS AND DISCUSSION

The following results were obtained on Linear Swell Meter (LSM) in which following samples were tested
with Bentonite pellet as shown in Table 3 in next page.
Table 3. Swelling of Bentonite pellet

Sr. no. Sample Bentonite pellet LSM run time Swelling
depth percentage
1. Water 0.589 4 Hours 22%
2. 2.5% CHS (Polyamine) 0.579 4 Hours 12%
3. 5% HCOONa + 2.5% CHS 0.591 4 Hours 10%
4. 10% HCOONa + 2.5% CHS 0.587 4 Hours 9.5%
5. 4% Potassium sulphate 0.581 4 Hours 11%
6. 3% Potassium sulphate + 2.5% 0.592 4 Hours 9%
CHS

4.1. Discussion
After running the following samples on LSM it is clear that combination of Potassium sulphate and CHS gives
better inhibition on Bentonite pellet as compare to other samples. And if combination of 3% Potassium
sulphate with 2.5% CHS gives better inhibition in Bentonite pellet than definitely it will give less inhibition on
cuttings obtained during well drilling, because Bentonite clay is the worst case. If any sample is giving better
inhibition in Bentonite then it will provide more inhibition on cuttings.
KCl can be replaced by this combination in drilling fluid design. And in few rigs potassium sulphate is already
using in drilling fluid. But potassium sulphate contains sulphur which makes toxic gases if used at the bottom
of well. So potassium sulphate is used only on the surface.
Conclusion
Hence, it is conclude that combination of potassium sulphate and CHS gives better inhibition than the other
samples and it can be used as substitute for KCl. But this combination can only be used in surface because it
has sulphur which will form toxic gases if use at the bottom. Further study is required to find more substitutes
which can replace KCl from drilling fluid.
Acknowledgment
It gives me immense pleasure to express my gratitude and indebtedness to IDT-ONGC, DEHRADUN for
allowing me to work in this prestigious institute. My heartfelt thanks to my project mentor Mr. Vishesh Nath,
GM (Chemistry), In charge-DF (R&D) TG, who allowed me to do this project in Drilling Fluids and has
been very supportive and helpful throughout the duration of training. Their constant guidance has been a source
of inspiration for me throughout this project. I express my special gratitude to and Mr. Ved Prakash for
delivering practical knowledge to me and making me aware about the different equipment’s used in laboratory.
Their constant help in all the experimental work is highly acknowledged.
References
[1] Drilling Fluid: state of art, Ryen Caenn & George V. Chillinger
[2] Drilling engineering, J.J.Azar & G. Robella Samuel.
[3] https://www.amcmud.com/product/potassium-chloride-kcl/
[4] https://www.lenntech.com/periodic/elements/k.htm.
[5]https://www.fann.com/fann/products/drilling-fluids-testing/shale-
test/lsm.html?nodeId=1_leveltwo_25&pageId=Products
[6]https://www.fann.com/fann/products/drilling-fluids-testing/filtration-api-lplt/lplt-
fp.html?nodeId=3_leveltwo_0&pageId=Products

Title: “Solutions to the carryover issues in the LPG Treating units: A case study”
-S. K. Ganguly1,*, S. Kumar1, C. B. Mazumdar2 & A. Ray1, 1CSIR-Indian Institute of Petroleum,
& 2Department of Chemical Engineering, Indian Institute of Technology
Keywords: LPG, NGL, Sweetening, Mercaptans, Catalyst, Carryover
1.0 Abstract
The unique Middle East (M.E.) configuration in LPG (propane-butane) treating units with common oxidizers
processing two different spent caustic streams (e.g., from the RFCC and CDU LPG units in refineries or
propane and butane sweetening units of Natural Gas Liquids (NGL) fractionation plants with variable and high
mercaptide loading often leads to higher foaming tendencies resulting in carryovers. The solution to this issue
demands a holistic approach, which includes process parameter optimization and reformulation of the catalyst
by incorporation of suitable additives.
The criterion for catalyst selection in the M.E. is therefore very stringent. M.E Refineries usually look for LPG
sweetening catalyst which not only are active, meet LPG (propane-butane) product quality requirements in
terms of mercaptan levels but also have a formulation which can sustain varying mercaptide loads with
minimum chances of carryover without compromising on catalyst activity.
The paper discusses in detail about the studies on the effect of operating process parameters like mercaptide
levels, temperature, shear, and catalyst concentration on carryover tendencies. The studies conducted indicated
the need for parameter optimization to reduce the occurrence of carryovers. Further, to minimize the chances of
carryover, detailed investigations on the effect of various additives on carryovers were conducted. It was found
that a formulation involving a mixture of two different additives gave the best results. This reformulated
catalyst was scaled up and trailed in the M.E refineries. On performance analysis, it was found that the average
catalyst consumption level reduced (concerning competing catalyst) by 50% with no instances of carryover.
Further, its higher activity resulted in 20% less caustic drainage, which is an added advantage from an
environmental standpoint.
It may thus be concluded that a combination of the optimization of operating process conditions and
reformulation of the sweetening catalyst resulted in a holistic cost-effective catalyst changeover in the LPG
(propane-butane) M.E. sweetening units.
2.0 Introduction
CSIR-IIP (“IIP”) in collaboration with Bharat Petroleum Corporation Ltd (“BPCL”) developed a catalyst
(Thoxcat ES) useful for sweetening of Liquefied Petroleum Gas (LPG) and light petroleum fractions like Light
Straight Run Naphtha (LSRN). This catalyst was commercialized in 2007.
To increase our client list, IIP and BPCL (R&D) are jointly working to implement the catalyst in refineries
outside India, starting with Middle East (M.E.) which holds 10-15% of the global sweetening catalyst market.
As a result of our efforts, we have been able to commercialize our catalyst first time outside India in 2016 at
Oman Oil Refineries and Petroleum Industries Company, Oman (ORPIC). Based on the success story of our
catalyst performance at ORPIC; Saudi Aramco, Saudi Arabia (Aramco) has also approached us for a trial run.

However, during our trial runs, we have noticed that the operating conditions in the M.E. refineries are quite
different than what we have in Indian refineries. One key issue we encountered during trials at ORPIC, Oman
was frequent carryovers. This is found to be dependent on higher foaming tendencies, which is attributed to
high and fluctuating mercaptide levels in the common oxidizer feed. This variation in mercaptide load was
being caused due to the processing of rich caustic streams from both Resid Fluidized Catalytic Cracking
(RFCC) and Crude Distillation Unit (CDU) LPG sweetening units in a common oxidizer. Further, the rich
caustic from the CDU LPG sweetening unit had high mercaptides with the variable flow, which explains the
high and variable mercaptides in the combined feed to the common oxidizer. A similar oxidizer configuration
exists in Aramco’s propane-butane sweetening unit as well.
This is quite a different design and not prevalent in the Indian Refineries. Apart from this, the average ambient
temperatures in the M.E. are much higher during the entire year than average Indian temperatures, which are
also hypothesized to augment this carryover phenomenon. It was essential for us to re-look at our strategies and
formulations to see how we may incorporate a better foam control feature to minimize the chances of
carryover.
3.0 Process Description

The extractive sweetening process involves two stages, starting with extraction and culminating with oxidation.
The lighter mercaptans are first extracted by caustic solution forming water and sodium mercaptide salts as
shown in eq. (1).
2RSH oil + 2NaOH aq 2NaSR aq + 2H 2 O aq

(1)
In the second stage, shown in eq. (2), these salts (NaSR) are oxidized by air injection in the presence of a
catalyst, to an organic disulfide (RSSR). This organic disulfide phase separates by gravity (separator) from the
aqueous caustic solution. After decantation of disulfides, the regenerated lean caustic solution is re-circulated
back to the top of the extractor to continue extracting mercaptans [1-7].
2NaSR aq + H 2 O aq +1/2O 2aq 2 NaOH aq + RSSR oil

(2)
Overall Reaction
Catalyst
2RSH oil + 1/2O 2aq RSSR oil + H 2 O aq
(3)
NaOH
4.0 Catalyst Development

Metal phthalocyanines are reported to be the most effective sweetening catalyst [8, 9]. However, the solubility
of metal phthalocyanine is low in an aqueous medium. To overcome this, derivatives like sulfonated and
carboxylated forms were developed. Cobalt phthalocyanine disulphonate is commonly used as a commercial
sweetening catalyst. The liquid form of this catalyst becomes viscous and forms a gel on extended storage. To
overcome this, a highly soluble tetrasulphonate form of the catalyst could be used; however, it also has lower
activity. To further improve upon the existing catalysts, a novel cobalt phthalocyanine sulfonamide catalyst was
developed [10, 11]. The catalyst was prepared using cobalt phthalocyanine by carrying out chlorosulphonation
in the temperature range of 110 – 1400 C for 4-6 h followed by amidation in the temperature range of 60 – 800
C for 1-3 h. The catalyst was characterized using elemental analysis and spectroscopic techniques like Infrared
spectroscopy (IR) and Fast atom bombardment mass spectroscopy (FAB). Analytical results confirmed that the
catalyst mainly consisted of cobalt tetra sulphonamide. Laboratory evaluation of this catalyst showed enhanced
activity as compared to a commercial catalyst with comparable stability. Details of synthesis, characterization,
and evaluation procedures are mentioned elsewhere [12].
5.0 Experimental Methods

5(a) Design of experimental set-up: An innovative set up was created to study the parametric effects on the
foaming tendencies of the catalytic thiol oxidation process. A column set up-fitted with sintered glass at the
base connected with a gas flow meter for introducing air with quantified airflow was fabricated. The system
was established to represent near industrial conditions to arrive at a logical conclusion. Further, the same
system was used to study the effect of additives on foam control tendencies.
5(b) Experimental procedures

Calculated amount of Thoxcat ES catalyst required for maintaining a catalyst concentration of 100 to 800 ppm
was dissolved in 14 wt.% NaOH solution used as the representative feed to the oxidizer. The mixture of NaOH
and catalyst solution was poured in the jacketed glass column reactor maintained at around 400 - 500 C under
nitrogen atmosphere. Ethane thiol was chosen to be the representative mercaptan. The desired amount of
ethanethiol to make initial mercaptide concentration 10000 to 30000 ppm was injected in the reaction mixture
along with nitrogen purge for a few minutes for thoroughly mixing of the thiols in the mix. The gas flow was
then quickly changed from nitrogen to air. This marked the zero time of the mercaptide conversion reaction.
The flowrates were varied in the range of 0.1 LPM to 1 LPM corresponding to 20 to 200 cm/min superficial air
velocity to get the parametric effects over the entire range. The color of the reaction mixture was initially found
to be dark brownish-black at the start of the reaction. The completion of the reaction was indicated by the
appearance of a light blue color. The time needed for complete conversion was noted as the reaction time. The
additives were added in such quantities so that it ranged from 37 ppm to 100 ppm when compared to plant
conditions. The results of these experimental runs have been reported in Table 1. The Inter Facial Tension
(IFT) measurements were carried out using Drop Shape Analyser (DSA 25) from Ms. KruSS GmbH, Germany.
6.0 Results & Discussions

Effects of various critical operational parameters and additives on carryover were looked at:
Effect of superficial air velocity: The experiments were conducted over a wide range of superficial air
velocities ranging from 20 to 200 cm/min. Considering that the primary medium inside the oxidizer during
oxidation is 15 wt. % caustic over a range of 40 0C to 50 0C, a detailed experiment was conducted shown in
Figure 1. The net foaming height was measured as a function superficial gas velocity both at 40 0C and 50 0C.
For comparison, the same experiment was repeated with water at similar conditions as well. We have calibrated
our foam studies experimental set up with industrial results, and it has been established from our experience
that, foaming tendencies above 15 cm have higher chances of carryover. Considering this as a basis, it is
essential to restrict the superficial air velocity to 60 cm/min to minimize the chances of carryover. To
investigate further to find a plausible reason for such a phenomenon IFT of water and 15 wt. % alkaline water
were determined to be 71.56 dynes/cm and 39.95 dynes/cm respectively. The reduction in IFT, possibly
explains the higher foaming tendencies of the alkaline water medium (compared to water) in the oxidizer.
Effect of mercaptides level in oxidizer feed: The experiments were conducted at two levels, i.e., 10000 ppm
as well as 30000 ppm at 40 cm/min and 40 0C. The increase in mercaptide levels led to increasing foaming
tendencies by a factor of 1.5 to 2 times. It is desirable to maintain the oxidizer feed mercaptide level below
10000 ppm. The caustic to LPG ratio is the deciding criterion for mercaptide levels in the oxidizer feed line.
The recommended ratios being LPG feed mercaptan level specific and can be optimized as per standard
industrial practices. Therefore, in the plant, the matter could be handled by increasing the caustic flowrates to
the extractor.
Effect of catalyst concentration: Catalyst (cobalt phthalocyanine tetra-sulphonamide) concentration was

varied in the range of 100 to 800 ppm. The experiments were conducted by at 10000 ppm mercaptide levels at
40 cm/min and 40 0C. Figure 2 shows the effect of increased dosage of catalyst on carryovers. As the catalyst
dosage level increases, the conversion time decreases, but at the same time, the foaming rates increases — the
optimum lies around 225 ppm.
Effect of additives: Further to parametric controls like shear, mercaptide levels, catalyst concentration,
foaming may also be controlled by the addition of additives (antifoams or defoamers). Different types of
additives were tried, and their net foaming heights were recorded, as shown in Table 1. It was observed that a
combination of polymeric and oxo-alcohol additives performed the best. The formulation was scaled-up and
trailed at the M.E. refineries.
Performance of the reformulated catalyst: The scaled-up catalyst was tried at both the M.E. refineries. At
ORPIC, RFCC LPG feed mercaptan level processed during the trial period ranged from 404 ppm to 921 ppm
with an average of 665 ppm. The processing capacity of RFCC LPG extractor was around 1 MMTPA. The
RFCC LPG product mercaptan ranged from 0.41 ppm to 3.65 ppm, with an average of 2.05 ppm, which meets
quality requirements (max 5 ppm). Similarly, the RFCC LPG product total sulfur ranged from 1.20 to 5.64
ppm, with an average of 3.36 ppm, which also meets product quality requirements (max 10 ppm). The results
of performance were similar for the Aramco trial as well with, 40 - 50% lesser catalyst consumption in both the
cases. The use of this catalyst resulted in 20% lesser caustic discharge in the case of Aramco, leading to
reduced release to the Effluent Treatment Plant (ETP) [13].
Effect of derivatization: Changing the substitutions leading to new derivatives of the cobalt phthalocyanine
have shown reduced foaming tendencies and could also be a complementary way of handling the carryover
issue. The performance of this molecule is shown in Figure 3. The experiments were conducted with
mercaptide levels of 16500 ppm at a superficial air velocity of 40 cm/min and temperature of 40 0C. This
performance is depicted without the addition of any additive. Results show that the activity of the modified
catalyst is comparable to the available industrial reference with acceptable foaming tendencies of 11 cm (the
threshold being 15 cm). Hence derivatization also appears to be an alternate method of foam control [14].
7.0 Conclusions
The salient conclusions for the reduction in carryover issues from this study were:
i. The maximum recommended superficial air velocity is 60 cm/min in the oxidizer.

ii. It is desirable to maintain feed mercaptide levels to oxidizers less than 10000 ppm.
iii. The maximum catalyst loading recommended is 225 ppm.

iv. A blend of two different types of additives, namely polymeric and oxo-alcoholic was successful in
handling carryover issues most effectively.
v. Substitutions of cobalt phthalocyanine ring to obtain ammonium salt of the sulfonated cobalt
phthalocyanine also appears to be a complementary solution for handling carryover issues.
Acknowledgments
The authors acknowledge the efforts and cooperation of the Speciality Chemicals and Petrochemicals team at
CSIR IIP (Dr. Suman L Jain and Dr. P K Khatri) in developing the greener catalyst which was evaluated in
Sweetening Lab. We express our gratitude to Sh. O. P. Sharma, TO of Surface Science team at CSIR IIP for
the IFT analysis.
References
[1] S. Prakash, Refining Processes Handbook, Gulf Professional Publishing, Burlington, MA, 2003.
[2]R. A. Meyers, Handbook of Petroleum Refining Processes, 3rd ed., McGraw-Hill, New York, NY 2004.
[3]G. D. Hobson, W.Pohl, Modern Petroleum Technology, Applied Science Publishers, Great Britain, GB
1975.
[4] A. Jain, N. Rathi, S. K. Ganguly, Pet. Sci. Technol. 2012, 30(23), 2494-2503.
[5] S. K. Ganguly, A. Jain, N. Rathi, Pet. Sci. Technol. 2013, 31(4),428-437.
[6]S. K. Ganguly, N. Rathi, A. Jain, Pet. Sci. Technol. 2013, 31(12), 1283-1293.
[7]S. K. Ganguly, G. Das, S. Kumar, B. Sain, M. O. Garg, Hydrocarbon Proc. 2013, 92(6), 77-81.
[8]B. Basu, S. Satapathy, A. K. Bhatnagar, Catal. Rev. Sci. Eng. 1993, 35(4), 571–609.
[9]T. J. Wallace, A. Schriesheim, H. Hurwitz, M. B. Glaser, Ind. Eng. Chem. Process Des. Dev.1964, 3(2),
237–241.
[10]B. Sain, S. N. Puri, G. Das, B. P. Balodi, S. Kumar, A. Kumar, V. K. Kapoor, V. K. Bhatia, T. S. R. P.
Rao, G. P. Rai, US Patent No. 6 740 619, 2004.
[11]B. Sain, S. N. Puri, G. Das, B. P. Balodi, S. Kumar, A. Kumar, V. K. Kapoor, V. K. Bhatia, T. S. R. P.
Rao, G. P. Rai, UK Patent No. GB 2 371 300, 2004.
[12]G. Das, B. Sain, S. Kumar, G. Muralidhar, M. O. Garg, Catal. Today 2009, 141(1-2), 152–156.
[13]Performance evaluation of Thoxcat ES for ORPIC, Sohar Refinery, CSIR-Indian Institute of Petroleum
Report-no: CCD-130/2016, 2016.
[14]Feasibility studies of Green LPG sweetening catalyst, CSIR-IIP HARIT Report, June 2019.
Figure 1: Studies on the effect of superficial air velocity on foaming tendencies

Figure 2: Laboratory studies on the effect of Thoxcat ES concentration on mercaptide conversion time
and frothing rates
Figure 3: Foaming behavior using ammonium salt of sulfonated cobalt phthalocyanine catalyst

Table 1: Comparative performance of different additives w.r.t foam control
S Catalyst Code Additive Reaction Initial Final Net Remarks

No. type time Liq. Liq. frothing
(min) Ht. Ht. obs. (cm)
(cm) (cm)
1. Thoxcat-ES wet cake Nil 20 19 52 33 Used in
(Batch R-16019) formulations
2. Ref catalyst 1 Yes but 51 25 40 15 R. time: 50 min
N/A Foam ht.: 15 cm
3. Ref catalyst 2 Silicon 31 25 37 12 R. time: 30 min
(Batch R-15011) Oil Foam ht.: 12 cm
4 Thoxcat-ES wet cake Polymeric 23 25 45 20 Failed at 500C
(Batch R-16019) also
(2% Polymer A)
5. Thoxcat-ES wet cake Polymeric 29 27 31 07-11 Acceptable
(Batch R-16019)
(2% Polymer B)
6. Thoxcat-ES wet cake Mineral 16 27 34 07 Contains mineral
(Batch R-16019) Oil oil so dropped
(2.5% Mineral Oil)
7. Thoxcat-ES wet cake Silicon 50 28 60 32 Failed
(Batch R- 17011) Oil
(2wt% Silicone oil)
8. Thoxcat-ES wet cake Polyol 19 21 48 27 Failed
(Batch R-16019) Ester
(5wt% Polyol Ester)
9 Thoxcat-ES wet cake Blend 27 27 35 8 Best
(Batch R-16019) Performance
(1.6% Oxo-alcohol +
Polymer B)

Title: “Future of the Oil and Gas Industry (Apply Data Science to Analyze the Reservoir’s Hydrocarbon
Content)”
-Syed Inayathulla, Khaja Abdul Rahman, Dhaanish Ahmed College of Engineering,
Keywords: Digitalization, data science, predictive models, seismology
Abstract
Traditionally, the oil and gas industry has been collecting a variety of data, such as production data, log data,
geological data, completion data, artificial lift data, maintenance records, and data from permanent down hole
sensors. However, more often than not, most of these data are not used to the fullest extent possible. Data
science has been a booming technology that has been successfully implemented in many industries. The oil and
gas industry is undergoing a major revolution and there is a constant challenge faced by the industrial giants to
reduce the manpower and include digitalized forms of analyzing the reservoir properties so that there is a very
good chance of error reduction while drilling. Data science can help in moving from reactive remedial solutions
to proactive decision making and closed-loop reservoir management. Data science enables this through
integrating different kinds of data into predictive models (predictive analytics), which can then be used to
predict future reservoir/well/surface facility behavior, and then optimize such decisions to maximize the asset
value. R&D spending in geophysics centers around four main categories – acquisition, processing,
interpretation and hardware optimization – all rich in the three Vs of big data (volume, variety and velocity).
One raw seismic dataset is usually in the hundreds of gigabytes, resulting in terabytes once the numerous and
expensive processing and interpretations are finished. These processing algorithms calculate many billions of
data points with each run, and hundreds of these runs occur globally every day, all for one goal – create a clear,
accurate picture of the Earth’s subsurface and identify all of the major components of the hydrocarbon
systems.3D seismic data has been the industry’s most impactful scientific breakthrough. This data vastly
improves the picture of the Earth’s subsurface and removes the need to drill an extremely costly hole that costs
millions of dollars, with very little data, to explore the reservoir rock. Seismology has exclusively received the
most research attention trying to better tune data acquisition and processing in an effort to get a clearer image.
This paper exclusively deals with the integration and mining of data produced in the hydrocarbon finding and
producing process that can offer extraordinary potential for answering some of the big questions facing the oil
industry. 1)Where is more oil, 2) How do we get substantially more out of the ground safely, with minimal
environmental impact and how do we use data that has such potential to unlock these answers. The answers
can save billions of dollars and plenty of time.
1. Introduction
One of the major issues faced by the oil and gas industry currently is to reduce the manpower, maintenance cost
and improve the ability to locate the reservoir zones properly. It has been reported that managing these datasets
is a major concern among oil and gas companies. A report by Brole stated that petroleum engineers and
geoscientists spend over half of their time in searching and assembling data [1].This viewpoint and future
prediction among executives for 2018 become more interesting once we compare the findings by Feblowitz[2]
in 2013. There are different techniques of predicting the parameters of the rock like well logging, well testing,
simulation model and seismic survey to name a few. However, these techniques are not always approximate
compared to the actual situation. Hence the operator and service companies face a lot of issues if the predicted

calculation fails to be proved. The paper mainly deals with the applications of data science in the oil and gas
industry to solve issues in analyzing and finding the hydrocarbon content of the reservoirs in 4 different zones
(drilling, production, exploration and reservoir calculations) which could probably save a lot of capital,
manpower and time.
2. Procedure
2.1 Data Science (Definition)

Data science includes unstructured (not organized and text-heavy) and multi-structured data (including
different data formats resulting from people/machines interactions). However, more recent articles have added
two more Vs to give a better definition for Big Data[3]. The additional Vs include veracity and value [4]
2.2 Data science tools

As the Big Data is involving huge data sets, it is very important to have access to innovative and powerful
technologies. These future giant technologies should be very fast and accurate. In this section the tools and
technologies which are available for Data analytics are listed and displayed.
2.2.1 Apache Hadoop

Apache Hadoop is a collection of open-source software utilities that facilitate using a network of many
computers to solve problems involving massive amounts of data and computation. It provides a software
framework for distributed storage and processing of big data using the MapReduce programming mode.
The base Apache Hadoop framework is composed of the following modules:
Hadoop Common – contains libraries and utilities needed by other Hadoop modules;
Hadoop Distributed File System (HDFS)–a distributed file-system that stores data on commodity machines,
providing very high aggregate bandwidth across the cluster;
Hadoop YARN) - a platform responsible for managing computing resources in clusters and using them for
scheduling users' applications.
Hadoop MapReduce – an implementation of the MapReduce programming model for large-scale data
processing.
2.2.2 R Programming
R is a modern, functional programming language that allows for rapid development of ideas, together with
object-oriented features for rigorous software development initially created by Robert Gentleman and Robert
Ihaka. The powerful set of inbuilt functions makes it ideal for high-volume analysis or statistical simulations. It
also supports the packaging system, which means that the code provided by others can easily be shared.
Finally, it generates high-quality graphical outputs, so that all stages of a study, from modeling/analysis to
publication, can be undertaken within R. It can be said that R is a specialized language which includes various
modules and toolboxes to mainly facilitate the statistical computations. It can help with loading data,
conducting complicated computations, and finally visualizing the results and outputs. However, from data
processing point of view, R's major drawback is working with datasets that fit within a single machine's
memory
2.2.3. Python
Python is one of the most popular programming languages of recent times. Python, created by Guido van
Rossum in 1991, is an open-source, high-level, general purpose programming language. Python is a dynamic
programming language which supports object-oriented, imperative, functional and procedural development

paradigms. Python is very popular in machine learning programming.Python is one of the first programming
languages that got the support of machine learning via a variety of libraries and tools. Python has demonstrated
significant improvement in analzing the well log and seismic data to generate potential graphs.
2.2.4. Java
Java is a general-purpose programming language that is class-based, object-oriented(although not a pure object-
oriented language, as it contains primitive types) and designed to have as few implementation dependencies as
possible. It is intended to let application developers write once, run anywhere (WORA) meaning that compiled
Java code can run on all platforms that support Java without the need for recompilation. Java applications are
typically compiled to bytecode that can run on any Java virtual machine (JVM) regardless of the underlying
computer architecture[5]. Java has proven to be extremely helpful to make 3D and 4D models which inturn
makes it easy for the reservoir engineers to create proper documentation mentioning the productivity, porosity,
type and the permeability and wettability to name a few. It’s ability to link between the client and server made
Java extremely beneficial in logging and testing often done by oil and gas service companies.
3. Applications of data science in different oil and gas sectors
3.1. Data analytics in Exploration

Big Data was utilized to analyze the micro-seismic data sets to model the fracture propagation maps during
hydraulic fracturing. In this research, the authors used the Hadoop platform instead of conventional tools to
manage the massive datasets generated by micro-seismic tools[6]. Seismic images are like an ultrasound for the
Earth, and provide detailed regional information about the structure of the subsurface, including buried faults,
folds, salt domes, and the size, shape, and orientation of rock layers. They are collected by using truck-mounted
vibrators or dynamite (onshore), or air guns towed by ships (offshore), to generate sound waves; these waves
travel into the Earth and are reflected by underground rock layers; instruments at the surface record these
reflected waves; and the recorded waves are mathematically processed to produce 2-D or 3-D images of
subsurface features. Furthermore, the success ratio was improved by detecting the potential anomalies based on
the previous failed jobs.

Fig 1. 2010 Encyclopedia Britannica, Inc
3.2. Data Science in drilling

There are a ton of information and data which can be obtained while drilling the zones. These data which are
gathered from different operations through drilling can be applied to conduct various analyses from scheduling
to drilling operation
3.2.1. Real-Time Torque and Drag Calculations using Neural Networks

In drilling, both contextual data (in the form of daily drilling log reports) and structured visual data (obtained
through logging and captured in the electronic drilling recorder), need to be analyzed. Due to the time-bound
nature of drilling operations, real-time decisions need to be made. To this end, companies are using neural
networks, and analyzing rig states for real-time data visualization, and for predicting drilling key performance
indicators. Torque and drag on the drill strings in any given well can be calculated in real-time now using AI,
by estimating coefficient of friction and normal contact forces between the string and the wellbore[7].
3.3. Data Science in Reservoir parameters calculations

Big Data and data-driven methods were utilized to improve the CO2 sequestration by predicting the possibility
of CO2 leakage. For this purpose, two permanent downhole gauges (PDG) were installed in an observation
well to collect the pressure data.Data has also been used to optimize the selection and application of costly
enhanced oil recovery (EOR) methods. the researchers employed Big Data analytics to optimize the application
of EOR projects through an improved hydrodynamic reservoir simulation[8].

3.4. Data science in production zone
Fig 2 Alfonso R. Reyes(14 April 2016)
Moreover, Big Data has been successfully used to optimize the performance of electric submersible pumps
(ESPs). Sarapulov and Khabibullin[9]utilized Big Data to evaluate the performance of ESPs by identifying
emergency situations such as overheating and unsuccessful start-ups. For their study a total of about 200
million logs were gathered from 1649 wells during one year[10] [11].This has led to an ultimate change in the
recovery factor considering that a typical production well lasts for about 5-20 years and even more depending
upon the availability and its origin.
Results
Therefore, the mission of taking advantage of data science has successfully been proved by a plethora of
successful projects. The key lies in the ability to drive operation excellence to save margins and ensure
sufficient capital for reinvestment necessary for the production. So, it is highly likely that in the upcoming
times, data analytics will make it extremely simple and easy to predict the oil and gas bearing zones. A very
good data to show can be the “September Big Lost Reservoir and Streamflow Graphs, Big Lost Reservoir and
Streamflow Graphs” provided by the USDA (United States Department of Agriculture).

Fig 3. USDA (United States Department of Agriculture), September Big Lost Reservoir and Streamflow
Graphs
Fig 4. University of California - Santa Barbara

Conclusion
Along with Data Science, Personal and cyber security also need attention since this remains a perceived barrier
in realizing the value of big data analytics. Big data real-time analytics surely presents innovative opportunities
to establish more efficient oil production, cost and risk reduction, safety improvement, more regulatory
compliance and better decision-making. Good expertise and strategic prudence while using big data tools, will
not only ensure success but also reduce the errors that can result in improper subsurface knowledge.
Fig 5. Microsoft Big Data Appeal (2017)
Acknowledgements
I am very thankful to IOGCA Conference, Ahmedabad for giving me this opportunity to present my ideas as a
speaker with “Mr. Khaja Abdul Rahman (Co Author)”in the topic “FUTURE OF THE OIL AND GAS
INDUSTRY (APPLY DATA SCIENCE TO ANALYZE THE RESERVOIR’S HYDROCARBON
CONTENT)”for providing this wonderful opportunity. I express my sincere gratitude toDr. J. Senthil,
Professor and Head, Department of Petroleum Engineering, Dhaanish Ahmed College of Engineering
Padappai and the other members in my department who gave us the opportunity to present our ideas.
References
[1]M.R. Brulé, Group IBMS
The Data Reservoir : How Big Data Technologies Advance Data Management and Analytics in E & P
Introduction – General Data Reservoir Concepts DataReservoir for E & P (2015).
[2]J. Feblowitz, Insights IDCE,Analytics in Oil and Gas: the Big Deal about Big Data (2013) pp. 5-7
[3]H.E. Pence, What is Big Data and Why is it Important ?. vol. 43 (2015), pp. 159-171, 10.2190/ET.43.2.d
[4]J. Ishwarappa, J. Anuradha
A Brief Introduction on Big Data 5Vs Characteristics and Hadoop Technology, vol. 48 (2015), pp. 319-324,
10.1016/j.procs.2015.04.188
[5]"Java is pure object oriented or not?". Stack Overflow. Retrieved May 24, 2019.
[6]P. Joshi, R. Thapliyal, A.A. Chittambakkam, R. Ghosh, S. Bhowmick, S.N. Khan, OTC-28381-MS Big Data
Analytics for Micro-seismic Monitoring, (2018), pp. 20-23

[7]Insights from the SPE Data Science Convention 2019, https://towardsdatascience.com/@shubham0189

[8] J. Xiao, X. SunBig Data Analytics Drive EOR Projects(2017), pp. 5-8.
[9]E. Udegbe, E. Morgan, S. Srinivasan, T. Pennsylvania, SPE-187328-MS from Face Detection to Fractured
Reservoir Characterization : Big Data Analytics for Restimulation Candidate Selection(2017)
[10] S. Gupta, L. Saputelli, F. Corporation, M. Nikolaou, Big Data Analytics Workflow to Safeguard ESP
Operations in Real-time(2016), pp. 25-27
[11]B.T. Rollins, A. Broussard, B. Cummins, A. Smiley, N. Dobbs, Continental production allocation and
analysis through Big data, Unconv. Resour. Technol. Conf, Society of Petroleum Engineers, Austin (2017),
10.15530/urtec-2017-2678296

Title: “Rheology and Microstructure Behaviors of Zwitterionic-Anionic Surfactant for Fracturing”

-Silvia John Mushi, Wanli Kang, Hongbin Yang, Pengxiang Wang, Xiaoyu Hou, China University of
Petroleum
Keywords: Rheology; Viscoelasticity; Viscoelastic Surfactant; Fracturing
Abstract
Viscoelastic surfactant (VES) fluids are widely used in the hydraulic fracturing process to increase oil and gas
productivity. Zwitterionic (carbon-18) surfactant solution has high critical micelle concentration which requires
high surfactants concentration and thus uneconomical. Application of viscoelastic surfactant fluids in high-
temperature reservoirs is of great importance; zwitterionic-C 18 surfactant fluid is limited to this kind of
reservoirs due to the inability of withstanding high-temperature conditions. In the present study, the rheological
performance of oleylamidopropylbetaine (OAPB) has been enhanced synergistically by combining with
anionic sodium dodecyl sulfate (SDS) surfactant. Viscoelasticity and structural morphology properties of the
mixed fluid have been investigated by rheology, dynamic light scattering, and transmission electron cryo-
microscopy measurements. The performance of mixed surfactant fluid was discussed against the individual
concentration of OAPB solution. At neutral pH and room temperature, 2-4 wt% OAPB demonstrated viscous
fluid behavior with zero shear viscosity (η o ) of 62 mPa.s whereOAPB-SDS (OADS) solution demonstrated
elastic gel-like fluid behavior with zero shear viscosity of 3.5×106 mPa.s. Theimproved rheological properties
in OADS solution is due to electrostatic attractions between head groups of OAPB and SDS surfactants which
increased micellar contour length and network entanglements. The viscoelasticity and microstructural
properties of OADS solution are influenced by concentration, pH and temperature. The rheological properties
of OADS solution increased with molar concentration ratios while decreased with raising the temperature. The
strength of electrostatic interactions between mixed OADS surfactant strongly depends on the pH conditions of
the solution.Different pH conditions triggeredmicellarmorphology transformation from spherical at low pH
values to wormlike micelles at moderate and high pH values. Moreover, 3 wt% OADS solution maintained a
viscosity 66 mPa.s for two hours under 170 s-1 and 90 °C which can effectivelytransport proppant during
fracturing. The proppant settling velocity rate, gel breaking ability, core permeability damage and residual
content performance of OADS solution were within the acceptable standards of fracturing fluids. This study is
useful in understanding the properties of mixed zwitterionic-anionic fluids which is thermo-pH responsive,
valuable in the fracturing. Likewise, the surfactant mixture is cost-effective with high performance at a low
concentration of its components.
Introduction
Hydraulic fracturing is a technique of stimulatinglow or damaged permeability formations to increase oil and
gas productivity [1]. The properties of fracturing fluid arean essential key in the fracturing process. Fracturing
fluid must have sufficient viscosity and elasticity properties to generate an artificial fracture and transport
proppant into the generated cracks[2, 3]. Compared to conventional polymeric fracturing fluids, VES fluids is
more advantageous because it is easy to prepare, have good prop pant carrying capacity, have good gel
breaking ability, have minimal residue, and low formation damage [4, 5]. Zwitterionic surfactants have both
positive and negative charges in their hydrophilic heads where the hydrophilic part of anionic surfactant is
negative charge[6, 7]. Zwitterionic surfactants are different from other types of surfactants due to their
properties including high biodegradability[8], thermally stable [9], high aqueous solubility[10], and salt
tolerance[11] and therefore it is promising surfactant to form wormlike micelles (WLM) solution. The betaines

represent zwitterionic surfactants, they are fairly mild to the eye and skin, biodegradable, low toxicity,
resistance to hard water. The characteristic of betaine surfactant is influenced by their large head group which
affects the packing parameter and change micelles aggregation shapes in mixed micelles with the anionic
surfactant system[12, 13]. It has been discussed that the properties of mixed surfactants particularly in
zwitterionic-anionic surfactant are superior to that of individual surfactants[14, 15]. The superior properties of
mixed surfactants are due to a strong synergetic effect in mixed micelles caused by reduced electrostatic
repulsion between the head groups two molecules of surfactant[16]. The strong electrostatic interaction
between these surfactant molecules lowers critical micelle concentration and raise surface activity than that of
individual surfactant solution [14, 17, 18]. However, the synergism in mixed zwitterionic –anionic surfactant is
not only contributed by electrostatic interactions between zwitterionic and anionic head groups but also steric
interactions between different head sizes of surfactant and different lengths of hydrophobic chains
aresignificant sources of synergism[19].
The rheological properties of carboxybetaine surfactants such as OAPB are different from other amphoterics,
their hydrophilic head region has carboxyl group as negative moiety and quaternary nitrogen atom as
permanent positive charge irrespective of pH of the solution. Thus, depending on solution pH these surfactants
exists in two forms that are cationic at low pH and zwitterionic at moderate to high pH. The cationic form has
higher CMC than that of the zwitterionic form [20-22]. The different properties at various pH conditions are
due to the strength of electrostatic interactions between hydrophilic head groups. When it is in cationic form the
electrostatic repulsion between the hydrophilic head groups is increased causing loose micelles packing and
thus poor viscoelasticity and a viscosity [13, 18].Various researchers studied synergistic effects of mixed
zwitterionic and anionic viscoelastic solutions; SDS and cocoamidopropyl betaine[14, 23], SDS and dodecyl
dimethylamino acetate [24]. To our knowledge, there is no study about rheological and microstructural
properties of mixed OAPB-SDS fluid useful for fracturing has been reported. Thus, the aim of the current work
was to study the rheology and aggregates behaviors of viscoelastic zwitterionic-anionic fluid. The effect of
concentration, pHand temperature on mixed zwitterionic- anionic surfactant solution has been presented. The
properties of the zwitterionic-anionic solution as fracturing fluid were also evaluated. The study is useful in
establishing a low concentration of zwitterionic surfactant with the addition of anionic surfactant to improve
solution viscoelasticity for the fracturing process. ThepH and thermo-responsiveness characteristics of OAPB-
SDS in transforming micellar structures between wormlike and spherical shapes are of wide industrial
application.The EDAB and SDSsurfactant are shown in Figure 15.
O
O O
C11H23 O
C17H33 N N S Na+
H O-
O O
OAPB SDS
Figure 15: The chemical structures of OAPB and SDS

Materials and methods
2.1Materials
OAPB and SDS were purchased from Tianjin Heowns Biochemical Technology Co., Ltd.; sodium hydroxide
(NaOH) and hydrochloric acid (HCl) were purchased from Xilong Chemical Company. The water was triply
distilled by a quartz water purification system. All reagents used as received.
2.2Preparation of samples
The samples were prepared by weighing the appropriate amount of surfactants and adding distilled water
directly into glass beakers. To obtain a homogeneous mixture the sample was stirred by a magnetic stirrer for
some hours. pH was adjusted by dropwise addition ofdilute 0.1M NaOH and/or HCl solution; pH was
determined by Sartorius basic pH meter PB-10(+0.01). Sample solutions were left at room temperature for at
least one day to allow equilibration before running experiments. The preferred expression for mixture solution
for OAPB with SDS solutions was abbreviated as OADS. Apart from examining effects of pH on OADS, the
experiments were carried at pH 7 where OAPB mostly exists in zwitterion form. Moreover, the concentration
percentage of OADS is used to represent the overall solution concentration.
2.3Rheology
Rheological experiments were done on a Physica MCR 301 (Anton Paar, Austria) rotational rheometer with
Searletype concentric cylinder geometry CC27 (ISO3219). Prior to the rheological measurements, samples
were equilibrated at the interested temperature for more than 10 minutes. Dynamic frequency spectra were
performed in the linear viscoelastic regime of the sample solutions as per dynamic stress sweep measurements.
The temperature accuracy was set to +0.1℃ by Peltier temperature control device. The rheological
measurements were carried at 80 and 90 °C. Furthermore, the temperature and shear tolerance, gel breaking
static particle settling and core damage test performances were assessed as per SY/T 5107-2005 [25].
2.4Dynamic light scattering (DLS)

DLS was carried out in a spectrometer (ALV-5000/E/WIN Multiple Tau Digital Correlator) and a Spectra-
Physics 2017 200 mW Ar laser (514.5 nm wavelength). The scattering angle was kept 90° whereas the intensity
autocorrelation was analyzed by using the Contin methods.The sample solution was transferred to a square
sample cuvette and the measurement was repeated three times to get more precise data. All measurements were
performed at 25±0.1 °C
2.5Transmission electron microscopy

Transmission electron microscopy (Cryo-TEM) experiments were performed to examine the micellar structure
of sample solutions. Cryo-TEM images of samples were prepared with a 120 kV JEM-2010 Plus TEM
instrument with a Gatan cryo Holder 626 and a Gatan US1000 894CCD monitor. The samples for cryo-TEM
were kept in a verification system under a controlled environment. About 5 mL of the sample was put onto a
carbon-coated holey film supported by a copper grid, this is to ensure that the thin film extends over the mesh
hole. After 10 seconds, the sample was instantly dipped into a -180 °C reservoir of liquid ethane and then
stored into liquid nitrogen (-196 °C). The stored sample remained in liquid nitrogen until observation

3.1The rheological properties of the OADS solution

The viscoelasticity of the WLMs solutions is influenced by concentrations of both zwitterionic and anionic
surfactant. Thus, it is necessary to examine the effect of concentration on the rheological behavior of OADS
solution. The OAPB concentration was kept to 2 wt% while the SDS concentrations varied between 0.032 and
0.25 wt%. Thesteady rheological behaviors of the shear viscosity of 2 wt% OAPB with different concentrations
of SDS is shown inFigure 16. The 2% and 4% OAPB showed Newtonian fluid behavior at low and high shear
rates. The solution 2% OAPB displayed the typical Newtonian fluid characteristics at low SDS concentrations
(0.032 wt%), the steady shear viscosity does not change with the shear rate meaning the micelles are mostly in
spherical shape[14]. When the concentration of SDS increased to 0.25 wt%, the solution displayeda non-
Newtonian fluid behavior with Newtonian fluid behavior at low shear rates which drops dramatically at high
shear rates.Shear banding due to instability flow of solution is the reason for differences influid behaviors from
low to high shear rates. This phenomenon accounts forthe presence of long worm-like micelleswhich
intertwined to forma transient wormlike micelle. Further increase of SDS concentration lowered the zero shear
viscosity, this has been caused by the formation of branched micellar network and shortening of WLMslength
whichcannot entangle form transient wormlike micelle networks [26]. The influence ofconcentration in mixed
micellestrend is similar to that of mixed oleyldimethylamine oxide and SDS solution[27]. From these results
the 0.25 wt% SDS has been chosen for further investigations.
107
2% OAPB
106 4% OAPB
2% OAPB + 0.032 % SDS
2% OAPB + 0.625 % SDS
105 2% OAPB + 1 % SDS
2% OAPB + 0.25 % SDS
ηο (mPa.s)
104
103
102
101
100
10-3 10-2 10-1 100 101 102
Shear rate (sec-1)
Figure 16: Steady rheological behaviors of OAPB surfactant solution with different SDS concentrations at
25°C.
Figure 17shows the effect of total surfactant concentration of 6:1 OAPB to SDS concentration ratio. The
viscosity of OADS increase with the total surfactant concentration.The increase in shear viscosity of OADS
solutions with concentration ratio has been associated with the growth of wormlike micelles [14, 17, 26]. The

shear viscosity increased with the concentration of OADS. Low shear viscosity at low OADS concentration i.e.
below 0.6 wt% might be due to the presence of spherical or short wormlike micelles. The OADS solution
demonstrated varied fluid behaviors from viscous, viscoelastic to gel-like fluid properties depending on
concentration as shown inFigure 18. The 0.5 wt% OADS solution was viscous, loss modulus dominated storage
modulus at low to high frequency whereas 0.6 wt% OADS was viscous at low frequencies and elastic at high-
frequency ranges. The gel-like fluid behavior was demonstrated by OADS with a high concentration that is
0.75 wt% and above, the storage modulus dominated loss modulus across all frequency ranges. The
viscoelasticity of solution is related to the long WLMs entanglement to form the three-dimensional micellar
networks. The plateau modulus (G 0 ) corresponds to the density of the micellar entanglement at a given
temperature. It is clearly demonstrated that G 0 increase with OADS concentration thus 2 wt% OADS solution
displays stronger viscoelasticity higher entanglement density[28].The relaxation time (t R ) is obtained by the
reciprocal of the equivalent angular frequency ω at the intersection point of storage and loss modulus curves. t R
describes the time taken for WLMs to experience relaxation processes, it is related to the average micellar
length[29]. The relaxation times increase with OADS solution indicating lengthening of WLMs as a function of
concentration.
107
106
ηo (mPa.s)
105
104
103
102
0.0 0.5 1.0 1.5 2.0
Concentration (wt %)
Figure 17: Zero-shear viscosity as a function of6: 1 OAPB:SDS concentration of mixed surfactantsolution at
25°C.

101
100
G'&G'' (Pa)
10-1
10-2
G' G'' (0.5% OADS)
G'' G'' (0.6% OADS)
G'' G'' (0.75% OADS)
10-3 G' G'' (1% OADS)
G' G'' (2 % OADS)
10-1 100 101 102

ω (rad/sec)
Figure 18: Dynamic rheological curves of 6: 1 OAPB:SDS concentration of mixed surfactant solution at 25°C.
A possible mechanism on the thickening mechanism in mixed OADS has been discussed to result from
hydrophobic interaction between OAPB and SDS chains andthe electrostatic interactions between the
quaternary nitrogen in the hydrophilic head of zwitterionic surfactant and the SO3- group in anionic
surfactant[28, 30]. The addition of SDS surfactant to OAPB reduces the surface charge density of the OADS
mixed micelles which decreases the charge repulsion between surfactant micelles and the effective head group
area causing close packaging of the surfactant molecules and consequently increase the viscosity of
solution[12, 16, 30].To evaluate structuralsizes of mixed micelles the DLS method was used. Figure 19shows
the hydrodynamic size distribution of the micellar aggregates in OAPB and OADS solution at 25 ºC. It can be
seen that the average hydrodynamic diameter of the micelles in the OADS solution was 16 nm which
corresponds to wormlike micelle sizes, this size was higher than that of 2 and 6 wt% OAPB solution which was
6.9 and 8.5 nm respectively indicating presence of spherical micelles[31]. DLS measurement results were
consistent with the rheological measurements. Thus, it has been confirmed that SDS can synergistically thicken
OAPB solution.

10 OADS
2% OAPB + 0.5 % SDS
2 % OAPB
6 % OAPB
8
Intensity (%)
4
100 101 102 103 104

Size diameter (nm)
Figure 19: The hydrodynamic diameter of the OAPB and OADS aggregates at 25°C.
3.2Effect of PH on the viscoelasticity of OADS solution

The influences of pH on WLMs have roused significant attention for the past decade due to their distinctive
rheological properties in prospective industry applications. The rheological properties of WLMschangeswith
avariation in pH valueswhich is of great application in oil production[32]. pH has a significant effect on the
viscoelasticity of the OADS system, thus the rheological properties of this solution were studied under different
pH conditions. Figure 20shows the storage and loss modulus of the OADSsolution as a function of oscillatory
shear frequencyat various pH values. At pH value 3 the solution showed viscousbehavior, the loss modulus
dominated the storage modulus across all shear frequencies. Addition of a few drops of 1 M NaOH increased
the pH value to 4 which was viscoelastic fluid, the loss modulus dominated storage modulus at low-frequency
ranges and storage modulus dominate loss modulus at high frequencies. Further increase of pH value to 7 and
10 transformed the solution to gel-like fluid behavior, the storage modulus dominated loss modulus at low to
high-frequency ranges. The plot of zero shear viscosityas a function of different pH values is shown in Figure
21. Zero shear viscosity values increase with the increase of pH values up to a maximum at pH 7, then followed
by an insignificant decrease as pH was increased to 10. The transition of OAPB from cation form to zwitterion
form can be described with the inflection point at pH 3.5, this value is equivalent with that reported by Danov et
al., and Różańska et al., [23, 26].The different rheological properties of OADS solution at different pH
condition are due to protonation and deprotonation of the carboxyl group in OAPB. At low pH values, the
protonation at this group triggers more electrostatic repulsive interaction between surfactants heads which
hinder micellization and thus low relaxation times and zero shear viscosity. At high pH values, the
deprotonation at carboxyl moiety increasesthe electrostaticattraction between head groups of surfactants which
is responsible for increased micellization as noted with increase relaxation times and zero shear viscosity[26,
33]. To confirm micellar transformation with pH changes the cryo-TEM measurements were used. The OADS
solution at pH 7 displayed long WLMs entangling with each other into transient network structures where at pH
3 the spherical micelles have been revealed (
Figure 22). The Cryo-TEM images confirm that the OADS micelle experience microstructural transformations
from a long WLMs to spherical micelles as the pH changes. It is structural transitions which caused different
relaxation times and zero shear viscosity at different pH conditions.Figure 23illustrates how the influence of pH
triggers reversible deprotonation/protonation in the carboxylate group of the hydrophilic head in
OAPBsurfactant.
101
100
10-1
G'&G'' (Pa)
10-2
10-3
10-4
G' G'' pH 3
G' G'' pH 4
G' G'' pH 7
10-5 G' G'' pH 10
10-6
10-1 100 101 102
ω (rad/sec)
Figure 20: The relationship of storage and loss modulus against oscillatory frequency for OADS solution with
different pH valuesat 25°C.

107
106
ηο (mPa.s)
105
104
103
102
2 3 4 5 6 7 8 9 10
Solution pH
Figure 21: Zero shear viscosity as function OADS solution with different values of pHat 25°C.
Figure 22. Cryo-TEM image of the OADS solution at pH of 2 (left) and 7 (right).

OH n
O n io
O act io O u ls
att
r re p
- N OH
N O H
O S O
O S O
Na+ OH
O O
HN HN
C11H23 C11H23
C17H33 C17H33
O O
Figure 23. Schematic representation of microstructures variation in OADS solution at neutral and low pH
values.
3.3pH-responsive viscoelastic behavior of OADS solution

The pH-responsivenesscharacteristic is attained by reversibly tuningviscoelasticity of solution for several times
without deterioration of its properties[31]. Two pH values (2 and 7) were selected to validate the pH-sensitive
ability between low and high viscosity. As displayed in Figure 24when the pH value of the solution was 7, the
viscosity was 3.5×106 mPa.s, the addition of 0.1M HCl lowered the pH value to 2where viscositydeclined
to213mPa. s. However, the high viscosity can be regainedby adding 0.1 M NaOH to pH value 2;this process of
reversibly switching between high and low viscosity by adjusting pH can be easily attained for more than three
cycles without any deterioration of viscosity.

107
pH 7
106
ηo (mPa.s)
HCl
105
NaOH
104
103
pH 2
2
10
0 1 2 3
Cycle
Figure 24: Viscosity switchability of OADS solution at 2 and 7 pH values.
3.4Effect of temperature
Influence of temperature for the wormlike micellar solution applications is of great importance, the effect of
temperature on the rheological properties of OADS solutionwere studied at 25-90 °C as shown in. The
relaxation times decreased with the increasing temperature as shown inFigure 25, this indicates that as the
temperature increases the micellar contour length and network mesh size decreases. Moreover, the viscosity of
solution decreases with temperature as shown in Figure 26, which is ascribed to the shortening of WLMs[26].
A similar trendon the influence of temperature in OAPB and sodium dodecylbenzene sulfonatewormlike
micelle solutions[34]. A linear relationship was attainedin Figure 27. It signifies that the main shear viscosity
fits the Arrhenius equation relation η o = G p AeEa/RT where; G p is plateau modulus, A is a pre-exponential factor,
Ea is the flow activation energy, Ris the gas constant, and T is the absolute temperature[34]. The activation
energy of describes the interaction between given micelles which is related to the energy required for single
micelle to escape from the micelle aggregate. From the slope of η o versus 1/T, the value of Ea was calculated to
be 197 kJ mol-1, which is comparable with the other wormlike micelle solutions[28, 34, 35].

10
1
G'&G'' (Pa)
0.1
G' G'' 25 °C
0.01 G' G'' 50 °C
G' G'' 40 °C
G' G'' 60 °C
G' G'' 70 °C
1E-3 G' G'' 80 °C
G' G'' 90 °C
1E-4
0.1 1 10 100
ω (rad/sec)
Figure 25: Effect of temperature on dynamic rheological curves for the OADS solution at 25°C.
107 25 °C
50 °C
106 40 °C
60 °C
105
70 °C
80 °C
ηo (mPa.s)
90 °C
104
103
102
101
100
10-3 10-2 10-1 100 101 102
Shear rate (sec-1)
Figure 26: Effect of temperature on steady rheological curves for the OADS solution at 25°C.

106
105
ηo (mPa.s)
104
103
102
2.8 2.9 3.0 3.1 3.2

1000/T (K-1)
Figure 27: Viscosity of OADS solutions against temperature in the Arrhenius plot.
3.5Temperature and shear tolerance

Temperature and shear resistance performances of fracturing fluids have a direct relationship to the quality of
fracturing operations includinginitiation of fracture and proppant transporting. Usually fracturing fluid with a
good temperature and shearing resistance has potential applicability in various formations. Figure 28shows the
temperature and shear resistance of OADS solution at 90 °C and a shear rate of 170 s−1 for 120 minutes. The 3
wt% and 4 wt% OADS solution maintained a shear viscosity of about 66 and 18 mPa.s respectively. According
tothe SY/T 6376–2008 on technical specifications of fracturing fluids, the 3 wt% and 4 wt% OADSsolutions
displayed a suitableviscosity and hence can be used as a fracturing fluid [25]. The 3 wt % and 4 wt% OADS
fracturing fluids can satisfy the requirements oftemperature (90 °C) and shear (170 s-1).

100
240
200
75
ηo (mPa.s)
Temperature (°C)
160
4 wt % OADS
120 50
80 3 wt % OADS
25
40
0 0
40 80 120
Time (min)
Figure 28: Shear resistance of OADS fracturing fluid at 90 °C, 170 s-1.
3.6Static sand settling test, gel breaking and core permeability damage evaluation
Sand carrying ability is a significant property in the assessment of fracturing fluid as it directly determines
affects the performance of fracturing construction. The viscosity and viscoelasticity of VES fluid directly
determine its sand carrying capacity[36]. The velocity range for sand suspension of VES fracturing fluid should
be between 0.008 cm/s - 0.08 cm/s. The sand did not settle for four days in3 wt% OADS solution at ambient
temperature. Increasing temperature to 90 °C accelerated settling velocity to OADS was 0.003 cm/s after two
hours. Thus OADS solution can efficiently transport proppant during the fracturing process.The viscosity of
good fracturing fluid should break after causinga fracture to reducedamage to the formation. The viscosity of
the broken gel is usuallyrecommended to be below 5 mPa.s [37]. To examine this property, ratios of different
volume of OADS to kerosene were used [38]. The viscosity of OADS has been reduced to less than 5 mPa.s
when different volume ratios of OADS to kerosenewere mixed at 25 °C 5 mPa.s as shown inTable 1. The
results show that the viscosity of OADS solution breaks quicklywith a high amount of kerosene. Besides, the
viscosity can be easily reduced easily by adjusting the pH value of OADS solution to 2.The good fracturing
fluid should not leak into the formation to reduce irreducible water saturation. The seepages of gel broken fluid
into the formation are adsorbed to the surfaces of fracture leading to formation damage by triggering core
plugging and thus reduce oil production efficiency. Thus it is important to execute core damage test to OADS
solution. The core permeability damage and residual content were found to be 6.05 % and 9 mg/L respectively,
the obtained values the values are within the recommended ranges of clean fracturing fluids.

Table 1: Viscosity breaking of OADS fracturing fluid at different fluid and kerosene ratios
OADS to Viscosity breaking Reduced viscosity
kerosene ratio time (min) (mPa.s)
5:1 100 4.4
5:2 60 3.8
5:3 25 2.9
Conclusions
In summary, the rheology and aggregate properties of OAPB-SDS solution as fracturing fluid has been
investigated. The micellar morphology of OADS solution transforms between spherical micelles and
WLMswhich was revealed by the rheological, DLS and cryo-TEM measurements. Interestingly, the properties
of this fluid were responsive to temperature, concentration, and pH. It was gel-like a fluid at 25-40 °C,
viscoelastic at 60-80 °C and totally viscous fluid at 90 °C. The OADS was viscous at 0.5 wt% concentration,
viscoelastic at 0.6 wt % concentration and elastic at 0.75 wt% concentration. The OADS solution showed
viscous, viscoelastic and elastic behaviors at pH value of 3, 4, and 7 respectively. The fluid exhibited viscosity
switch ability where the high and low viscosity was obtained by reversibly altering pH values. A distinctive
benefit of the studied fluid is the use of low surfactant concentration than that of individual surfactant
component for improved viscoelastic and aggregation properties. Thesettling velocity rate, core damage
percentage, gel breaking ability and residue content of OADS solution were all within good fracturing
properties. This study widens understanding of the formation mechanism of mixed smart WLM which is
sensitive to concentration, temperature, and pH applicable in the fields of oil and gas, including fracturing.
Acknowledgements
The work was supported by the National Natural Science Foundation of China (51774309), Shandong
Provincial Natural Science Foundation, China (ZR2017LEE001), Key Research and Development Plan of
Shandong Province (2019GGX102074, 2018GGX102010), the Fundamental Research Funds for the Central
Universities (18CX02166A) and Scientific Research Fund for Introducing Scholars of China University of
Petroleum (YJ201601088).
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Tilte: “Synthesis of Newly Developed Re-Assembling, Self-Healing Nanocomposite PPG (R-PPG) For
Permeability Modification in Heterogeneous Reservoirs”
-Seth Oppong Agrippa, Milan Mandal, and Keka Ojha, Department of Petroleum Engineering
Indian Institute of Technology (ISM), Dhanbad
Abstract:
Heterogeneity in petroleum reservoirs has undoubtedly been ubiquitous, especially when it comes to the
matured reservoir. High levels of heterogeneity lead to excess production of water which can throttle back the
production rate of the hydrocarbons and cause financial and environmental concerns to the petroleum industry
which ultimately leads to the abandonment of the well; therefore, the urgent need to remediate this problem.
Researches have come up with numerous ways for rectifying these problems, and the most used methods are
the in-situ gelation system and the preformed particle gel (PPG). Among the two, PPG has proven to be more
effective because of the numerous advantages it has over the in-situ gelation system. The most recent
advancement in the development of PPG is the Re-Crosslinked Performed Particle Gel (R-PPG) which was
pioneered by Pu Jingyang, Bai Baojin, and Schuman Thomas in 2017. The R-PPG was designed as an
improvement of the traditional PPG to overcome some drawbacks posed by the PPG. Despite the numerous
advantages of the PPG studies have shown that it is unable to successfullyblock large openings and abnormal
fractures, however, the newly developed R-PPG has a plugging efficiency which is significantly higher than the
PPG.
In this paper, synthesis, characterization, and evaluation of a Self-Healing Nanocomposite R-PPG are described
which is used to modify the high permeable streaks in the heterogeneous reservoir using sand pack flooding
studies. The self-healing R-PPG was synthesized using a copolymer of three different monomers, a re-
assembling agent, and modified bentonite as additive through free radical polymerization. The results from the
rheological studies showed that the infusion of the modified bentonite into the synthesis was able to strengthen
the mechanical and chemical properties of the R-PPG. Also, results during the sand pack flooding revealed that
the breakthrough pressure and plugging efficiency of the R-PPG are significantly higher than that of the
traditional PPG.
Introduction
The problems associated with heterogeneity in petroleum reservoirs have undoubtedly been ubiquitous, and
although this problem is mostly experienced in matured oil reservoirs, we can also see its effect on some newly
developed wells as well [1]. Heterogeneity in reservoirs creates water channels, which can reduce the sweep
efficiency of oil thereby producing excess water instead of oil[2]–[4]. The problems associated with the
production of excess watercan be detrimental to the financial and environmental sectors of the petroleum
industry which can ultimately lead to the abandonment of the well; therefore, the urgent need to remediate this
problem[5]. Excess water production through highly permeable conduit reduces the sweep efficiency during
water injection and canseverelythrottle back the oil production rate. Also, due to the chemical make-up of the
produced water disposal of the water becomes an issue;therefore environmentally friendly means of water
disposal must be ensured to meet specific international regulations. Corrosion and formation of scales are
eminent when these unwanted waters come into contact with the production equipmentwhich shortens the life
span of the equipment [1], [5].
The technologies developed to remediate this problem can be subdivided into two, which are: the mechanical
method and the chemical method. The mechanical method employs the use of packers and plugs to seal off

water channels whiles the chemical method involves the injection of chemical compounds into the reservoir to
seal off highly permeable streaks and fractured zone to limit the movement of water [5]. Among the remedies
for profile modification or water shut off jobs, gel treatment (which is a chemical method) has proven to be the
most efficient and cost-effective method[1], [4], [6].The gel treatment can improve the oil sweep efficiency and
divert injected water or aquifer source to the unswept oil-rich zones to ameliorate oil production whiles reduce
excess water. Based on the treating materials, gel treatment can be categorized into an in-situ gel,preformed
particle gel (PPG), microgel[7] and recently re-crosslinked preformed particle gel (R-PPG). In-situ gel system
was the first gel treatment to be successfully implemented in 1985, and since then has been widely used in the
petroleum industry to combat the production of excess water [8]. Like all other technologies, the in-situ gelhad
its drawbacks. Preformed Particle Gel (PPG) was developed to overcome some to the limitations that were
posed by the in-situ gel such as, dilution or change in gel composition during placement, chromatographic
adsorption, gel uncertainty, and uncontrollability[8]–[11].
PPG has been successfully applied since 1999 as a conformance control agent in more than 10,000 wells by
most Chines oil companies [2], [9]. However, inspite of its successful field implementation, further studies
reviled that PPG is limitedwhen it comes to its application inblocking large opening fractures such as
wormholes and conduits [9], [12]. In light of this, (V. Gisbergen and J Maria(2017)[12] developed a novel Re-
Assembling Polymer Particle Packageunder the “Patent Cooperation Treaty” (PCT)for conformance and fluid
loss control. It was found that the novel Re-Assembling Polymer Particle, when injected into the reservoir can
re-assemble with each other to form a stronger, more elastic, bulk gel material for conformance control
applications. In this work, we aim at studying the effect of nanocomposite in the synthesis of R-PPG. In this
studies, modified bentonite was used as an auxiliary for nanocomposite because bentonite is less expensive
readily available and environmentally friendly.
Methodology
Preparation of Modified Bentonite
In laboratory scale, modified bentonite was prepared by first weighing a measured amount of bentonite powder
and placing it in a beaker containing deionized water. The mixture was placed on a magnetic stirrer and
constantly stirred at 400 rpm overnight. The resulting solution was then sonicated using an ultrasonic sonicator
for 2 hours to ensure the complete exfoliation of the bentonite in order to form a homogeneous mixture. An
increase in temperature of about 45oC from the initial temperature of (35oC) was observed afterthe ultra-
sonification.
Synthesizing of Nanocomposite R-PPG
The nanocomposite R-PPG was synthesized via free radical crosslinking polymerization using the following
procedures. First, a measured amount of acrylamide was weighed added to the modified bentonite solution and
stirred continuously until it was completely dissolved, after which AMPS was also added and stirred. When the
two chemicals were completely dissolved in the solution, 1 wt.% of zirconium (IV) acetate crosslinker was
added to the solution whiles stirring was still in progress for another 5 minutes. The resulting solution was then
placed in a three-neck round-bottom flux and purges with nitrogen for 40 minutes. KPS initiator of 0.1 wt.%
was then added to the solution and stirred whiles nitrogen purging seized. The mixture was then transferred into
a beaker and placed in a 40oC oven for 10 hours for complete polymerization process to occur to form a bulk
gel. Followed by the complete polymerization of the PPG, the bulk gel was cut into pieces and dried in an oven
at 60oC till no additional weight loss was observed after which it was crushed into a granular powder sieved
and separated into different particle sizes. Overall, three different R-PPGs were synthesized with different
chemical composition as shown in table 1.
Equilibrium Swelling Ratio

The significance of the swelling ratio test is to determine the maximum allowable swelling limit of the PPG,
which in turn can be used to determine and predict the plugging efficiency of the gel in highly porous and
heterogeneous reservoirs. The swelling ratio was determined by immersing a weighed amount of R-PPG into
NaCl brine of 0.5, 1, 3, and 5 wt. % until it was fully swollen. The extent of swelling was determined using the
following formulae.
𝑊𝑊𝑊𝑊−𝑊𝑊𝑊𝑊
The degree of swelling (DS) or equilibrium swelling ratio𝐸𝐸𝐸𝐸𝐸𝐸 = � 𝑊𝑊𝑊𝑊
× 100%�
Where: ‘Ws’ indicates the weight of swollen PPG, ‘Wd’, the weight of dried PPG, ‘Vs; the volume of swollen
PPG and ‘Vd’, the Volume of dried PPG.
Gel Strength (Rheological) Studies
The storage modulus (G) and loss (G) modulus of the gel were measured on a Bohlin Gemini Rheometer (M/S
Malvern Instruments Ltd., U.K) The experiment was carried out at a constant frequency of 1Hz and controlled
stress of 1.0 Pa as a function of time.
Core flooding Studies

Figure 1 shows the experimental setup used for the sand pack core flooding experiment. It consists of an ISCO
syringe pump which is used to inject the brine, oil, and R-PPG into tot sand pack core model. The model also
comprises of an oven for heating the core to the desired temperature, and core holder to pack the sand. A
beaker was placed at the exit point of the setup to collect any effluent of water, oil or R-PPG that may come
out. Quartz sand with a mesh size of 420-700 microns was filed and well compacted in the sand pack core (45
cm long, ID 3.5 cm) to simulate a heterogeneous reservoir medium. The sand pack core filled with the quartz
sand was placed in an oven at a desirable temperature for the entire duration of the core flooding to simulate
reservoir temperature conditions. The Residual Resistance Factor (RRF) and Permeability Reduction Factor (ɳ)
were determined from the data obtained from the core flooding studies
Table 2 Chemical composition of the different R-PPGs

Samples Acrylamide (wt. %) AMPS (wt. %) Modified Bentonite (wt. %)
R-PPG 1 30 Na Na
R-PPG 2 30 2 Na
R-PPG 3 30 2 2
Figure 29 Core Flooding Setup

Effect of Brine on Swelling Ratio

It was observed from the swelling test in Figure 2 that salinity has an adverse effect on the swelling ratio of the
R-PPGs. The samples swollen in distilled water exhibited a very high swelling ratio as compared to the samples
swollen in brine. There was a drastic reduction in the swelling ratio as the gel samples were introduced to brine.
The reduction in the swelling ratio continued to gradually reduce as brine concentration increased until the
difference in reduction became negligible. This action can be elucidated by the charge balance and the electric
repulsive force between the R-PPG and the solution used [13]. The negatively charged particles in the
polymeric chain of the gel react with the metallic ions in the brine solution to result in an ionic crosslinking
which reduces the volume of the PPG. However, in distilled water, there is a high affinity of the negatively
charged particles in the polymeric chain of the R-PPG to water because of the absence of the metallic ions [14].
Figure 30 Swelling Ratio of R-PPG at Different Salinities
Effect of AMPS and Modified Bentonite (MB) on R-PPG

The effect of AMPS and MB on the swelling kinetics was investigated in this paper and the results showed that
there was a tremendous increase is the swelling ratio as observed in Figure 3. The resulted divulged that R-PPG
2 (with AMPS) had the highest swelling ratio of 105.58 followed by R-PPG 3 (with AMPS and MB) with a
swelling ratio of 102.88 and finally R-PPG 1 with a swelling ratio of 70.85. The addition of MB to the R-PPG
caused a slight reduction in the swelling ratio in distilled water; however, in saline solution, the reduction in the
swelling ratio seamed negligible. Suffice it to say that the addition of AMPS and MB had a positive effect on
the swelling ratio of the R-PPG.
Rheological Studies
The strain sweep test is illustrated in figure 1 a-d; the test was conducted at a fixed frequency of 1 Hz at
ambient temperature. The polymeric gels were prepared in room temperature and allowed to age for 24 hours at
room temperature . The rheological measurement was conducted using a Bohlin Gemini II Rheometer (Malvern
Instruments, New Delhi, India) equipped with a Peltier device for temperature regulation.

Effect of Modified Bentonite (MB) on Gel Strength
As seen in figure 3(d) R-PPG 3 with the proved to be the strongest of all the gel.The elastic module is
consistent from 30.358 Pa up to 24.75 Pa for strains lower than 4562%. In this region, the gel depicts a
behavior known as Hookean, and the region is called linear viscoelastic region (LIV region) while the elastic
modules dominant the viscous modulus. At a strain ranges of 4500 % to 5277 %, the elastic modulus begun to
decrease drasticallyto 24.75 Pa where both the elastic modulus and viscous modulus meets. In other words, R-
PPG 3 could be stretched up to 5277 % strain without tearing/breaking. However, for strain greater than 5277
% the elastic modulus decreases drastically representing the irreversible breakage of the gel and intercepts with
the viscous modulus. The point of interception between the elastic and viscous modulus indicates the beginning
of degradation of the gel to form a liquid. The reason for degradation of the gel to at this point can be attributed
to the fact that, as the strain increases, the bonds in the gel network holding the gel together weakenswhich
cause a reduction of the elastic modulus till the bonds are not able to withstand any more strain and tearing
/breakdown of the gel is imminent[15], [16].Similarly, R-PPG 1 and 2 were able to stretch up to 3597 % and
2423% respectively. By comparison, R-PPG 3which contained the modified bentonite had the highest
stretching ability with a strain up to 5277 % without tearing at which the elastic modulus decreased from 37 Pa
to 25 Pa; this shows that introducing the modified bentonite particles to the gel increases the bonding within the
polymeric gel network.
Effect of Temperature on Gel Strength

Figure 3(a) and 3(b) represents R-PPG 1 at room temperature and R-PPG 1 after 10 months in an oven at 80oC
respectively. From the rheological data, R-PPG 1 at ambient temperature exhibited a higher resistance to strain
as compared to when it was exposed to heat. On the other hand, the elastic modulus of R-PPG 1 after spending
time in the oven incensed tremendously as compared to R-PPG 1 room temperature. An elastic modulus of
2.13 Pa and 32.63 Pa was recorded for R-PPG 1 and R-PPG 1 at 80oC respectively. Heating of the R-PPG
caused to increase in elastic modulus, but the resulting gel was not strong enough to resist higher strain.
FTIR Analysis
Fourier-transform infrared spectroscopy (FTIR) was as well used to characterize how well a sample absorbs
light at every wavelength (cm-1)owing to the presence of various functional groups[17]. From figure 4, the
polymers demonstrated a broad absorption peak at 3600 cm-1, which is a characteristic for hydrogen bond
(OH) groups. The band relating to the stretching of the CH group erupted at 2500 cm-1. The polymers used for
the experiment exhibited additional broadband at 1900 cm-1, which representthe stretching of the C=O,
showing the presence of COO- group. The CO stretching bonds can also be seen at 1050 cm-1. The above
absorbance was similar for the different synthesized polymers, which suggest that the modified bentonite gel
was successfully synthesized.

Figure 31 Strain sweep test for (a) R-PPG 1, (b) R-PPG 1 at 80oC, (c) R-PPG 2, and (d) R-PPG 3
Figure 32 Fourier Transform Infrared Spectrometer analysis of R-PPG
Table 3 Data from core flooding studies
samples PPG Water residual Oil residual Residual Permeability

Resistance resistance resistance Resistance Reduction
Factor factor (Frrw) factor (Frro) Factor (RRF) Factor (ɳ)
(RFPPG)
R-PPG 1 103.72 283.092 186.06 1.52 98.38 %
R-PPG 2 152.8 295.82 182.3 1.623 98.9 %
R-PPG 3 315.35 456.28 192 2.38 99.82 %

Core Flooding Results

The data obtained from the core flooding studies were used to analyze the Residual Resistance Factor
(RRF)and Permeability Reduction Factor (ɳ)to get a better understanding about how the different R-PPGs were
able to function in reservoir simulated conditions. From Table 2, it was established that the residual resistance
factor was highest in R-PPG 3 at 2.38 whiles R-PPG 1 and 2 maintained an RRF of 1.52 and 1.623
respectively.The increment in residual resistance factor in R-PPG 3 can be attributed to the infusion of
modified bentonite during the syntheses of the gel. As showed in Figure 4, the addition of modified bentonite
was able to intensify the physical and mechanical properties of the R-PPG 3, thereby, making it more
susceptible to high strain. A higher RRF indicates a possibly higher recovery factor. It was also observed that
the permeability reduction in R-PPG 3 was significantly higher than that of R-PPG 1 and 2. A higher
permeability resistance factor signifies that the polymer gel was successful in reducing the permeability and
restricting the flow of water to a higher degree than oil or gas. The result in table 2 shows that a higher residual
resistance factor and a higher permeability reduction factor can be achieved by introducing modified bentonite
in the synthesis of the R-PPG.
Conclusion
In this work, aRe-AssemblingPerformed Particle Gel (R-PPG) was synthesized with the infusion of modified
bentonite and AMPS to determine its effect on the rheological properties, swelling ratio, and core flooding
studies. From the swelling ratio test, it was evident that the infusion of the AMPShad an immense effect on the
swelling ability of the R-PPG. Although the addition of the modified bentonite slightly reduced the swelling
ability of the R-PPG in distilled water, in saline water the reduction in the swelling ratio was almost negligible.
Also, looking at the rheological test, one could observe that by adding the AMPS in R-PPG 2, there was an
increase in the elastic modulus of the gel; however, the gel was not strong enough to resist higher strain and
breakdown quickly. The infusion of the modified bentonite nanocomposite was able to significantlyimprove the
strength of the R-PPG making it more elastic in nature and resistance to higher strain and pressures. Overall, it
can be concluded by the characterization studies that the infusion of modified bentonite nanocomposite in the
synthesis or R-PPG was not only successful, but it was also able to augment the mechanical and chemical
properties of the gel making it a possible candidate for profile modification in heterogeneous reservoir wells.
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Title: "Speciality Chemicals usage in the Crude Oil Refinery and Oil fields and its related R&D and
application tests in Laboratory"
-Sanjayendu Bikash Gope, TCG Life Sciences
Key Words : speciality chemicals, refinery process chemicals ,additives for finished products,oil field
chemcials ,emulsion breaker, bottle test, reverse emulsion breaker,BS&W,ASTM,Total Acid
Number(TAN),corrosion inhibitor, biocide, antifoam,asphaltine inhibitor, asphaltene dispersant test, pour point
depressor, cold filter plugging point, cold finger test,tankage dehydration,cetane improver,
antioxidants,hydrogen sulphide scavenger,desalter chemical,antifoulant,ash settling test,salt in crude,dewaxing
aid, lubricity improver test etc.
Abstract
Speciality chemicals are a more recently developed and emerging sector in world’s chemical industry for all
applications. Historical facts say that term “Speciality” has arisen since around 100 years back. Currently this
sector of chemical industry is categorized into many sectors. Recent market research statistics suggest that
specialty chemicals market is growing further with major shift of growth towards China, India and Japan. This
technical paper presentation covers usage of different Speciality Chemicals in the crude oil refineries and Oil
Fields and its benefits to the user. The presentation also covers, in brief about the types of R&D work on
chemistries and of applications for the different chemicals that certain analytical laboratories can offer to the
different types of company in the Oil and Gas sector of India.
Introduction
The chemicals industry can be broadly classified based on various parameters such as value addition
(basic/specialty), end-use (water treatment/construction/agrochemicals), process (batch/continuous), etc.
In the value addition segment of chemical , basic chemicals are more likely to be manufactured in continuous
process plants because of their high volume demand and there is no major product differentiation or difference
in product attributes among several manufacturers. Market of basic chemicals is primarily driven by price.
Specialty chemicals are low-volume and high-value products sold on the basis of their quality or utility or
perceived value, rather than their composition. Specialty chemicals are more likely to be prepared and
processed in batches for their low volume requirement.
In order to deal with ( buying,selling and using ) the Products and services in the specialty chemicals industry ,
it requires intensive knowledge of the products as well as the end user’s process including innovation in both.
The requirement of laboratory involvement in the formulation of the speciality products and mainly the
application tests of speciality chemicals is of prime importance. In most of the cases, the formulations of
speciality chemicals are proprietary in nature and are intellectual properties of the suppliers . We will be
talking more about the application tests for these products.
There is a wide range of speciality chemicals that is used in the production of adhesives, agrochemicals,
hydrocarbon industries process and water side chemicals, lubricants, cosmetic products, flavors and food
additives, fragrances, textiles, and construction materials who are earning significant revenues for the industry.

In this paper we are going to do a study and analysis of types of speciality chemicals used in crude oil refinery
sector ie Refinery Process Chemicals (RPC) and oil field sector ie Oil Field Chemicals (OFC) and the different
application tests and laboratory related works that are done for these speciality chemicals.
Different types of Speciality Chemical of Refinery and Oil Field , market brief , its usage ,and the related
Application Tests .
6. A) Refinery Process Chemicals
Global oil refinery chemical demand will rise 3.5 percent annually through 2013, driven by growth in many
Asia Pacific countries and also stringent environmental laws that will further boost gasoline and diesel fuel
yields. The Global RPC market is expected to reach around USD 50 Billion by 2023.
The major challenge in the Refinery Process Additives market is in terms of Research and Development. The
new regulations set by the government authorities in various countries in terms of air pollution control is also a
challenge in this market. The refinery process chemicals and finished product additives market( which is a part
of RPC only) requires constant innovations so as to provide better performing products to the Energy, Oil and
gas and Petrochemical segments so that that they can compete against the rising prices of raw materials,
increasing competition and meet the increasing demand of rising global population efficiently without hiking
their prices to unaffordable levels.
Different products that fall under the category of RPC (including finished product additives)and a brief
on their usage are as follows–
i)Crude Oil Tankage dehydration – removal of Basic Sediment and Salt(BS&W) from crude storage tank.
ii)Desalter Chemicals – removal of water with salt and sediments from deslater by demulsifier in desalter.
iii)Overhead corrosion inhibitor ( neutralizer and filmer type)- for atmospheric and vacuum distillation
column overhead system corrosion control.
iv)Antifoulant and Dispersants for crude units and other downstream units/equipments.
v)Antifoam-Si based and organic based antifoam for different units like coker,DHDS,etc .
vi)Crude Tank Cleaning and Hydrocarbon recovey Chemicals
vii)Corrosion Inhibitors for all the downstream units like FCCU, Visbreaker,DCU etc.
viii)Pipeline Corrosion Inhibitors ( product and crude oil)

ix)Ni passivator chemicals for FCC units.
x)H2S Scavenger chemicals for all the applications in a refinery.
xi)Flocculation Aid/Deoiler –Used in ETP
xii)PPD for Diesel blends and heavier blends of refinery( fuel oil, LSHS etc).

xiii)Diesel Dehazer chemicals xiv)CFPP improver.
xv)Diesel ( HSD) Lubricity improver chemical. xvi) Diesel Stabilizers.
xvii)Dewaxing Aids, xix)Gasoline antioxidants ( all types). xviii)Cu corrosion inhibitors.
Tests related to process side chemicals of refinery:
i)Asphaltene Dispersant Test (ADT) used for Antifoulant application. This procedure is routinely used for
comparing asphaltene contents of crude oils, for evaluating the ability of various products to disperse
asphaltenes, for monitoring the asphaltene content of crude unit charge and for isolating the asphaltene fraction
from crude oil. ASTM D6560 – 17 is the Standard Test Method for Determination of Asphaltenes (Heptane
Insolubles) in Crude Petroleum and Petroleum Products.
ii)Carbon Residue (Micro Method) - ASTM D 4530 – For recommending any antifoulant chemical
application in a refinery or petrochemical plant, the foulant sample needs to tested for CHONSP( Carbon,
Hydrogen,Oxygen,Nitrogen,Sulphur and Phosphorous to determine type of foulant sample ) C testing is one of
the critical tests to find out the organic contents also. Determination of Carbon residue gives a measure of the
carbon depositing tendenciesof a fuel oil.
iii)Phosphorous testing : ASTM D 4951 is the standard procedure for testing phosphorus which si required
before recommending an antifoulant program.
iv) Carbon, hydrogen and nitrogen content : ASTM D5291 Standard Test Methods for Instrumental
Determination of Carbon, Hydrogen, and Nitrogen in Petroleum ProductsCarbon, hydrogen, and particularly
nitrogen analyses are useful in determining the complex nature of foulant samples sample types .
v)Ash Settling Test ASTM D 482 used for Downstream antifoulants like FCCU slurry circuit antifoulants.
vi)Basic Sediment & water(ASTM D4007 ) and Sediment, total particulates

(ASTM D4807)determination of sediment and water (water only D4007, which give "BS&W" - basic sediment
and water,) in crude oils. It is required for tankage dehydration as well as desalter chemical application tests.
Sediments (suspended solids) and water is not a part of the crude itself, but follows the crude from the
reservoir. Both water and sediments are separated from the crude on production site, however, a complete
removal is not possible. There are specifications of maximum content of sediments and water for traded crudes
(typically limits vary from 0.5 - 2 wt% BS&W). Knowledge about the sediment content of crude oil is
important in refinery operations and determination of water and sediment content is also required to measure
accurately net volumes of actual oil in sales, taxation, exchanges, and custody transfers.
vi)Chloride by Silver Nitrate titration and Chloride(Hach by Mercuric Nitrate) used for salt in crude for
tankage dehydration, desalter as well as water analysis for corrosion control application monitoring.
vii) Acidity, TAN - total acid number : TAN is expressed in mg of KOH per g of sample. The acid number
is a measure of the amount of acidic substance in the oil. The TAN value indicates to the crude oil refinery the

potential of corrosion problems. It is usually the naphthenic acids in the crude oil that cause high temperature
region corrosion problems. This type of corrosion is referred to as naphthenic acid corrosion (NAC). In order
to design and apply the right kind of corrosion inhibitor (Npathenic acid corrosion control)application program
the TAN no. of the crude and the different cuts and streams are very important to be known as input data .It is
also important to know the other parameters like MOC , viscosity, temperature velocity of the stream and crude
sources .Total acid ( for liquid and vapour phase) Test is also used for corrosion inhibitor applications
(selection , monitoring, optimizing and trouble shooting due to unit upsets). ASTM D664 Standard Test
Method for Acid Number of Petroleum Products by Potentiometric Titration.
vii)Salt in crude oil: Determination of the approximate chloride (salts) concentration in crude oil. The range of
concentration covered is 0 to 500 mg/kg (D3230) or 2 to 1500 mg/kg (ASTM D6470) as chloride
concentration/volume of crude oil. This test method measures conductivity in the crude oil due to the presence
of common chlorides, such as sodium,calcium, and magnesium. Other conductive materials may also be
present in the crude oil. The method is used to determine the approximate chloride content of crude oils, which
is important to decide whether or not the crude oil needs desalting. The efficiency of the process desalter and
the performance of the demulsifier used in the desalter can be accessed or can be evaluated. Salt in crude Tests
are done for tankage dehydration , desalter chemical , and corrosion control ( Process side) applications
(selection , monitoring, optimizing and trouble shooting due to unit upsets). Excessive chloride left in the
crude oil frequently results in higher corrosion rates in refining units and also has detrimental effects on
catalysts used in these units. This test method provides a rapid and convenient means of determining the
approximate content of chlorides in crude oil and is useful to crude oil processors.
viii) Determination of mercaptan sulfur : Mercaptan sulfur has an objectionable odor, an adverse effect on
fuel system elastomers, and is corrosive to fuel system components. Fuel sweetener application tests are done
based on these types of tests to correct the odor specifications of the fuel. ASTM D3227 Standard Test Method
for (Thiol Mercaptan) Sulfur in Gasoline, Kerosine, Aviation Turbine, and Distillate Fuels .
ix)Sulfur, total – ASTM D4294A is the method followed for measurement of sulfur in diesel, naphtha,
kerosine, jet fuels, crude oils, gasoline and other distillates. The applicable concentration range is 0.0150 to
5.00 mass % sulfur.
While analyzing the type of foulant and cause of fouling the ‘s’ content data is required before recommending
an antifoulant inhibitor program. There are also environmental statutary regulations that restrict the amount of
sulfur present in some fuels. This test method provides a means of compliance with specifications or limits set
by regulations for sulfur content of petroleum products.It comes in use for application tests of additives meant
for this purpose.
x)Chemical residual tests for corrosion inhibitor ( filmer type ) or antifoulant applications.- These are
proprietary tests of some companies who use it for determining the residual chemicals in the downstream of
application to ensure that adequate chemical is present in the system to solve the problem for which it is meant
for.
xi)Oil in Brine(High Level and low level) , used in tankage dehydration, deslater chemical applications,
Effluent treatment plant and water discharge of all the units of refineries.

xii)Portable Electrical Deslater test is done for desalter chemical application selection , monitoring,
optimizing and trouble shooting due to unit upsets.
xii)Spot test for ferrocyanide and free cyanide tests are done to monitor the hydrogen blistering tendencies
and also corrosion due to high PH in different units of a refinery.
xiii)Total Iron by Tirimetric Method or by portable instruments are mainly used for the corrosion control
applications in different units( site tests/spot tests) and also to monitor the fouling tendency in different units
while investigating on the foulant samples available .
xiv)Foaming tests- In order to screen different antifoam and evaluate at different temperature and conditions,
different types of ASTM methods are used in the Industry. Following are some of the methods used :
ASTM D3519-88(2007),Standard Test Method for Foam in Aqueous Media (Blender Test).
ASTM D3601-88(2007),Standard Test Method for Foam in Aqueous Media (Bottle Test).
ASTM D4921-95(2006),Standard Test Method for Foaming Tendencies of Engine Coolants at
RoomTemperature.
ASTM D6082-06, Standard TestMethod for High Temperature Foaming Characteristics of LubricatingOils.
ASTM D892-06e1, StandardTest Method for Foaming Characteristics of Lubricating Oils.
Tests related to additives used finished products of refineryto meet specifications :
xv)Antioxidant test in gasoline - The gasoline specification ASTM D-4814 requires gasoline which is
marketed and sold to have a minimum level of resistance to oxidative degradation. This resistance is
determined by test method ASTM D-525 and matched against the spec with or without addition of chemicals(
antioxidants).This serves as an application test.
An alternate test is Oxidation Stability (ASTMD-873/IP138)of Aviation Fuels (Potential Residue Method) .
xvi)Distillate Fuel Stability - Distillate fuel can darken in color and can degrade to form sediment after
exposure to air and/or heat for a period of time. Degradation is also accelerated by exposure to dissolved metal
ions, especially copper. During this process, oxygen in the air reacts with fuel components to form compounds
which are often dark in color and unstable. Also, condensation-type reactions can occur and result in the
formation of high-molecular-weight, insoluble organic compounds.Typically DuPont F21 Stability Test ,
ASTM D-6468 , ASTM D-4625/IP 378 or ASTM D-2274/IP 388 are used. This servesas application test for
diesel additives and detergents to meet the spec as and when required.
xvii)Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test ( ASTMD-
130/IP154).Copper corrosion inhibitor test application uses this test method.
xiii) Cetane Number ASTM D 613 – Standard Test Method for Cetane Number of Diesel Fuel Oil. It is
required not only during normal QC test of diesel but also after addition of cetane improver as an application
test.
xix)Hydrogen Sulphide Determination in Fuel and Hydrocarbon liquids – H2S scavenger chemical is often
added in the fuels like Diesel, Fuel oil etc to meet the H2S specifications. After and before addition of the
chemicals , the ASTM D-5705 test is done that gives the effectiveness of the H2S scavenger chemical added.

So it serves in the application test for the evaluation of performance of H2S scavenger. An additional concern is
corrosion that can be caused by the presence of H 2 S during refining or other activities. ASTM D7621 Standard
Test Method for Determination of Hydrogen Sulfide in Fuel Oils by Rapid Liquid Phase Extraction:
Procedure A has been shown to eliminate interferences such as thiols (mercaptans) and alkyl sulfides.
Procedure B can give elevated results if such interferences are present .
xx) Acid Number of Petroleum Products by Potentiometric Titration (ASTM D-664) :

This test is used to Identify the presence of organic or inorganic acids in fuel, Identify possible causes of
ferrous and nonferrous metal corrosion in fuel systems, Identify possible causes of fuel instability or low
induction time ratings, With the findings a suitable chemical package can be designed to control corrosion that
results in fuel degradation and maintain the specifications.
xxi) Electrical Conductivity of Aviation and Distillate Fuels (ASTM D-2624 )-

This test is used to determine the tendency of fuel to develop and hold static charge during pipeline transport
and during high velocity flow through transfer lines, Identify the need and do the application tests for use of an
electrical conductivity improver in fuel.This serves as the application test for static dissipater additives or
antistatic additives of fuels( including Jet fuels)
xxii) Low temperature operability of diesel – The test that is used as application tests after addition of Cold
Filter Plugging Point(CFPP) improver in diesel is ‘Institute of Petroleum’ (IP) 309 . The other tests that are
used for CFPP determination in Fuel oil are ASTM D 6371 and ASTM D 4539 for Filterability of Diesel Fuels
by Low-Temperature Flow Test (LTFT).
xxiii) Diesel Lubricity improver application test is ASTM D 6078 – Scuffing Load Ball-On-Cylinder
Lubricity Evaluator (SLBOCLE) and ASTM D 6079 – High-Frequency Reciprocating Rig (HFRR). It is used
to evaluate the Diesel Lubricity additives ie performance before and after addition of the chemical at certain
dosage. The field evaluation and monitoring is also done by this method.
xxiv) Pour Point /Cloud Point test for different type of fuel oils:.
The pour point test(ASTMD-97/IP15) is used to determine the lowest temperature at which a fuel can be
effectively pumped.The Cloud Point of Petroleum Products(ASTM D-2500/IP219) is the temperature that
identifies the point when wax begins to form into crystals large enough to become visible in the fuel.
Chemicals for improvement of cloud point and or pour point of the fuels are tested by these methods for the
performance.
xxv) Corrosion test used for fuel oil corrosion tendency of iron in the pipelines which is .This is used for
monitoring and application test of product pipeline corrosion inhibitors. Refiners and marketers have adopted
the National Association of Corrosion Engineers (NACE) Corrosion Standard Method TM-Ol- 72-93 as a
specification. Product pipeline corrosion inhibitors are evaluated and monitored by using this test as an
application test after addition ion the fuel either in lab or doped samples brought from the pipeline site.
xxvi) Test Methods used to determine the emulsion tendency of fuel: Application test for dehazer of
emulsion breaker of fuel. a) ASTMD-1401/IP79 - Water Separability of Petroleum Oils and Synthetic Fluids.
b) ASTM D-1094/1P 289 - Water Reaction of Aviation Fuels .
c) ASTM D-3948 - Determining Water Separation Characteristics of Aviation Turbine Fuels by Portable
Separometer (Microseparameter (MSEP) Test) which is often called the "Water Separation Index, Modified"

(WSIM) test, named after the original water separation index procedure. d) ASTMD-4176 - Free Water and
Particulate Contamination in Distillate Fuel (Visual Inspection Procedures).These tests are used as application
test in different ways for dehazer chemicals of demulsifiers for fuel blends.
xxv) Solvent dewaxing aid test in laboratory – Many companies have proprietary test methods to evaluate
performance of solvent dewaxing aids used in the dewaxing unit to help separate wax from lube oil from
raffinate by use of a solvent ( like propane or MEK/Toluene mixture) by adding a dewaxing aid chemical and
by vacuum filtering under subzero temperature( as per the parameters in plant). The reported application test
result includes the yield of dewaxed oil , the oil in wax content(ASTM D721),filtering rate and dosage of
chemical which gives a fair idea on the efficiency of the dewaxing aid chemical in a lab scale.
6.B) Oil field Chemicals :
Global Oilfield Chemicals (OFC)Market was valued at $42 billion in 2016, and is anticipated to grow at a
CAGR of 5.2% to reach $60 billion by 2023.
Over the past few years, the global energy landscape has changed significantly as a result of technological
advances in the recovery of unconventional hydrocarbon resources such as tight oil and shale gas. A number of
researches have been done to examine the impacts of extraction and production of unconventional
hydrocarbons on surface water, groundwater, and local air quality. The extraction and utilization of such
unconventional hydrocarbons brings in, concerns about their contribution to the atmospheric chemistry and
global climate change. Nevertheless, their application ( as statutory requirements)in operations including
drilling, production, cementing and work over and completion is expected to drive the demand for oilfield
chemicals. This is apart from the new fields production as well as EOR(Enhanced Oil Recovery) operations of
the existing ones.
Different types of applications are Drilling & Cementing, Enhanced Oil Recovery, Production,Well
Stimulation and Workover & Completion
Some of the products for the above applications that are widely used in Oil Fields and their relevant
laboratory application tests are as follows:
Production and Drilling Chemicals:
i)Asphaltene Inhibitors - Helps in inhibiting the deposition in the crude pipelines.
ii)Viscosity Reducers – Addition of chemical in viscous crudes to reduce the viscosity to improve the
pumpability and smooth operations.
iii)Paraffin Inhibitors – These chemicals are added to stop deposition of paraffin in the pipelines to avoid
choking and fouling and increase in deltaP across the pipeline that severely restricts the operation.
iv)Pour Point Depressor- These chemicals are added to improve the pour of the crude that is required for
better operations as well as to meet the specification of the clients who buy the crude oil.Already discussed in
RPC section.
v)Wax Dispersants – These chemicals can disperse the wax that are already formed in the pipeline or in the
operations equipment creating severe limitations to the processing or operations.

vi) Scale Inhibitors – Scale inhibitors are added into the crude oil production tubular so as to control or
prevent the deposition of scale. Formation of scale may cause different types of problem like Well plugging,
Reduction in pipe carrying capacity,insufficient heat transfer,localised corrosion failure, safety hazard and over
all ncrease of operational cost.
vii) Corrosion Inhibitors – These chemicals reduce the corrosion of metals in the crude oil pipelines and
equipments when applied properly into the fluids/crude oil. In oil gas industry, gas system requires vapor phase
corrosion inhibitor while liquid containing system requires film forming corrosion inhibitors.
viii) Biocides – The chemicals that kill or help kill microbiological organism(mainly bacteria) are called
biocides. Biocides are used to control sulfate reducing bacteria, lime forming bacteria, iron oxidizing bacteria
and also those bacteria which attack polymers used in fracturing and secondary recovery fluids. By using
biocide, formation of large biomass due to degradation of fuel by bacteria can be avoided which can plug the
formation and reduce the permeability of the formation.
ix) Oxygen Scavenger - These are chemical formulations that are used to reduce or completely remove
oxygen in fluids and enclosed spaces to prevent oxygen-induced corrosion. These can be used in drilling ,
production, EOR etc operations in different places under different conditions.
x) Demulsifier – It helps separation of water from oil in water in oil emulsions of oil field.
xi) Reverse emulsion breaker–It helps in separation of oil from water in Water in Oil emulsion.
xii) Schmoo Remover - Schmoo is a term used which is a collection of oil field organics deposits (viz.
hydrocarbon, paraffin, asphaltene, iron sulfides or biomass). Usually , Schmoo builds up in produced water,
injection water systems and reduces operational performances by reduction of injectivity, pore plugging, flow
restrictions etc. The “Schmoo Remover” chemical dissolves and removes all the components of schmoo ,
there by generating a cleaner water system.
xiii) Antifoam – Antifoam is typically used for breaking oil foam in the oilfield.
xiv) Deoiler – Deoiler is typically used in the effluent plants or in the injection water plant to remove oil from
water (oil in water emulsion, ppm level).
xv) Rheology Modifiers – these formulations provide high viscosity at lower shear rates which is useful for
drilling operations in high anle or horizontal drilling.
xvi) Friction Reducers – These additives are used to reduce the friction forces experienced by tools and
tubulars in the wellbore when used in horizontal and highly deviated well drilling.
xvii) Surfactants – Typically surfactants can be cleaning chemicals, dispersants or even different types of
emulsion breakers which are used in the oil fields.
xviii)Foamers – Foamers are used in gas fields for increasing production by unloading fluid and reducing
hydrostatic pressure. Foamers are also used in artificial lift technique of oil production.

xix)Pipeline cleaning chemicals – surfactant based specially formulated cleaning chemicals.
xx)Chemicals of ETP – Polyelectrolytes, deoilers, antifoam etc are used.
xxi)Hydro testing chemicals – Commonly used chemicals are biocides, corrosion inhibitors and oxygen
scavengers.
xxii)Scale and paraffin squeeze- Scale inhibitors and paraffin inhibitors are used in this type of application as
per direction of the chemical and service provider to clean up the old and aged wells and to help it revive
production.
Water Injection Chemicals: It is also a part of OFC.
xxiii)Calcium Scale Inhibitors – It inhibits formation of CaCao3 scale and there by not allowing it to block or
hinder fluid flow through pipelines, valves, and pumps used in oilproduction and processing
xxiv) Sulfate Scale Inhibitors- Inhibitors of barium sulfate and strontium sulfate.
xxv)Biocides for Water Floods & Production Systems – explained RPC section.
xxvi)Corrosion Inhibitors – These chemicals are added in the injection water to protect the pipe and
equipment internals from corrosion.Already explained in RPC section.
xxvii)Defoamers – Water based defoamers are often used in injection water to avoid foaming in the system.
xxviii)RO Membrane Antiscalant etc.-Typically when sea water is used as injection water after cleaning the
same by RO , the RO systems create salt concentrated water streams that could produce scale or fouling.The
antiscallant chemistries are used to prevent the scale formation and fouling.
Tests related to Oil Field Chemicals (OFC), application wise :
i)Demulsifier Emulsion Breaking Survey & bottle test used for the application of demulsification of
crude oil ( separation of water from crude oil) - The bottle test is performed to assist in the selection of the right
formulation of demulsifier which will most effectively break the emulsions from any given well. The bottle
test results may also be used as an indication of the ratio of treating compound to emulsion which will be
required to achieve salable oil. The methods used for bottle testing are described in the American Standards for
Testing and Measurement publication ASTM D-96 for field measurements and ASTM D-4007 for laboratory
procedures.
ii)Antifoam Efficiency Test Method used for the evaluation , monitoring and troubleshooting of antifoam
chemical application. The ASTM method number for this test is ASTM E2407 - 04(2015):
iii) Tests for Asphaltene removal chemical application in oil field.The first step is to find out the amount of
asphaltene present in the crude oil. ASTM D6560 – 17 is the Standard Test Method for Determination of
Asphaltenes (Heptane Insolubles) in Crude Petroleum and Petroleum Products.This test method is used before
and after addition of Asphaltene dispersants in the crude to do the application test to do the screening of the

right chemicals and also to find out the efficiency of the chemical chosen at different dosages and other
parameters.
iv) Corrosion Inhibitors application test replicating Field Conditions in the Laboratory and also evaluation
and monitoring in the field. Several standards( mainly ASTM and NACE) and industry best practices are used
to evaluate and monitor these properties. Those are :ASTM(A) G170, “Standard Guide for Evaluating and
Qualifying Oilfield and Refinery Corrosion Inhibitors in the Laboratory, ASTM G184, “Standard Practice for
Evaluating and Qualifying Oil Field and Refinery Corrosion Inhibitors using Rotating Cage , ASTM G185,
“Standard Practice for Evaluating and Qualifying Oil Field and Refinery Corrosion Inhibitors using Rotating
Cylinder Electrode, ASTM G202, “Standard Test Method for Using Atmospheric Pressure Rotating Cage,
ASTM G205, “Standard Guide for Determining Corrosivity of Crude Oils , ASTM G208, “Standard Practice
for Evaluating and Qualifying Oil Field and Refinery Corrosion Inhibitors using Jet Impingement , NACE
1D182, “Wheel Test Method Used for Evaluation of Film-Persistent Corrosion Inhibitors for Oil Field
Applications, NACE 1D196, “Laboratory Test Methods for Evaluating Oil Field Corrosion Inhibitors .
v) Tests for different chemical applications of Injection water system. – A water injection system must
produce water of such quality that it will not reduce the permeability of the formation i.e. ASTM D4520 -
18 for Standard Practice for Determining Water Injectivity Through the Use of On-Site Floods can be
followed.
vi)Paraffin inhibitor chemical application’s identification, Field Tests and relevant lab tests. Paraffin
inhibitors are used in oil production operations to control wax deposition and reduce viscosity and gelling of
high wax present in some crude oil. The paraffin inhibitor formulations can change in different wells or fields
or regions. Hence the right chemistry has to be determined for a particular crude stream by laboratory
evaluation before trying the same in the field. While using in the field also several confirmatory and evaluation
tests are required to ensure the chemical performs as per expectation to deliver the desired results of flow
assuarance with repeatability.The following laboratory methods and apparatus are used to assist in the paraffin
inhibitor selection and monitoring process:
a) Cold Finger (or Cold Coil) Deposition Test: The Cold Finger Deposition test helps to predict whether a
particular oil will have paraffin or wax deposition under pipeline conditions. Standard test methods are Test
method IP 309 or ASTM D 6371-17a.
b) For most pour point tests the standard ASTM D-97 procedure is used, however, on occasions it is necessary
to deviate from the ASTM D-97 procedure to match field conditions.
c) Constant Temperature Ramp Down Pour Point Unit: This devise is like the standard ASTM D-97 pour point
units. The main difference is the temperature ramp down rate is variable. This allows for a more accurate pour
point test.
d)TA 1000 Viscometer: This is a viscometer that can measure the viscosity of a crude oil during cooling, the
shear stress versus shear rate profile at a fixed temperature, and yield point. This viscometer will also measure
cloud point.
e)Brookfield Viscometer: This viscometer measures the viscosity of a crude oil during cooling and shear stress
versus shear rate profiles at a fixed temperature.
f)Paraffin Flow Loop: This instrument is a highly technical instrument designed to emulate pipeline conditions.
This instrument’s primary function is to measure paraffin deposition rates and pressure increases under pipeline
conditions.

vii) Testing of different types of scales and scale inhibitor chemical applications.- While selecting the
scale inhibitor to treat a particular problem as well as considering the type of scale to be prevented, the
selection process is designed to take the following into account: means of application, conditions prevalent
where inhibition is required, composition of the scaling water, means for determining residual inhibitor levels
and compatibility of the chosen chemical with other chemicals in the system. Following tests are done to
achieve the above objectives:
a)Scale tendencies- Using the data given by the customer (water composition, pressure and temperature data
across the process) scale predictions for both downhole and topside conditions are carried out. Different
software packages that are available these days in the market, are used to identify the areas of high scaling
tendency and the types of scale likely to be formed.
b)Inhibitor Performance testing – This includes Static Efficiency Tests(TM0374-2016-SG of NACE for
Laboratory Screening Tests to Determine the Ability of Scale Inhibitors to Prevent the Precipitation of Calcium
Sulfate and Calcium Carbonate from Solution (for Oil and Gas Production Systems).Dynamic Efficiency
testing - The MIC (minimum inhibitor concentration) versus carbonate, mixed carbonate/sulphate and sulphate
scale formation is determined using a dynamic loop deposition test. This is an effective method used to study
the performance of inhibitors in a scaling environment under dynamic conditions. High temperature and
pressure conditions can be simulated if required (up to 200oC/6000psi).
c)Brine and scale inhibitor compatibility - Scale inhibitors can display a degree of incompatibility when mixed
with high calcium/magnesium formation water. To assess the degree of incompatibility scale
inhibitor/formation water mixtures are prepared and heated to reservoir temperature. Over this heating stage
any changes in physical state of the chemical is noted. This test indicates the bulk fluid compatibility.
d)Thermal Stability – Scale inhibitors must be thermally stable at system and reservoir conditions to be
effective. Long term temperature and pressure stability tests on each inhibitor candidate both in its neat form
and in diluted form in formation/produced water are carried out when reservoir temperature exceeds 120oC to
ensure there is no degeneration of the effectiveness.
e)Production chemical and scale inhibitor incompatibility – Of all the production chemicals used the largest
impact of scale inhibitor performance/compatibility is methanol. In cases where methanol is applied for well
start up the compatibility with methanol should be checked at seabed and typical flowing wellhead temperature.
It is possible for compatibility problems to manifest themselves in terms of interference with other production
chemicals. The most common interference is between the scale inhibitor and a corrosion inhibitor. The
performance of a scale inhibitor should be assessed both in absence and presence of corrosion inhibitor as
performance can be affected.
g)Analysis for Scale Inhibitor residuals - For squeeze application it is essential that the residual level of
inhibitor in returning fluids be known to assess the timing of re-squeeze. For topside application it is useful to
know what the level of inhibitor is throughout the separation train to ensure that adequate inhibitor is present to
inhibit downstream scaling. In either case, most of the companies use proprietary test methods to determine low
levels of inhibitor in production fluids.
viii) Tests for Pipeline Pigging applications: The following tests are done for the oil field operations to have
a successful pigging operation:

a)Analysis of wax(UOP 46)/asphaltene(ASTM D6560-17) samples recovered from the pig trap
b)Lab tests can be used to determine the molecular weight of the wax and its softening point that will
indicate the type of wax chain and can put some light on the remedial solution required to stop similar
precipitation in future.
c)The efficiency of the cleaning application is sometimes difficult to measure and will be dependent on the
type of pig used. Some service provider recommend a maximum thickness of deposit that can be removed
while others recommend a total volume or mass that can be removed from the pipeline.
ix)Relevant tests for water clarification and deoiling applications.- The Oilfields produced water that often
contains residual quantities of oil and solid particles. The oil can be either a source of income if removed
efficiently or a source of problems if left with the water. Apart from that it has got environmental issues also.
For both reasons many types of equipment are used to remove as much oil as possible. Chemicals are used to
improve the efficiency of equipment and reduce the cost of operation.The solids found in produced water are
commonly particles of silt, sand and clay from the formation or can be the byproducts of corrosion and scale
formation. These solids are usually removed along with the oil. They are eventually removed from the system
as a waste material or passed to the refinery with the salable oil which is not welcome by the refiners.
The different laboratory tests that are done for proper application of the chemicals and running the operations
are as under:
a)Bottle Test for reverse emulsion breaker – Bottle testing is widely used water clarification test in the
industry.
b)Jar Testing – When water enters a large system like a pit or wash tank, the fluids experience only a slight
amount of agitation. These larger systems are actually designed to minimize agitation to encourage the natural
separation of oil and solids from the water. Jar testing is simply a way to test chemicals for use in these low
agitation systems.
c)Gas Floatation testing – System simulation by the action of gas bubbles to float both oil and solid
contaminants out of the water phase is common in the Industry. These systems usually have high amounts of
agitation and create foam or froth above the water phase. Gas flotation testing is usually done with a unit called
a bench Wemco to simulate these systems.
d)Other tests - oil ppm in water,use of turbidity meters, infrared spectro photometers( for low oil ppm
values),membrane filter analysis of water,deposit analysis ( oil, sand and scale forms a coating inside the
equipment and pipe walls – analyzing samples of these deposits can often help determine sources of water
problems) etc
Many laboratory chemical application tests specially for the emulsion breaking, cleaning ,water treatment etc
are common to both RPC and OFC applications and hence the procedures followed can be same.
Conclusion.
Speciality Chemicals application in refinery and Oil Field segment is a major growth area for present as well as
future. With this growth however the stringent statutory environmental compliance requirement and cost

optimization factor has brought new challenges to improve on technology and innovation apart from the other
growth sustenance requirements . Laboratory and R& D does not only play a critical role in discovering new
molecules/products but also improvement of the existing molecules/products. Similarly , the laboratory
application tests for new areas of treatment and monitoring for the ongoing chemical treatment program in the
field and sites play a very critical role in sustaining the existing market as well as the future expansion of
market.
Since laboratory plays a pivotal role for the growth , some of companies are investing on the infrastructures and
expanding their laboratory capability . Many chemical companies( who want to focus on the operational and
marketing expertise) are also looking for outsourcing the research work for new molecular development and
also the application / monitoring tests to third party who are capable of such manpower and equipment centric
work load.
Infact there is a current trend of many analytical laboratories being set up in the market as the future demands a
focused approach in these types of work.
So in a nutshell the analytical and industrial laboratories will play a big role in adding further value to the
speciality chemical market in the hydrocarbon sector for profitable and sustainable growth.
Acknowledgments
I would like to express my deepest appreciation to all those who provided me all the help and assistance to
complete this technical report. A special gratitude I give to my current company colleagues whose contribution
in stimulating suggestions and encouragement helped me to coordinate my efforts in writing this report.
References
Reference used in this paper are :

1. Guide to ASTM Test Methods for the Analysis of Petroleum ProducR. A. Kishore Nadkarnits and
Lubricants 2nd Edition.
2. Manual of petroleum measurement standards. Chapter 10 : Sediment and water Section 4 :
Determination of sediment and water in crude oil by the centrifuge methods (field procedure)
3. All Oil & Gas Manuals and Monographs – ASTM International(https://www.astm.org/industry/oil-and-
gas-mnls.html)
4. Oil Field Chemical Market watch journal.( https://www.marketwatch.com/press-release/oilfield-
chemicals-market-foresees-growth-in-the-coming-years-with-cagr-of-52-from-2017-to-2023-2019-07-
24)
5. Oshas Technical Manual (https://www.osha.gov/dts/osta/otm/otm_iv/otm_iv_2.html)
NACE International (http://nace.org/standards/nace-standards

Title: “Application of Low Salinity Water Flooding: Effect of Dilution on Sea Water in Carbonate
reservoirs”
-Rohit Kumar Saw, Ajay Mandal, IIT(ISM) Dhanbad
Abstract
Low salinity water flooding has gained a tremendous response in recent past years due to its ability to produce
oil in a very cost-effective way. Although many works have been done in this area but the mechanism behindit
is still controversial due to which a very few number of cases on field implementation has been reported so far.
Most of the studies conducted in this area have focused mainly on Rock-Brine interaction and very few studies
have been conducted which are based on Oil-Brine interaction, which is also believed to be a major
contributing factor in defining the mechanism of low salinity water flooding. Understanding of both Rock-
Brine and Brine-oil interaction can give a better insight into the mechanism of low salinity water flooding.
In this work, an attempt has been made to understand both the oil-brine and rock-brine interaction upon dilution
of sea water and its effect on low salinity with respect to carbonate cores. Oil-Brine interaction has been
assessed with the help of interfacial tension of sea water and its subsequent dilutions and the Rock-brine
interaction has been evaluated mainly by zeta potential, contact angle studies on carbonate cores based on the
data obtained from Brine-Rock interaction. Interfacial tension was measured by pendent drop method.
Synthetic Sea water was used for this study. Crude oil was characterized by FTIR and SARA analysis and the
core samples were characterized by XRD and FESEM analysis. Results of this paper showed that as dilution of
sea water takes place it affects both the Rock-Brine and Brine Rock interaction to a greater extent. The results
showed that oil-water interfacial tension showed no effect upon dilution of sea water. Zeta potential studies
showed that charge present on the carbonate core shifted from positive value to negative value upon dilution,
which give an immense opportunity to understand why dilution of sea water worked in this study, Contact
angle studies showed that there exists an optimum dilution level upon which the wettability changed from oil
wet condition to neutral wet conditions, leading to oil recovery. Maximum change in contact angle was
obtained on that brine whose charge were found to be negative in zeta potential results. From the above study it
can be said that low salinity water flooding has a huge potential to be applied in the carbonate fields to recover
more oil as compared to high saline water injection practices that are being followed till now.
Keywords: EOR, Low salinity water flooding, Sea water, Dilution.
Introduction
Out of all proven reserve in the world, more than half of it are carbonates reservoirs. To improve the oil
recovery different method have been applied throughout the reservoir production life cycle. Waterflooding is
one of the most widely used oil recovery method that has been applied in the field since
decades.Initiallyinjection brine salinity was not considered as a influencing factor foroil recovery until various
researchesfocusing on recovery with brine variationwere published by authors around the world[1–4].Injection
of low salinity brine in carbonate formation for enhanced oil recovery purposes gained momentum only in last
decade[5–7] due to its uncertainty in dominant mechanism because ofheterogeneity and complex natureof
carbonate reservoirs in comparison to sandstone reservoirs.
Researchers have demonstrated the positive effect of LSWF with dilution of formation water or sea water as
injection fluid. Yousef studied [5] on limestone reservoir cores, it was showed that injection of different
dilution of sea water sequentially led to an increase in incremental oil recovery of 19% to that of sea water with
a dilution of 10 times sea water. Rezazaeri[8]studied the effect of temperature ,salinity, permeability and

connate water by spontaneous imbibition studies. They found out that oil recovery was enhanced by increasing
the dilution ratio of sea water, and there existed an optimum dilution ratio at which the highest oil recovery was
achieved. Temperature also showed a major impact on oil recovery from carbonate rocks.Nasralla studied
[9]the effect of salinity and mineralogy of reservoir carbonate cores were studied and it was found that extra oil
was produced when brine was switched from formation water to sea waterand diluted 0sea water thus
confirming the low salinity effects by both Amott test and core flooding. It was also stated that oil recovery by
LSWF can be maximized by injection of brine at a certain salinity threshold, at which lowering the brines
salinity further did not lead to additional recovery improvement. They also stated that the LSWF effect and
optimal brine salinity varied in different layers of the reservoir which indicates that within the same reservoir
the LSWF effect is quite dependent on the rock type/property and mineralogy.
In this study an attempt has been made to see the low salinity effect of sea water for enhancing the oil recovery
in carbonate reservoir with the help of IFT, Zeta Potential and contact angle studies. Results found in this study
shows that lowering the salinity up to a threshold limit can increase the amount of oil recovery. Above the
threshold limit lowering the salinity can lead to detrimental effect on recovery.
1.0 Material
s and Methods
2.1 Characterization of Core Samples
Carbonate reservoir cores were used in this study. Carbonate cores were characterized with the help of X-Ray
Diffraction (XRD) and FESEM techniques. XRD was used to determine the mineralogy of rock surface and is
shown in Figure-1. From XRD image it can be said that the rock is mainly composed of calcite mineral.
4000
3500
3000
Intensity (cps)
2500
2000
1500
1000
500
0
0 10 20 30
2theta 40
(deg) 50 60 70
Figure -1 XRD of carbonate rock
FESEMimage were obtained to reveal the surface morphology of rock surface as surface roughness can affect
the contact angle between the rock surface and aqueous medium.FESEM image of rock surface is shown in
Figure-2.

Figure -2FESEM of carbonate rock
2.2 Crude oil

Characterization of crude oil was done with the help of SARA and FTIR. A detailed characterization of crude
oil is as shown in Table-1 and Figure-3 shows the FTIR spectrum of crude oil used in this study.
Table-1 Properties of crude oil
Properties
API 28.40
Specific gravity 0.8849
Saturates (%) 56.3
Aromatics (%) 25.8
Asphaltenes (%) 6.3
Resins (%) 11.5
40
35
30
Trancemittence(%)
25
20
15
10
-5
500 1000 1500 2000 2500 3000 3500 4000
Wave number(cm-1)
Figure-3 FTIR spectrum of crude oil

2.3Brine Composition
All the brines were prepared with the help of deionized water by mixing the reagent grade salts (NaCl,
MgCl 2 *6 H 2 O, CaCl 2 *2H 2 O, NaHCO 3 , MgSO 4 , KCl and Na 2 SO 4 ). Sea water was prepared by standard
procedure as mentioned in IS:8770-1978and further dilution of sea water was done with the help of deionized
water. The formulation of sea water and its further dilution with other physical parameters are as shown in
Table-2.
Table: -2 Composition of sea water and its subsequent Dilution
Ions SW 2dSW 4dSW 8dSW 10dSW 20dSW 40dSW

(mol/l) (mol/l) (mol/l) (mol/l) (mol/l) (mol/l) (mol/l)
Na+ 0.45937 0.229685 0.114843 0.057421 0.045937 0.022969 0.011484
Cl- 0.53582 0.26791 0.133955 0.066978 0.053582 0.026791 0.013396
Mg2+ 0.052511 0.026256 0.013128 0.006564 0.005251 0.002626 0.001313
So 4 2- 0.027456 0.013728 0.006864 0.003432 0.002746 0.001373 0.000686
Ca2+ 0.009911 0.004956 0.002478 0.001239 0.000991 0.000496 0.000248
K+ 0.0088528 0.004426 0.002213 0.001107 0.000885 0.000443 0.000221
HCO3- 0.00238 0.00119 0.000595 0.000298 0.000238 0.000119 0.0000595
TDS (ppm) 34360 17180 8690 4295 3436 1718 859
IS (mol/l) 0.683 0.3415 0.1707 0.0859 0.0683 0.03415 0.017075
Density 1.00184 0.98528 0.98255 0.97546 0.97499 0.97201 0.97032
@90℃(g/cm3)
pH@25℃ 7.47 7.61 7.48 7.65 7.28 6.93 6.60
2.4 IFT
IFT between the aqueousphase and oil phase were measured by pendent drop method. Crude oil droplet was
injected with the help of “J” needle mounted on a Drop Shape Analyzer 25(KRUSS). The crude oil droplet was
positioned at the tip of needle and then image of drop was recorded and was further analyzed for IFT
determination. All the measurement of IFT values were taken at 90℃.
2.5 Zeta Potential

Zeta potential was measured with the help of Horiba scientific Nano partica Nano particleanalyzer SZ-100.It is
basically based on Electrophoresis method and measures the Electrophoretic mobility of charged particle in a
colloidal suspension. All the suspensions were made according to standard procedure. All the measurement of
zeta potential and pH were done at 25℃.
2.6 Contact Angle Measurement

For contact angle measurement carbonate core were cut into thin slices, whose surface were made smoother
with the help of sand paper so that hysteresis effect due to surface roughness on contact angle can be
minimized. Firstly, the slices were placed under vacuum for 24 hrs. and then it was aged with formation water
for another 24 hrs. Then the slices were put into crude oil and left for ageing for about 4 weeks at 90℃. After
the ageing process, the slices were placed in respective preheated brine and a drop of crude oil was placed into
the rock slice in a sealed vessel. The time variant behavior of crude oil droplet was observed with the help of
digital photograph taken at fixed interval of time. All the measurement of contact angle was done at 90℃ to
mimic the prevailing reservoir conditions.

Result &Discussions
3.1 Interfacial tension measurement
Reduction of IFT is a very important criteria to be screened for a reservoir in which EOR activities has to be
implemented. For this purpose, IFT of SW with subsequent dilutions were measured. From results it was
observed that for 2dSW, IFT values were found to be minimum and for further dilution the values of IFT
increased. This type of trend in IFT reduction has been reported by other authors[10,11]as well. Researchers
also claim that ascending trend of IFT after the threshold salinity at which IFT is minimum is due to hydrogen
bond around the salt ion which are established when polar compound exist in aqueousphase. The presence of
hydrocarbon lowers the salt concentration at the interface resulting in higher IFT values.[11][12].
25
23.64
20 19.22
16.84
IFT (mN/m)
16.07
15 13.79
11.58
10.87
10 8.67
0
SW 2dSW 4dSW 8dSW 10dSW 20dSW 40dSW DW
Salinity (ppm)
Figure-4 Effect of dilution of Sea Water (SW) on IFT
3.2 Zeta potential

Zeta potential is mainly used to quantify thecharges that are present on the rock/brine and brine/oil interfaces.
A type of charges present on these interfaces basically governs the stability of water film that is present in
between the rock and oil interface. If charges present on the two interfaces are of same kind then it will lead to
repulsion between the interfaces and hence leading to a thick and stable water film. On the contrary if the
charges present on the both the interfaces are of opposite in nature then it will lead to attraction between them
and hence the water film will be thin and unstable in nature. Thickness and stability of water film leads to
wettability alteration, if water film is thick and stable then rock will be more water wet and if water film is thin
and unstable then it will lead to oil wet system. From literature it can be said that the charges present on the
brine/oil interfaces are negative in nature above pH 3[13] so the charges on oil/brine interface were assumed to
be negative in nature.
From the result it can be seen that as we go on diluting the SW the charges present on rock/water interface
started to shift from positive to negative side which is very much desirable in nature. From fig-5(b) it can also
be seen that as dilution of SW takes place the pH of solution also increases leading to a more negative zeta
potential value, Iso-electric point was found to be at pH of 8.40 which is well in agreement with literature.
From fig-5(a) it can be seen that the potential candidate for wettability alteration based on zeta potential values
are 10dSW,20dSW and 40dSW.

6 5.9 6 Iso-electric point at 8.40 pH
4 4
2.7
Zeta Potential (mV)
Zeta Potential (mv)

2 1.5 2
0.4
0 0
-2 1.6 -2
-4 3.5
-4
-6 5.6 -6
SW 2dSW 4dSW 8dSW 10dSW 20dSW 40dSW 7.6 7.8 8.0 8.2 8.4 8.6
Salinity pH
Fig-5 (a) Effect of Salinity on Zeta Potential (b) Effect of pH on Zeta Potential
Contact Angle
Measurement of contact angle is one of the most widely accepted technique to characterize the wettability of
rock surfaces and wettability alteration is so far the most leading mechanism in context with low salinity
waterflooding. Wettability alteration mainly depends upon the complex interaction of rock/brine/oil which is
mainly governed by mineralogy of rock, properties of brine and oil composition. Hereit can be seen that all the
rocks were in highly oil wet condition as indicated by the initial contact angle of each samples which varied
from 160º to 145º.
It can be seen from Fig-6 that contact angle decreases as dilution of sea water takes place. So, it can be stated
that lowering the salinity of sea water can lead us to enhanced effect of oil recovery. It can be seen that 10dSW,
20dSW and 40dSW showed the maximum change in contact angle with respect to others which is well in
agreement with the results found in zeta potential described above. Among the 10dSW, 20dSW and 40dSW
maximum change in contact angle was found to be with 20dSW which is considered to be optimum salinity.
Concept of optimal salinity in low salinity effect has been described by various other authors[8,9] and it was
also argued that the maximum recovery of oil was found at optimal salinity.
160
Contact Angle (Degrees)
150
140
SW
130 2dSW
4dSW
8dSW
10dSW
120 20dSW
40dSW
DW
0 20 40 60 80 100 120 140

TIME (hrs.)
Fig 6- Effect of Salinity on Contact Angle

Conclusions
In this paper potential of low salinity waterflooding via Sea water and its subsequent dilution are studied with
the help of different experimental technique such as IFT,Zeta potential and contact angle. From this work
following conclusions can be drawn:
1. Decreasing the salinity can reduce the IFT between oil and water up to a threshold salinity level above
which IFT may starts to increase.
2. Zeta potential study showed that there is a shifting of charge from positive to negative upon dilution of
SW.
3. Twenty times diluted sea water showed the maximum change in wettability alteration through contact
angle measurement which was considered as optimum salinity for injection as it is in well agreement
with zeta potential results.
4. Salinity on which IFT was found to be minimum doesn’t have much impact on zeta potential and
contact angle results. This shows that reduction in IFT is not a prominent mechanism in low salinity
waterflooding as found in other EOR processes. From our result wettability alteration is found to be the
leading mechanism but further experiments need to be done for confirmation.
References
[1]Jadhunandan PP, Morrow NR. Effect of Wettability on Waterflood Recovery for Crude-Oil/Brine/Rock
Systems. SPE Reserv Eng 1995;10:40–6. doi:10.2118/22597-PA.
[2]Mcguire PLL, Chatham JRR, Paskvan FKK, Sommer DMM, Carini FHH, Exploration BP. Low Salinity Oil
Recovery: An Exciting New EOR Opportunity for Alaska's North Slope. SPE West Reg Meet 2005:1–
15. doi:10.2118/93903-MS.
[3]Seccombe JC, Lager A, Webb KJ, Jerauld G, Fueg E. Improving Wateflood Recovery: LoSalTM EOR Field
Evaluation. SPE Symp Improv Oil Recover 2008:1–19. doi:10.2118/113480-MS.
[4]Morrow N, Buckley J. Improved Oil Recovery by Low-Salinity Waterflooding. J Pet Technol 2011;63:106–
12. doi:10.2118/129421-JPT.
[5]Yousef AA, Al-Saleh SH, Al-Kaabi A, Al-Jawfi MS. Laboratory Investigation of the Impact of Injection-
Water Salinity and Ionic Content on Oil Recovery From Carbonate Reservoirs. SPE Reserv Eval Eng
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[9]Nasralla RA, Mahani H, van der Linde HA, Marcelis FHM, Masalmeh SK, Sergienko E, et al. Low salinity
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Title: “Trend Analysis of Heavy Metals, Ni and Pb, in Marine Sediments – A Case Study around
ONGC’s Western Offshore Installations inMumbai High Region, Arabian Sea”
-Nikita Chiripal, G. L. Das, Atul Garg, IPSHEM- ONGC
Keywords: Heavy metal pollution, Mumbai High, sediment
Abstract
Heavy metal pollution, in the aquatic ecosystem, especially sediments, has become an area of concern
garnering increasing attention since the past few decades. Heavy metals like Nickel (Ni) and Lead (Pb), are
non-essential and are introduced into the marine ecosystem mainly due to anthropogenic activities. These heavy
metals when discharged into the marine ecosystem may be absorbed in suspended solids, remain in seawater,
etc., but ultimately end up in the sediments which act as a “sink” and later the “source”, due to their restricted
mobility. Hence, monitoring the heavy metal concentrations in these marine sediments over a period of time is
of great help in checking the pollution level and identifying the trend, which in turn will be instrumental in
formulating sustainable practices.
In this paper, the effect of E&P activities of ONGC in Mumbai High Region is studied, by carrying out a trend
analysis of heavy metal concentration (Ni and Pb) in the sediments from this region. Sediments were collected
from the vicinity of various ONGC offshore installations in Mumbai High North, Mumbai High South and
Satellite fields (using Paris commission guidelines and OSPAR commission guidelines) and the heavy metal
concentration values averaged out. These average values are used to analyse the trend for a period extending
from 2008 upto 2018.
In the years 2012 and 2013, the pollution level recorded was minimum. Overall, from 2008 to 2018, Ni shows a
decreasing trend line, but Pb shows an increasing trend line. Albeit the increasing trend of Pb concentration is a
matter of concern, but all the values are below the ERL (effects range low) set by the National Oceanographic
and Atmospheric Administration (NOAA), USA. Hence, it can be concluded that the oil field activity of
ONGC in the Western Offshore has not made any significant impact on the marine environment, in terms of
heavy metal pollution.
A statistical analysis in terms of Relative Contamination Factors and Pollution Load Index has also been done
in the paper.
Introduction
Marine environmental pollution is a growing concern today. There are a lot of activities (both anthropogenic as
well as natural) that may contribute to marine pollution, E&P activities of Oil and Gas companies being one of
them. ONGC, one of the most valued Maharatnas of India, is committed to adopting sustainable E&P practices
in its offshore installations, in order to protect and preserve our marine ecosystem. Hence, ONGC through its
institute IPSHEM, has been conducting regular offshore environmental monitoring in the Western Offshore
region. The aim of this study is to paint an overview of the environmental status and trends over time in
relation to our offshore E&P activities- to indicate whether the environmental status is stable, deteriorating or
improving.
The study of heavy metals in the marine sediments is particularly important in comparison to other parameters
due to their non-biodegradable nature, accumulative properties and long biological half-lives. Heavy metals
like Nickel (Ni) and Lead (Pb), are non-essential and when discharged into the marine ecosystem may be
absorbed in suspended solids, remain in seawater, etc., butthrough various physical, chemical or biological
mechanisms ultimately end up in the sediments which act as a “sink” and later the “source”, due to their

restricted mobility. They are potential threats to the ecosystem because they could be concentrated and
biomagnified at sufficiently high concentrations, and sometimes be converted to more toxic organic
compounds. Therefore, the distribution of such toxic metals in sediments,over a period of time, might provide
evidence for human activities and their effects on the marine ecosystem. For this reason, sediments are most
commonly chosen as environmental indicators of the quality and potential risks within aquatic systems.
In this paper, analysis of distribution of two non-essential heavy metals, Ni and Pb, has been done in marine
sediments around ONGC installations in Mumbai High Region, from 2008 to 2018.
Study Area
From 2008 to 2018, the study has been carried out in the Western Offshore region, covering different
installations – platforms, drilling rigs – spread across Mumbai High North & South, Neelam-Heera Asset and
Satellite region. The study area extends from 18ºN to 21ºN and 70ºE to 73ºE. In the study area, the depth of
water column varies from 20-80 m. The distance from the coast varies from 60 km to 180 km.
Figure 1: Study Area of 2018

Sampling Methodology
From 2008-2014, the sampling strategy was in line with PARIS Commission Guidelines[2], as shown in Figure
2.From 2015-2018, OSPAR (Oslo and Paris) Commission Guidelines[3] have been followed, as shown in
Figure 3.
Figure 2: PARIS Commission Sampling Strategy
Figure 3: OSPAR Commission Sampling Strategy

A Van Veen Grab of 25 cm x 30 cm dimension and approximately 1.5 kg capacity having a penetration depth
of 10 cm was used for collection of sediments, from the sampling vessel. This medium version of the grab was
used to prevent likely damage to pipelines etc. in case of any accidental strike on flow lines.Prior to
deployment, the grab was cocked with the safety key in place. The grab wasthen hoisted over the side, the
safety key was removed, and the grab was lowered at2 m/sec until it was 5 m above the bottom. From this
point, it was lowered at 1 m/secto minimize the effects of bow wave disturbance. After bottom contact had
been made(indicated by slack in the lowering wire), the tension on the wire was slowly increased,causing the
lever arms to close the grab. Once the grab was back on board, the topdoors were opened for inspection.
Procedure for Sample Analysis

From the bulk sediment, a representative subsample was transferred to an oven and dried at 50 ± 2 ºC. The
homogenized samples were then ground to powder in granite mortar with a pestle and kept in a pre-cleaned
container for further analysis.Trace metal extraction was carried out following the standard method EPA 3052.
Approximately 200 mg of homogeneous sediment sample was digested with 6 mL of nitric acid and 3 mL of
perchloric acid in Teflon vessels for 50 minutes using a closed microwave reaction system for 12 h. After
cooling the vessel completely, dissolved samples were then filtered through Whatman filter paper and diluted
to 25 mL with milli Q water. The extract was stored in polythene bottles at 4°C for the analysis of trace metals.
In order to obtain more accurate data, all the glassware and Teflon sample cups in this study were soaked with
5% nitric acid, rinsed with milli-Q water, and dried to eliminate potential contamination.
Upto 2014, an inductively coupled plasma optical emission spectrometer (ICP-OES; model 2000 DV, Perkin
Elmer made) was used for determination of trace metals concentration. Background correction and matrix
interference were monitored throughout the analysis. The accuracy was examined by analysing all samples in
duplicate.
From 2015 onwards, an inductively coupled plasma mass spectrometer (ICP-MS; model 7700series Agilent
made) was used for heavy metal determination. The measurement method was standardized and instrument
accurately calibrated using standard metal solutions and standard reference samples.
Data
The distribution of Ni and Pb, over the Western Offshore region, was determined annually from 2008 to 2018.
For each year, the values were averaged out for both Ni and Pb.The average concentration of these elements in
the Western Offshore Region have been tabulated year-wise in Table 1.
Also, added to the table are values of ERL (Effects Range Low) and ERM (Effects Range Medium), of the
respective elements, set by NOAA (National Oceanographic & Atmospheric Administration, US)[4].

Year Concentration in ppm

Nickel (Ni) Lead (Pb)
2008 26.78 2.72
2009 31.31 3.22
2010 61.79 3.20
2012 0.61 0.15
2013 0.17 0.03
2014 6.52 1.75
2015 10.25 2.46
2016 14.92 3.28
2017 28.46 4.21
2018 25.64 5.29
ERL 21 47
ERM 52 220
Table 1: Concentration of Ni and Pb in sediments from 2008- 2018
Graphical Representation
Data from Table 1 has been graphically plotted in Graphs 1 and 2.
Trendline (y = -1.6352x + 3312.6, R² = 0.0913) ERL ERM

ERL ERM

Graph 1: Concentration of Ni in sediments from 2008- 2018
ERL = 47 ppm; ERM =
Graph2: Concentration of Pb in sediments from 2008- 2018
Trend Analysis
Nickel (Ni)
• Average values of Nickel in sediments fluctuate from 0.17 to 61.79ppm during the years 2008-2018, the
highest being in 2010 and lowest in 2013 (Table 1).
• Considering concentration of Nickel from around the overall study areas, a trend analysis has been
made from 2008 to 2018 as shown in Graph 1.
• The trendline has a negative slope, and hence the concentration of Ni is showing a decreasing trend with
time. However, from 2014 to 2018, the average concentration of Ni has increased by nearly three times.
• The trendline is below the ERL set by NOAA, though few data points are above ERL but below ERM.
Only in 2010 did the average concentration exceed ERM, but has been controlled since then.
Lead (Pb)
• Average values of Lead in sediments fluctuate from 0.03 to 5.29 ppm during the years 2008-2018, the
highest being in 2018 and lowest in 2013 (Table 1).
• Considering concentration of Lead from around the overall study areas, a trend analysis has been made
from 2008 to 2018 as shown in Graph 2.
• The trendline has a positive slope, and hence the concentration of Pb is showing anincreasing trend with
time. Alarmingly, from 2013 to 2018, the average concentration of Pb has increased by more than 100 times.
• However, the trendline and all average concentrationsarewell below the ERL set by NOAA.

Statistical Analysis
Sediment quality can be assessed in terms of Contamination Factor (CF) and Pollution Load Index (PLI).
CF metals is the ratio between the content of each metal to the background values.
i.e., CF metals = C metal /C background
CFcan be classified into four grades for monitoring the pollution of one single metal over a period of time: low
degree (CF < 1), moderate degree (1 ≤ CF < 3), considerable degree (3 ≤ CF < 6), and very high degree (CF ≥
6). Thus,the CF values can monitor the enrichment of one given metal insediments over a period of time.
The PLI is defined as the nth root of the multi-plications of the contamination factor of metals
PLI = (CF 1 × CF 2 × CF 3 × . . . × CF n ) 1/n
PLI valueof zero indicates excellence, a value of one indicates the presence ofonly baseline level of pollutants
and values above one indicate progressive deterioration of the site and estuarine quality[5].
Taking values of 2008 as baseline, CF and PLI has been calculated for 2009-2018.
CF metal = C metal in required year /C metal in 2008
PLI = (CF Ni × CF Pb ) 1/2
Year CF Ni CF Pb PLI
2009 1.17 1.18 1.18
2010 2.31 1.18 1.65
2012 0.02 0.06 0.04
2013 0.01 0.01 0.01
2014 0.24 0.64 0.40
2015 0.38 0.90 0.59
2016 0.56 1.21 0.82
2017 1.06 1.55 1.28
2018 0.96 1.94 1.36
Table 2: Statistical Analysis of Sediment Quality
Nickel (Ni)
• CF is near to 1 or less, indicating very low degree of Ni contamination, relative to values recorded in
2008.
Lead(Pb)
• CF is near to 1 indicating very low degree of Pb contamination, relative to values recorded in 2008.
However from 2016 onwards, CF is seen as steadily increasing from 1.21 to 1.94
PLI values are near 1, indicating presence of only baseline level of pollutants.

Conclusion
1. The trend analysis (2008-2018) of contamination of sea sediments around the study area reveals
that concentration of Ni is decreasing whereas Pb is observed to be increasing. However, this trend is due to the
trough in 2012-13. From 2014 till 2018, however, the concentration of both heavy metals is steadily
increasing.Nonetheless all values are well within toxicity range, either below ERL or just slightly higher.
2. From the statistical analysis it is clear that CFs are near to 1 and hence there is low to moderate
contamination of sediments by Ni and Pb. PLI values are also around 1, indicating presence of only baseline
level of pollutants. However, PLI is increasing with time, indicating that the sediment quality is deteriorating,
in terms of Ni and Pb content.
3. It is evident that offshore E&P activities of ONGC has not alarmingly polluted the marine
ecosystem. However, the increasing trend in the metal concentrations needs to be arrested. The future E&P
activities have to be planned, keeping in mind sustainability of the marine life.
Acknowledgement
This research was a part of the ONGC project“Offshore Environmental Monitoring of Western Offshore
Region” being carried out by IPSHEM-ONGC since 1994. Authors acknowledge the contribution of everyone
associated with the project through the years.
Authors are also honestly grateful to Shri A. K. Dwivedi, Director (Exploration),ONGC, for his encouragement
for preparation of this paper.
References
[1] IPSHEM, ONGC. Offshore Environmental Monitoring Projects of Western Offshore Region from 2008-09
to 2018-19 (Unpublished reports).
[2] Paris commission (1989) Guidelines for monitoring methods to be used in the vicinity of Platforms in the
North Sea, Paris Commission.
[3]OSPAR Guidelines for Monitoring the Environmental Impact of Offshore Oil and Gas Activities, 2004-11.
[4]https://www.nrc.gov/docs/ML0720/ML072040354.pdf
[5] Mir Mohammad Alia, et al. Preliminary assessment of heavy metals in water and sediment ofKarnaphuli
River, Bangladesh.

Title: “Role of low dosage hydrate inhibitors for the control of hydrate formation in oil and gas field
operations: an overview”
-Vikas Mahto, Barasha Deka, Bineet K. Tripathi, A. K. Misra, M. V. Lall, Gaurav Dixit, Mohinish Deepak,
Department of Petroleum Engineering, IIT (ISM), Dhanbad, Gas Hydrate Research and Technology Centre
Abstract
Although gas hydrate is a potential source of energy, but its formation during different oilfield production
operations is undesirable. During drilling of gas hydrate reservoirs or transporting multiphase fluids along with
crude oils through pipeline experience gas hydrate formation and leads to disastrous conditions. Petroleum
industry is dependent on use of thermodynamic inhibitors, which are required in large quantities as well as
toxic for different conditions. To overcome these issues, application of low – dosage hydrate inhibitors
(LDHIs) have gained attention since the last decade. Requirement of very small amount, its non-toxicity and
minimal surface facilities are the beneficial effects obtained with LDHIs. There are two categories of LDHIs:
kinetic hydrate inhibitors (KHIs) and anti – agglomerants (AAs) and have different mechanisms of hydrate
inhibition in the system. Kinetic inhibitors inhibit hydrate formation, whereas anti-agglomerants inhibit hydrate
plugging in the systems. The mechanism behind their working is discussed in this paper. This review article
focuses on discussion of different LDHIs developed by the researchers throughout the world and their
beneficiation effects. It also explains the applicability of LDHIs in different oilfield operations.
Introduction
Hydrates formed in gas or oil pipelines would imperil thesafety of the transportation since the hydrates could
moderately agglomerate and stack and finally block the pipelines. Therefore, to effectively prevent the hydrate
formation during transportation in pipeline is extremely essential. Gas hydrates were a major problem in the
containment of the oil leak causing well blowout of the Macondo well in the Gulf of Mexico and also caused
failure of a 100-ton containment structure. Figure 1 shows a hydrate plug recovered from a pipeline, which
caused plugging of the complete diameter of the pipeline.
Figure 1: Gas hydrate plug formed in a subsea pipeline (Courtesy: Petrobras)

There are three different structures of hydrates, based on thetype and number of cavities and various sizes of
guest moleculeswhich cause the different arrangements of water molecules surrounding them. These three
structures are named structure I (sI), structure II (sII) and structure H (sH).Figure 2 shows different hydrate
structures. Structure II represents hydrates which commonly occurin hydrocarbon production and processing
conditions.
Figure 2: Three hydrate unit crystals and constituent cavities (Reference & Courtesy: Sloan, 1998)
Gas hydrate is easily formed during the transportation of oil and gas when it contains a certain amount of water,
resulting the damage to oil and gas industry. Since Hammerschmidt, discovered in 1934 that gas hydrate would
block the gas pipeline; the prevention of hydrate formation has become an important matter. During the
transportation and processing, especially when the product gases contain saturated water steam and under cold
weather conditions, gas hydrate will plug the pipeline, valve, and equipment. Therefore, the investigation on an
effective method for preventing and eliminating the formation of gas hydrate has aroused significant
interest.The problem of the gas hydrate has not only effected the transportation industry but also the drilling
industry and petroleum industry as a whole. With the petroleum industry endeavoring to develop oil and gas
fields in deepwater and to increase its activities in onshore arctic environments, greater emphasis should be
placed on quantifying the hazards to drilling operations posed by gas hydrates. The necessary conditions for
their formation could exist within the sediments of continental margins where thermogenic or biogenic sources
of gas are present.

There aremany methods for hydrate formation prevention such aschemical injection, thermal insulation, lower
the pressure and removal of water. Under chemical injection method, there are mainly three types of inhibitors,
thermodynamic inhibitor, kinetic inhibitor and antiagglomerants (AA) hydrate inhibitor which are as follows:
• Thermodynamic Hydrate Inhibitors (THIs):Traditional inhibitors such as methanol and ethylene

glycol shifts the condition at which hydrates are stable. If enough thermodynamic hydrate
inhibitorsare injected, hydrate will never form in the system. The difficulty comes in being able to
inject enough.
• Kinetic Hydrate Inhibitors (KHIs): It slows down the hydratenucleation or/and growth rate for a
period of time known as induction time. KHIs are highly effective in low to moderate subcooling
applications. Sub cooling is the difference between the hydrate equilibrium temperature (281.5 K)
and the operating temperature (274.5 K) at a given pressure (6 MPa).
• Anti-agglomerant hydrate inhibitors (AAs):It inhibits the agglomeration of hydrates to form big
cluster but keeps the hydrate dispersed in the system. Fluid velocities remain low, allowing the
hydrate to transport along with the produced fluids without depositing.
• Conventional hydrate control methods like thermal insulation, removal of water or application of
thermodynamic inhibitor may not give desired prevention of hydrate growth and are uneconomical.
Kinetic hydrate inhibitors and anti-agglomerants which fall under the category of low dosage
hydrate inhibitors are cost effective and are proven to be highly effective compared to most of the
traditional thermodynamic hydrate inhibitors.
1. Mechanism of hydrate nucleation
a. Labile cluster nucleation

Proposed bySloan &Fleyfel and Muller-Bongartz et al. that nucleation of hydrate particles is a series of
four consecutive reaction stages. In the first stage, free water molecules around the guest molecule to
form unstable cavities. The cavities may either decompose into the original water molecules or
agglomerate to form sI or sII hydrate. In second stage, cavities that encage guest molecule mayoscillate.
In the third stage, they eventually form small units.In fourth stage, the hydrate units reach the critical
nucleus size.
b. Reaction nucleation
This mechanism was proposed by Lekvam and Ruoff.Three dynamic elements are considered in this
model for hydrate formation. First, methane gas molecules dissolve into the water.An oligomeric
precursor of methane hydrate is then established, followed by the autocatalyticgrowth of methane
hydrate.
c. Interface nucleation
Long and Kvamme proposed nucleation of hydrates at the interface. Gas molecules move to the suitable
location and get absorbed where water molecules rearrange around theabsorbed gasesand form a cluster.
Then the clusters agglomerate to reach critical size.
d. Two-step hydrate nucleation

A two-step hydrate formation mechanism was proposed by Chen and Guo. Dissolved gas molecules
combine with water molecules to form labile clusters.Formed clusters will then combine with each

other to form hydrate and another empty cavity is created automatically. In the next step, theempty
cavities absorb small gas molecules.
e. Local structuring nucleation

Local structuring nucleation mechanism was proposed by Radhakrishnan and Trout. Mechanism
suggests a local structuring method for formation of hydrates rather than by the labile clusters. Because
of the thermal fluctuation, gas molecules are arranged in a clathrate phase configuration. Water
moleculesthen surroundthe gas molecules to form hydrates.
f. Blob nucleation
Jacobsen et al. suggested blobhypothesis which is a combination of labile cluster mechanism and local
structuring mechanism. Dissolved gasesform amorphous clusters in water called blobs and transform
into the amorphous clathrate nucleus. Then the amorphousclathrate nucleus converts to crystalline
clathrate.
Development of low dosage hydrate inhibitors

In 1991, the first kinetic hydrate inhibitorwas developed by Colorado School of Minesnamedpoly
(vinylpyrrolidone), which delayed the formation and the agglomeration of THF hydrates. According to the
previous studies, thosematerialwith strong electrostatic charges or/andstrong hydrogen-bond are effective to
inhibit hydrate formation, including NaCl, methanol, poly ethylene oxide (PEO), poly N-vinylpyrrolidone,
etc.Also based on this concept, ionic liquid (IL) has been developed as their structure and physical properties
could be fine-tuned for different applications.The first useful class of AAs were alkylarylsulfonates which was
developed by Shell.Exxon filed patents on a number of classes of polymer containing amide groups as hydrate
inhibitors. These included polyalkylacrylamides, polydialkylacrylamides, polyvinylamides, polyallylamides,
polymaleimides, and polymers of cycliciminoetherssuch as polyacylalkyleneiminesand polyalkyloxazolines
(ring-opened and ring-closed) and amides or esters of N-acyldehydroalanine.Yongjunet. al. reported that
Chitosan is a linear polysaccharide composed of randomly distributed b-(1-4)-linked d-glucosamine
(deacetylated unit) and Nacetyl- d-glucosamine (acetylated unit) moieties. Chitosan is water insoluble, but it
does show the tendency to participate in hydrogen bonding in the presence of water and it can be dispersed in
water at high rotation speeds (200 rpm). Asheesh Kumar et. al. reported that the hydrate decomposition kinetics
in the presence of the LDHIs are temperature dependent and show an enhanced rate of hydrate decomposition
relative to that of the pure water hydrate at 293 K.Lee et al. have reported that the induction times differs in
specified solutions with and without a non-aqueous condensate phase and it have been observed that non
aqueous condensate phase lowers induction time by a factor of two.Jeong-HoonSa et. al. have reported that the
amino acids L-Serine and Glycine are the best KHI for inhibition of both hydrate nucleation and growth.
The review of different low dosage hydrate inhibitors is carried out from different literature are given in the
table 1.

Table 1: Different of low dosage hydrate inhibitors developed over time
Sr. No. Name Courtesy

1 Poly(vinylpyrrolidone) (PVP) Colorado School of Mines
2 Poly vinylcaprolactum (PVCap) Colorado School of Mines
3 Butylated PVP Shell
4 Alkylarylsulfonates Shell
5 Alkyl glycosides Shell
6 Polyalkylacrylamides Exxon
7 Polyacryloylpyrrodene (PolyAP) Exxon
8 Butyl glycol ether (BGE) French Petroleum Institute
9 Polyvinyloxazolines ExxonMobil
10 Polyalkylacrylamide ExxonMobil
11 Chitosan Yongjunet. al.
12 PVCap& Polyvinyl alcohol (VOH) Musa & Co-workers
Copolymer
13 Glycine Jeong-Hoon Sa et. al.
14 Poly (N-isopropylacrylamide) Pei Cheng Chua et. al.
15 Poly (N-methyl N-vinylacetamide) Exxon
[VIMA]
16 Tetrabutylammonium bromide Shell
(TBAB)
17 Tetrapentylammonium bromide Shell
(TPAB)
18 2-butoxyethanol Andrea Perrin et. al.
19 Polyaspartamides Andrea Perrin et. al.
20 Tyrosines British Petroleum (BP)
21 Polydialkylacrylamides Exxon
22 Polyvinylamides Exxon
23 Polyallylamides Exxon
24 Polymaleimides Exxon
25 L-Serine Jeong-Hoon Sa et. al.
Working of Low Dosage Hydrate Inhibitors (LDHIs)

Unlike thermodynamic inhibitors, LDHIs do not significantly change the hydrate equilibrium curve, but work
on the mechanism of surface adsorption or interference with the nucleation or growth of hydrate crystals,
depending on the types.
Anti-agglomerants are surface active agents that get attached to the hydrate particles dispersed in the system
and prevent them from agglomeration. Tiny hydrate particles remain dispersed in the oil layer as their surface
becomes hydrophobic due to attachment with the anti-agglomerants molecules. Working for low water cut

system in the range of 40 – 60% and formation of emulsions, as these are surfactant are the two limitations of
anti-agglomerants.
Kinetic hydrate inhibitors are low molecular weight polymers that are soluble in water and they work
differently than anti-agglomerants. Anti-agglomerants do not prevent hydrate formation, but prevents their
agglomeration; whereas kinetic hydrate inhibitors delay the formation of hydrate in a system. They increase the
induction time of hydrate formation. KHIs have a subcooling limitation of around 12 0C. So, to get the better
beneficiation effects at higher subcooling conditions, KHIs are used in combination with methanol. KHIs have
a limitation of higher temperature and high salt content of water, where their solubility decreases.
1. Benefits of low dosage hydrate inhibitors

Application of LDHIs reduce the total cost of operation in terms of the following:
a. Reduced inhibitor requirement: Shifting from thermodynamic inhibitors to LDHIs, hydrate volume
requirement is reduced by 90%, leading to a potential cost saving of the operation. The chemical cost,
transportation cost and manpower cost for handling of inhibitors are drastically reduced. LDHIs are
used at levels between 0.25 to 5 vol.% of the produced water, which is dramatically lesser volume
compared to widely usedthermodynamic inhibitors like methanol or mono-ethylene glycol.
b. Pumping facilities: Smaller pumps are required for injection of LDHIs, as amount to be pumped is
very less compared to methanol or other thermodynamic inhibitors.
c. Piping requirement: Reduction in piping facilities is another benefit obtained with LDHIs. As LDHIs
can be co-formulated with other additives like corrosion inhibitors or wax inhibitors, thus the chemical
injection lines can be minimized. Hence, fewer umbilical lines and smaller umbilical line diameter leads
to potential cost saving.
d. Recovery operation: Since very less quantity of additives are used, so there is no requirement of wash
and recovery operations, which saves a huge part of CAPEX.
e. Storage requirement: Due to lesser volume requirement of LDHIs, lighter storage capacity serves the
operation.
f. HSE risk: LDHIs are less volatile and flammable compared to the thermodynamic inhibitors and
comparatively more environmentally friendly. The risk of explosion is eliminated, which was a major
concern in case of use of methanol.
Conclusion:
In this article, it has been focused on reviewing the studies that have been conducted on low dosage hydrate
inhibitor development. LDHIs are the key solution for hydrate plug issues because of the beneficial effects as
discussed in this article. Modification to LDHIs are required depending on the condition of hydrate formation.
Different parameters such as water cut, subcooling etc. effect the performance of LDHIs from case to case. So,
in different areas and under different conditions, modification to LDHIs is required on which industry needs to
focus now.
Acknowledgement
Authors thank Gas Hydrate Research and Technology Centre, Oil and Natural Gas Corporation Limited,
Panvel, Navi Mumbai for providing financial assistance to carry out this study and permission for presentation
in IOGCA – 2019.

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Technology, Doha, Qatar, 21-23 November, 2005.
2) Erfani, A., Varaminian, F., Muhammadi, M., “Gas hydrate formation inhibition usinglow dosage
hydrate inhibitors”, 2nd international Iranian conference on Gas Hydrate, Semnan University.
3) Frostman, M.L. et al., “Low dosage hydrate inhibitors (LDHIs): reducing costs in existing systems and
designing for the future”, SPE international symposium on oilfield chemistry held in Houston, Texas,
U.S.A., 5 – 8 February, 2003.
4) Jr. E., D., S., 1991. Natural Gas Hydrates. Journal of Petroleum Technology, 1414-1417.
5) Kelland, M. A., 2006. History of the development of Low Dosage Hydrate Inhibitors. Energy & Fuels,
825-847.
6) Kelland, M. A., Monig, K., Iversen, J.E., Levkam, K., 2008. Feasibility Study for the Use of Kinetic
Hydrate Inhibitors in Deep Water Drilling Fluids. Energy & Fuels 22, 2405–2410.
7) Kelland, M. A., Svartaas, T. M., Ovsthus, J., Tomita, T., Mizuta, K., 2006. Studies on some alkylamide
surfactant gas hydrate anti-agglomerants. Chemical Engineering Science 61, 4290-4298.
8) Kumar, A., Sakpal, T., Kumar, R., 2015. Influence of Low-Dosage Hydrate Inhibitors on Methane
Clathrate Hydrate Formation and Dissociation Kinetics. Energy Technology, 717-725.
9) Perrin, A., Musa, O., M., Steed, J., W., 2013. The chemistry of low dosage clathrate hydrate inhibitors.
The Royal Society of Chemistry, 42, 1996-2015.
10) Peytavy, L. J., Glenat, P. Bourg, P., “Qualification of low dose hydrate inhibitors (LDHIs): field
casesstudies demonstrate the good reproducibility of the resultsobtained from flow loops”, 6th
International Conference on Gas Hydrates (ICGH 2008),Vancouver, British Columbia, CANADA, July
6-10, 2008.
11) Sa, J. H., Kwak, G. H., Han, K., Ahn, D., Cho, S. J., Lee, J. D., Lee, S.H., 2016. Inhibition of methane
and natural gas hydrate formation by altering the structure of water with amino acids. Nature, 1-9.
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14) Salmin, D. C., Majid, A. A. A., Wells, J., Sloan, E. D., “Study of Anti-Agglomerant Low Dosage
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15) Turner, J. D. et al., “Formation of hydrate obstructions in pipelines:hydrate particle development and
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Title: “Effect OfImidazolium Based Ionic Liquid on Interfacial and Wettability Alteration Behavior for
Application In Enhanced Oil Recovery”
-Prathibha Pillai, Ajay Mandal, Petroleum Engineering Department, IIT(ISM) Dhanbad
Keywords: Enhanced oil recovery, Ionic liquid, Interfacial Tension, Wettability Alteration
Abstract:
Ionic liquids are emerging as one of the promising environmental friendly solutions to enhance the oil
recovery. Ionic liquids are salts having melting point below 100°C and are in liquid state at room temperature.
This research is aimed at showing the suitability of ionic liquid as a new chemical system which can be used as an
alternative to conventional surfactants in EOR. In this study an imidazolium based ionic liquid (1-dodecyl-3-
methylimidazolium bromide) was synthesized and used as a surface active agent for enhancing oil recovery.
The CMC of the [C 12 mimBF 4 ]in aqueous solution was observed to be very low in comparison to conventional
surfactantsused in EOR. IFTof the crude oil systemwith aqueous ionic liquid solution was determined by
spinning drop technique. It was observed that ionic liquids were able to significantly reduce IFT and remained
stable at elevated temperature and saline conditions. Wettability tests using contact angle measurements were
conducted to study the efficiency of ionic liquid in altering the wettability of oil-wet sandstone sample towards
more water-wet. Contact angle measurements confirmed that ionic liquid was able to favorably alter the
wettability of oil-wet sandstonesurface towards water-wet. Emulsification tests confirmed the capability of the
ionic liquids to emulsify the trapped oil, which is an important mechanism of chemical EOR. Micro-emulsion
study showed Winsor type III behavior with ultra-low IFT, which is beneficial for EOR application. Thus it can
be stated that ionic liquid shows greater ability of improving oil recovery compared to conventional surfactants
especially at high saline conditions and temperature conditions.
1. Introduction
With the increase in global demand and declining petroleum reserves, focus is laid on developing new chemical
systems which are able to tolerate harsh conditions (i.e. high temperature and salinity) of reservoir as well as
reduce interfacial tension (IFT) and improve rock-wetting characteristics for enhanced oil recovery.After
primary and secondary oil recovery significant fraction of original oil in place (OOIP) still remain trapped in
the reservoir as residual oil [1]. The trapping of the non-wetting oil phase in the pores of the rocks is due to the
capillary forces which exist in the form of interfacial tension (IFT). Enhanced oil recovery techniques are
developed as a promising method aiming to reduce residual oil saturation [2]. Among the various EOR
techniques, chemical flooding is one of the most successful techniques that has been used worldwide for
decades because it is capable of reducing oil/water IFT and controlling mobility ratio [3]. Chemical flooding
method adopted also has various disadvantages such as high toxicity, high cost and inability to perform in harsh
environments [4]. Additionally, insoluble residues left by a surfactant or other chemical formulations can
damage the oil reservoirs developing environmental impacts [5]. This lead to the research of chemical systems
that are environmentally acceptable and can be used in EOR.
The increasing demand for energy has directed the oil industry to explore other surface-active chemicals, which
can alter wettability as well as reduce the adsorption compared to conventional surfactants. IL is emerging as
an alternative to the conventional surfactants and various studies highlighting its surface-active nature have
been investigated [6–8]. ILs are organic salts, which are liquid in the room temperature with some encouraging
properties such as high thermal stability, nonvolatility, salt tolerance, nonflammability, and low critical

micellar concentration (CMC), and so forth.Various studies to investigate the effect of IL on IFT and its
favorable impact on the recovery of oil have been conducted [9]. ILs are acknowledged for their surface
activity and micelle formation behavior, which play a pivotal role in flooding processes [10]. ILtunability
allows them to be utilized in different reservoirs, with different fluid properties.
In our earlier work [10], the surface activity of three synthesized ionic liquids namely, C8mimBF4,
C10mimBF4 and C12mimBF4 were determined to understand the structure–property relationships for
industrial applications. Surface activity of the ionic liquids was found to be improved with increasing alkyl
chain length. This work is an extension of the previous work and focuses on determining its effectiveness, in
reducing surface tension, IFT and wettability alteration of oil-wet quartz surface for its potential application in
EOR. The phase behavior of the ionic liquid was also investigated.
2. Experimental
2.1. Materials required
1-bromododecane (99.5%), 1-methylimidazole (99.5%), dichloromethane (99.5%) and sodium
tetrafluoroborate (98.5%) were obtained from SRL chemicals. Ethyl acetate and acetone, which were used as a
solvent for the synthesis route, were purchased from TCI chemicals. NaCl and organic alkali triethylamine
(TEA) purchased from Sigma–Aldrich Co. LLC. The crude oil sample used was procured from ONGC
(Ahmedabad, India). The oil has 29.21° API at 30 °C. Double distilled water was used to prepare the aqueous
solutions.
2.2. Synthesis
The reaction mechanism for the synthesis of the ionic liquid is presented in Fig. 1. As shown in Fig. 1,
reactions between 1-methylimidazole and alkyl bromide (1-bromooctane for [C 8 mimBF 4 ], 1-bromodecane for
[C 10 mimBF 4 ] and 1-bromododecane for [C 12 mimBF 4 ]) in a ratio of 1:1 were carried out for 48 h under reflux
condition at 70 °C. To eliminate unreacted materials, the reaction mixture was washed with ethyl acetate and
then heated up to 70 °C to remove the rest solvents. A pale-yellow liquid was obtained, which was vacuum
distilled and then vacuum dried at 80 °C. The product was further reacted with NaBF 4 in the presence of
acetone for 10 h under 40 °C. Dichloromethane was then added to remove the residue. The final product was
vacuum dried and traces of dichloromethane were eliminated[10,11]. The characterization of synthesized ionic
liquid was performed using FTIR, NMR and TGA and discussed in detail our earlier works [10].
Br
N N
N N+
R
Br-
1-Methylimidazole Alky-bromide 1-Methyl-3-alkylimidazolium
bromide
F
F
N N+ F B- F
N N+ F B- F
Na+ F
Br- F
1-Methyl-3-alkylimidazolium Sodium tetra fluroborate

bromide 1-Methyl-3-alkylimidazolium
tetrafluroborate
Fig 1. Reaction Scheme of Ionic Liquid synthesis

2.3. Surface tension

The surface tension of synthesized ionic liquids was measured using Easy Dyne K20 Tensiometer (KRUSS
Germany) at 30 °C with an accuracy of ±0.1 mN/m. The aqueous solutions of varying ionic liquid
concentrations were prepared. The platinum ring used for surface tension measurement was cleaned with
acetone and flame-dried before each measurement. The surface tension of each solution was repeated three
times and average value was taken.
2.4. Interfacial tension

Interfacial tension between the ionic liquid aqueous solution and crude oil was measured by spinning drop
method using SVT20 tensiometer (Dataphysics, Germany) with a precision of 0.02 mN/m and temperature was
maintained with an accuracy of ±0.03 °C. IFT of crude oil/water system with varying concentration of ionic
liquid, salinity and alkali was investigated. The ionic liquid aqueous solution as an outer phase and crude oil as
an inner phase was injected into the capillary tube with the help of the syringe and it was rotated at 6000 rpm.
IFT values for individual samples were measured multiple times to ensure the accuracy of results. Prior to each
measurement it was ensured to clean the capillary tube to remove any residual oil present.
2.5. Wettability Alteration

Wettability alteration studies were performed using Drop Shape Analyzer (Kruss DSA25, Germany) by Sessile
drop method and the contact angles were measured with an accuracy of ±0.3°. Contact angle measurement was
performed on quartz rock sample (70 × 70 × 5 mm) which was aged initially in crude oil for a month to alter
the wettability of the sample to oil wet. The contact angle of the ionic liquid solution with varying
concentrations was measured by carefully dropping a very small drop of 10 μL sample solution through the 0.5
mm outer diameter needle tip on the surface of the rock, and the reduction of the contact angle was measured
with respect to time at 30 °C. To eliminate cross contamination samples were dropped on unaltered part of
quartz surface. Measurements were repeated thrice and average values were reported.
2.6. Emulsion stability test

To develop an idea about the emulsifying ability of synthesized ionic liquid, emulsion stability tests were
conducted. In each set of tests, a group of vials was used, each of which contained different aqueous phases
with different ionic liquid concentrations mixed with crude oil in a ratio of 2:1. The vials were then sealed and
agitated vigorously by hand until each mixture appeared to be homogenized as one phase. Consequently, the
tubes were then left for several hours to monitor the partitioning of the crude oil and ionic liquid solution to
study the rate of separation was also studied. Pictures of vials containing the mixture were taken at different
times of t = 5 min, 60 min and 1 week. Further to investigate the effect of the salinity on C 12 mimBF 4 , 1:1 ratio
of crude oil and ionic liquid solutions (at CMC) with increasing salinity (0%, 3%, 5% and 7%) were mixed
with an ultrasonic homogenizer Hielscher UT 200 Ht to form microemulsion. The formed emulsion was kept at
75 °C in an oven to analyse the effect on emulsion stability. Photographs of the vials containing the mixture
were taken with time.
3. Result and Discussion

3.1. Surface tension measurements
The variation of surface tension with increasing ionic liquid concentration are presented in Fig. 2(a). As
observed from the figure initially with increasing concentration surface tension decreases and after attaining a
certain concentration no further reduction is observed. This particular concentration above which surface
tension remains constant is known as critical micelle concentration (CMC) [12]. Before attaining CMC,

adsorption is in a dynamic equilibrium with ionic liquid molecules and as the concentration increases
adsorption of the ionic liquid molecules onto the air–water interface increase and hence surface tension
decreases. As the CMC of ionic liquid attains, the interface is at its maximum coverage and to minimize further
free energy, aggregation of molecules in the bulk phase occurs. Above the CMC, optimized adsorption of ionic
liquid monomers at the air–water interface takes place and the system then attains an equilibrium state with
adsorbed monomolecular layer, free monomers and micellized surfactant in the bulk [13]. Hence surface
tension attains constant value after CMC. The minimum surface tension value was recorded to be 27.32 mN/m
at 2000 ppm CMC value. The ability to lower the surface tension between the aqueous solution and other phase
is one of the most significant aspects of chemicals that raise their applicability in chemical enhanced oil
recovery [6].
3.2.1. Interfacial tension of aqueous ionic liquid solution and crude oil
The effect of concentration of ionic liquid on the IFT between their aqueous solution and crude oil were
investigated to check the potentiality for EOR application. From Fig. 2(b), it has been observed that there is a
sharp decline in IFT as the concentration of ionic liquids increases and further attains a minimum value. The
concentration of minimum IFT represents the CMC of the ionic liquid. As the CMC of the ionic liquid was
achieved IFT becomes nearly constant and the further increase in concentration increases the IFT value
slightly. The dependence of IFT on the ionic liquid concentration was due to the adsorption/desorption of the
ionic liquid molecules at the oil− water interface. At CMC the rate of adsorption and desorption was equal will
results in a minimum value. Above CMC, increase in IFT is due to the high desorption rate of the surfactant
from the interface[14]. As IFT decreases and capillary forces acting on the oil droplets reduces hence, oil starts
to flow. For synthesized ionic liquid a minimum IFT value was observed to be 2.1 mN/m at 2000ppm.
60
C12mimBF4 C12mimBF4
(a) (b)
10
50
Surface Tension (mN/m)
IFT (mN/m)
40
30
Critical micellar
concentration (cmc)
1
20 0 2000 4000 6000 8000 10000 12000 14000
100 1000 10000
Concentration (ppm) Concentration(ppm)
Fig. 2. Effect of ionic liquid concentration on (a) Surface tension and (b) Interfacial tension at 30℃
3.2.2 Effect of NaCl concentration on IFT

The effect of saline environment on the IFT of ionic liquids was examined by measuring the IFT of different
ionic liquids at their CMC by varying the salinity of the solutions. The effect of salt concentrations on IFT
reduction by the ionic liquids is shown in Fig. 4(a). From the figure, it was seen that there was relatively more
drop in IFT values in presence of NaCl. The presence of opposite ions of salt in the aqueous solution causes
electrical attraction between the positively charged cationic part of ionic liquids and the negative ions of the
salt, which reduces the electrical repulsion between cationic charges of ionic liquid head groups, thus improves
the IL molecule adsorption at the interface [15]. Hence, ionic liquid molecules will compactly occupy the
interface which leads to the higher IFT reduction. With increasing salt concentration IFT decreases and reaches
a minimum value beyond which IFT increases. The salt concentration corresponding to the minimum IFT is
known as optimum salinity. As observed IFT is low at NaCl concentration of 7%, which is considered as the
optimum salinity of the solution for C 12 mimBF 4 .At lower salt concentration, surfactant is more soluble in
brine, while at higher salt concentrations, solubility of surfactant is higher in oil [16]. The surfactant molecules
adsorbed on the oil/water interface desorbed constantly and entered into the oil phase with the increase in
salinity [16]. The obtained results demonstrate that for salts, the IFT decreases significantly at the beginning,
then increases with further addition of the salt but with a lower gradient. The addition of NaCl to the crude
oil/water system reduces the IFT from 2.1 to 0.56 mN/m for C 12 mimBF 4 . It can be concluded that the ionic
liquids are able to reduce IFT and remain stable at high saline conditions, thus ionic liquids are better than the
conventional surfactants in terms of their performance in high saline reservoirs.
3.2.3. Effect of organic alkali on IFT of Ionic liquids

Addition of alkali which has charged group in the solutes has a profound influence on the IFT, particularly if
the crude oil is having high acid number. Inorganic alkalis which are most commonly used in oilfields induces
clay swelling, scales formation, and other problems when large doses were injected into reservoirs. These
problems lead to the research of organic alkali which is non-toxic in nature, biodegradable and can be used for
environmentally sensitive areas [17]. In this study organic alkali, triethanolamine (TEA) was used in instead of
conventional inorganic alkalis. Experiments were performed using a solution of synthesized ionic liquid at
CMC, prepared in brine (3wt%) and varying alkali concentration (0 to 1.5wt%) and the results are shown in
Fig. 4(b). It may be found that when the concentration of TEA was increased from 0% to 1.5% a continuous
decrease in IFT values was observed. TEA reacted with organic components of the crude oil and generated in
situ surfactants thus inducing synergistic effect which reduces IFT [18]. In addition, TEA was also considered
as a surface active substance that can also adsorb at the water-oil interface to reduce [17]. But the decrease in
IFT after 1 % TEA was only marginal. The results showed a significant decrease of the IFT from 0.56 mN/m
to 0.036 mN/m for C 12 mimBF 4 at 1.5 % alkali concentration.
3
C12mimBF4 C12mimBF4
(a) (b)
1
2
IFT (mN/m)
IFT (mN/m)
0.1
1
0.01
5 10 15 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
NaCl ( wt. %) TEA conentration ( wt. %)
Fig. 4. IFT between crude oil and aqueous solutions of ionic liquid at CMC (a) with increasing NaCl
concentration and (b) at 3 % NaCl with increasing alkali concentration at 30 ℃
3.3Wettability Alteration
Wettability of a reservoir rock has a major effect on interface movement and associated displacement of oil
through porous media [19]. The main focus is laid on changing wettability from oil-wet to water-wet to
increase the oil recovery. Ionic liquid solution in contact with oil-wet quartz preferentially adsorbs at the
surface to displace the adsorbed oil, which causes the change of wettability. Fig. 6 depicts the change of contact
angle with time for three synthesized ionic liquids. As observed from the figure, the contact angle initially in
case of distilled water was 115° which indicates clearly that the rock sample was oil wet. With increasing
concentration, contact angle decreases rapidly due to the interaction between a hydrophilic group of ionic liquid
and a non-polar group of oil adsorbed on oil-wet rock surface [20]. As the ionic liquid solution gets adsorbed it
changes rocks wettability. The equilibrium contact angle reduces with increase in the concentration of ionic
liquid solution but the decrease is only marginal after CMC because of saturation of the surfactants at the rock-
fluid interface. For C 12 mimBF 4 contact angle was found to decrease to to 13° at CMC (2000ppm) after 60 min.
An average contact angle were obtained with an error of ± 0.31°-0.5° in the readings. Therefore, the
synthesized ionic liquid shows good results in changing the wettability of the rock from oil wet towards water
wet that ultimately enhance the oil recovery from the oil reservoir during the EOR process.
120 0 ppm
1000 ppm
2000 ppm
100
5000 ppm
Contact Angle (deg)
80
60
40
20
0
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Time (Min)
Fig. 5. Variation of contact angle with varying concentration of C 12 mimBF 4 aqueous solutionon oil-wet quartz
surface at 30 °C
3.4Emulsion stability test

Microemulsion can be considered as a subdivision of one phase into another phase in the form of small
droplets. Formation of these small droplets require the breakdown to phase surface area into new smaller
surface. For EOR applicability, surfactant in the aqueous solution must be able to solubilize oil from the
hydrocarbon phase to form microemulsion and reduce IFT so as to significantly improve oil recovery [21].
Emulsion stability tests were performed to study the behavior of synthesized ionic liquids toward the formation
of the stable emulsion. As observed ionic liquid with varying concentrations form emulsion once agitated and
separate slowly with time under static condition. The emulsion test concluded that C 12 mimBF 4 can form stable
emulsion, as the emulsion was stable even after one week and exhibited lower water separation rate.The
effectiveness of a surfactant flooding process was closely related to the phase behavior of the brine-oil-
surfactant system [22]. Thus, emulsion phase behavior test was performed for C 12 mimBF 4 with varying salt
concentration at 75 °C. At lower concentration of salt, the solubility of ionic liquid was more in water phase
and it forms water-external microemulsion at the bottom with oil phase at the top. This two phase
microemulsion is known as Winsor type I. At higher salt concentration, the solubility of ionic liquid is more in
oleic phase and oil-external microemulsion is formed at the top and excess water phase is at the bottom. This
type of two phase microemulsion is known as Winsor type II. However, at intermediate range of salinity, the
ionic liquid forms a bicontinuousmicroemulsion phase at the middle with oil phase at top and water phase at the
bottom. This three phase system in known as Winsor type III microemulsion[23]. This middle microemulsion
phase is in equilibrium with the either phases and is beneficial for EOR applications. Fig. 6 shows the pictures
of Winsor type III microemulsion formed at different concentrations on NaCl (3%, 5% and 7%).
Fig. 6. Phase behavior of C 12 mimBF 4 at varying salt concentration at 75°C
3. Conclusion
In the present study, the potentiality of synthesized ionic liquids was analyzed for its application in EOR in
terms of surface activity, IFT reduction, wettability alteration, adsorption behavior, emulsification and oil
recovery. The surface activity of synthesized ionic liquid was evaluated by means of surface tension and it was
observed that the surface activity increased with increase in alkyl chain length. Interfacial activity as a function
of the concentration of the ionic liquid, salt and alkali were measured and results revealed that the synthesized
ionic liquid was efficient in reducing IFT and the minimum IFT of 0.041 mN/m was obtained. Wettability
measurements proved that the ionic liquids were able to change the wettability of the reservoir rock toward
more water-wet conditions for more oil recovery efficiency. Emulsions showed stability at high temperature
and Winsor type III behavior was observed.Lastly, it can be concluded that ionic liquids can be considered as a
new generation of surfactants which could be utilized in the chemical EOR processes especially for the
reservoir with harsh conditions.
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Title: “Rheological Study of Slick water Fluid Systems Consisting of High-Vis Friction Reducers
Additives for Hydraulic Fracturing Applications”
-Navneeth Kumar Korlepara, Sandeep D. Kulkarni, Sumanth Ruttala, Ashok Deva Kumar, Sree Karthik
Dangeti, IIPE Vizag, Avinash Kumar Singh, IIT Kharagpur
Keywords: Friction Reducer (FR), High Viscous Friction Reducer (HVFR), Polymer concentration, Brine
composition
Abstract
Slickwater fracturing was developed in the late 1990’s to address the issue of clean-up of gels from the
fractures; the better clean-up using slickwater systems would improve performance of fractures created
compared to those created by guar gums or cross-linker fluid systems. The reach of slickwater treatment is to
create fracture network and fracture connectivity using huge amounts of water with additives like friction
reducers (FR) and hybrid FR/gellant combination. This approach enables the pumping rates to go as high as 60-
100 bbl./min and beyond that may help in proppant suspension as well as creating efficient fracture network.
Viscosity impact of Friction Reducers (FR) in slickwater fluid systems was not considered as an essential
component of the fluid system initially. However, the modern FR additives not only impart friction reduction
but also increase the fluid viscosity; providing a key advantage in proppant transport and suspension from the
perforations into the formation. These modern FRs, termed as high-vis FR (HVFR) additives, influence the
viscosity behaviour of the fluid system which may vary significantly with the fluid properties like TDS (Total
dissolved solids), hydration approach, polymer concentration, additive interaction and applied temperature
conditions.
Anionic FRs are known for having effective impact on viscosity and friction reduction of high-TDS slickwater
systems. In this work, a specific anionic FR was chosen for the study. The paper focuses on viscosity effects of
the chosen FR evaluated for different slickwater compositions with variation in the salt types (NaCl and CaCl2)
and salt concentrations up to 250k ppm whereas different concentrations of the chosen FR added into the
system (0.5 – 5 gpt). The viscosity response was investigated at room temperature (85 oF) using API
recommended practices. The time evolution of viscosity was also studied. Based on the data, a statistical model
was derived to predict the viscosity of a slickwater system for a given fluid TDS (monovalent/divalent salt
concentrations) and the FR concentration. The model also captures the effect of temperature and time on the
viscosity behaviour of the fluid system.
This work would enable the estimation of viscosity impact of the FR additive; accordingly, it would assist in
minimizing the trial-and-error approach in designing/optimizing a slickwater fluid system. The developed
models can also help in providing on-the-fly recommendation for the FR-additive concentration in a given
produced-water/slickwater system; thus providing real-time solution for effective fracturing treatment.
Introduction
In the 1860’s, well stimulation was performed with explosive fluids like nitro-glycerine. Development of well
stimulation fluids from explosive to non-explosive started in the first half of the 20th century. Acid stimulations
were commercialized in the 1930s. During the late 1940s and early 1950s, commercial hydraulic fracturing has
been in practise for well stimulation (Montgomery 2010). Later half of the 20th century, hydraulic fracturing

has become arguably one of the most leveraging completion technologies in unlocking the potential of several
reservoirs specifically, the unconventional ones (Palisch 2010). The fluids are known as hydraulic fracturing
fluids or HydraFracs (Clark 1949), which are specifically designed in propagating fractures to enhance
hydrocarbon production from wells. Fracturing fluids are mostly comprised of water and proppant sand for
99.5% of the fluid, along with additives of 0.5%, which characterize the fracturing fluids. Linear gels and
Cross-linked gels are used in the early stages; the shift is towards in employing slickwater fluids.
A Slickwater fluid is a water-based fluid with proppant combination having low viscosity. This is an advantage
in using slickwater, as the conventional fracturing fluids pumping rates are pre-60 bbl./min whereas the
slickwater fluids pumping rates can exceed 60bbl./min. The high pumping rates helps in generating narrow
fractures with low concentrations of proppant. Designing slickwater fluids is crucial, as the fluid rheology is the
key for proppant transport. The slickwater fluids have additives like surfactants, friction reducers, acids, gelling
agents, scale inhibitors which characterize the fluid rheology. The weakness in slickwater fluids is the low
viscosity, which exhibits low proppant transport and to overcome the weakness, the slickwater fluids must be
pumped at high rates which creates friction in the tubing (Zhou 2011).
Friction reducers are utilized to address the friction in the tubing. It is one of the critical additives in slickwater
fluids, which facilitates higher pump-rates. Commonly used FRs are polyacrylamides (PAM) and based on the
salinity concentration in slickwater fluid, anionic PAM or cationic PAM is utilized. The general challenge faced
in slickwater fluids is proppant transport, as the fluid is less viscous. If the slickwater fluids are designed/
comprised with additives which can address both friction reduction and viscosity, the proppant transport can be
dealt off. These additives are acknowledged as High-Vis Friction Reducers (HVFRs), which are adequate to
cope the viscosity required for proppant transport and friction reduction in the tubing.
HVFRs are widely applied in oil and natural gas development primarily as a friction reducer to minimize
frictional losses during pumping (Sun 2010; Aften 2009; Fink 2013; Al-Sarkhi 2010). PAMs exhibit drag
reduction properties which arise from polymer elongation that dampens the vortices which is a characteristic of
turbulent flow (Dubief 2005; Usui 1988; White 2008). Anionic PAMs perform better as drag reducers in a fresh
water environment to low TDS levels (Rodvelt 2015); at high salinities, cationic PAMs have shown better
performance (Paktinat 2011).
There is limited literature on modelling of the time dynamic viscosity response was of the FR fluids. This work
primarily focuses on consistent dynamic viscosity measurement of FR-brine solutions which can vary
depending on FR hydration, FR concentration and brine concentration (Aften 2018).
Experimental Procedure
FR-brine solution preparation: High-Vis Friction Reducers (HVFRs) have complex chemistry which are
primarily polymers developed from acrylamide. The first step of the experimental procedure involved
preparation of a synthetic brine solution of 400 ml volume and desired salinity at a constant speed at ambient
temperature. Salt weight was determined; to be added in the water for desired salinity. Water and salt were
mixed in a constant speed mixer at 1500 RPM for 90 seconds (1½ minutes). The selected anionic Friction
Reducer (FR) with determined FR concentration was added to the brine solution. The constant speed mixer was
operated again at the 1500 RPM for 10 seconds. The FR–brine solution was then transferred for further testing
on the viscometer.

Viscosity measurements: The FR-brine solution was tested for viscosity using API recommended practice, i.e.,
300 RPM on a FANN 35 viscometer (R1B1 geometry) and ambient temperature (85 oF). The viscosity
measurements were conducted at the intervals of 1 minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 60
minutes, to study the dynamics of the polymer hydration. The testing
Procedure was repeated for the FR-brine solutions with different FR concentrations and different salinities (salts
of NaCl and CaCl2).
This work focusses on study of impact of three test parameters on FR-brine solution viscosity: time dynamics,
FR concentration and brine salinity. Table 1 shows the test parameters with intervals/ levels at which FR –brine
solution viscosities were determined.
Table 1: Parameters with levels considered in Design of Experiment (DoE).
S. No. Parameter Levels
1 Time, minutes 1, 3, 5, 10, 30, 60
Friction Reducer Concentration,

2 gpt 0.5, 1.5, 2.5, 3.5, 5
50,000; 100,000; 150,000; 200,000;

3 Salt Concentration, ppm 250,000
Design of Experiment (DoE) was constructed to study the two parameters: FR concentration and brine salinity
considering the levels shown Table 1. The DoE consisted a half factorial (½ factorial) approach and,
additionally testing for the four corners of FR concentration and brine salinity domain as shown in Fig. 1 and
Fig. 2. Thus, the total test points were sixteen for each type of the brine considered as depicted in Fig. 1 and
Fig. 2.

The experiments were conducted at ambient temperature (85 oF) at randomly generated test points from Design
of Experiment (DoE). The viscosity of FR – brine solution was captured at different time intervals (from the
instant of the FR addition) and plotted Fig. 3 and Fig. 4 to depict the time dynamics of FR–brine solution
viscosity for both salts: NaCl and CaCl2.

Figure 4: Plot for viscosity vs. time for different FR-brine solutions comprising of CaCl2 salt.
The following observations were made based on the dynamic viscosity data of the FR–brine solutions.
I.FR-brine solutions comprising of NaCl salt
a. a.NaCl concentration had an incremental effect on FR–brine solution viscosity.
b. b.FR concentration has an incremental effect on FR–brine solution viscosity.

c. c.FR–brine solution viscosity has peaked at about10 minutes for the studied combinations of salinity and
FR concentration.
d. d.FR–brine solution viscosity reached to a plateau beyond about 30 minutes for the studied
combinations of salinity and FR concentration.
II.FR-brine solutions comprising of CaCl2 salt
a. a.CaCl2 concentration had an incremental effect on FR–brine solution viscosity.
b. b.FR concentration has an incremental effect on FR–brine solution viscosity.
c. c.FR–brine solution viscosity has peaked at about10 minutes for the studied combinations of salinity and
FR concentration.
d. d.FR–brine solution viscosity reached to a plateau beyond about 30 minutes for the studied
combinations of salinity and FR concentration.
e. e.Exothermic nature of brine formulation using the CaCl2 salt needs to be carefully compensated to
obtain consistent data.
Based on the above data and interpretations, statistical models were developed to estimate the dynamic viscosity
of the FR-brine solutions for a given concentration of the anionic FR and brine salinity. The generic form of the
model is represented as:

The constants “a”, “b” and “d” were obtained separately for FR-brine solutions consisting of the two salts:
NaCl and CaCl2. The model accounts for the baseline viscosity of the brines in absence of the FR as depicted in
the above equations.
Based on the developed models, FR–brine solution viscosity was predicted and plotted against experimental
values; Fig. 5 depicts FR-solution viscosity prediction (blue curve) at different concentrations of the FR for the
salinity of 50,000 ppm NaCl brine (at 30 minutes of polymer hydration interval). The figure also shows the
corresponding experimental data points (orange dots). The model prediction agrees reasonably with the
experimental data points. Fig. 6 depicts FR-solution viscosity prediction (blue curve) at different concentrations
of the FR for the salinity of 250,000 ppm NaCl brine (at 30 minutes of polymer hydration interval). The figure
also shows the corresponding experimental data points (orange dots). The model prediction agrees reasonably
with the experimental data points.
Fig. 7 depicts FR-solution viscosity prediction (blue curve) at different concentrations of the FR for the salinity
of 50,000 ppm CaCl2 brine (at 30 minutes of polymer hydration interval). The figure also shows the
corresponding experimental data points (orange dots). The model prediction agrees reasonably with the
experimental data points. Fig. 8 depicts FR-solution viscosity prediction (blue curve) at different concentrations
of the FR for the salinity of 250,000 ppm CaCl2 brine (at 30 minutes of polymer hydration interval). The figure
also shows the corresponding experimental data points (orange dots). The model prediction agrees reasonably
with the experimental data points.
The average error between predicted dynamic viscosity and corresponding experimental data was 0.76 ± 0.38.

Conclusions
• The polymer hydration of the studied anionic FR (i.e. APAM) in brines is a time-dependent
phenomenon.
• The FR investigated in this study was found to be more effective in NaCl brines that CaCl2 brine in
terms of viscosity improvement.
• The viscosity dependence of the FR-brine solution on the FR concentration was found to be exponential.
• The empirical based exponential models predict the dynamic viscosity of the FR-brine solution with
reasonable accuracy of the measuring viscometer.
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16. Usui, H., Kodama, M. & Sano, Y. Laser-Doppler measurements of turbulence structure in a drag-
reducing pipe flow with polymer injection. J. Chem. Eng. Jpn. 21, 134–140 (1988).
17. Virk, P. S. Drag reduction fundamentals. AIChE J. 21, 625–656 (1975).
18. White, C. M. & Mungal, M. G. Mechanics and prediction of turbulent drag reduction with polymer
additives. Annu. Rev. Fluid Mech. 40, 235–256 (2008).
19. Zheng, H., Ma, J., Ji, F., Tang, X., Chen, W., Zhu, J., Liao, Y., and Tan, M. Synthesis and Application
of Anionic Polyacrylamide in Water Treatment: A Review, Asian J. Chem., 2013, 25(13), pp 7071-7074.
20. Zhou, M. J., Sun, H., Qu, Q., & Bai, B. (2011, January 1). An Effective Model of Pipe Friction
Prediction from Laboratory Characterization to Field Applications for Friction Reducers. Society of Petroleum
Engineers. doi:10.2118/146674-MS.

Title: “Crude Oil Flow Assurance Water Base Surfactant – A Case Study Conducted On A Heavy Waxy
Crude Oil At Various Temperature Range.”
-Mr Noor Hisham Bin Ab Hamid, Euro-Circuit Technology Sdn Bhd
Key words: Flow assurance, viscosity, heavy waxy crude oil, water base surfactant
Abstract:
This Paper Discusses on a case study conducted on a heavy waxy crude oil with the viscosity characteristic of
up to 8000cps at 20 through to 6 cps 40, where with the influence of a water base surfactant, was capable of
reducing the viscosity to between 50% to 95% at those tempertures, depending on the dosing rate making it
flowable and pumpable. Flow assurance a relatively new term in oil and gas industry. It refers to ensuring
successful and economical flow of hydrocarbon stream from reservoir to the point of sale. Flow assurance is
extremely diverse, encompassing many discrete and specialized subjects and bridging across the full
gamut of engineering disciplines. Besides network modeling and transient multiphase simulation, flow
assurance involves effectively handling many solid deposits, such as, gas hydrates, asphaltene,
wax, scale, and naphthenates. Flow assurance is the most critical task during deep water energy production
because of the high pressures and low temperature (~4 degree Celsius) involved. The financial loss from
production interruption or asset damage due to flow assurance mishap can be astronomical. What compounds
the flow assurance task even further is that these solid deposits can interact with each other, and can cause
catastrophic blockage formation in pipelines and result in flow assurance failure. Some guidelines are given in
this paper for managing emulsion crude oil system issues with respect to temperature gradient that significantly
affecting the viscosity.
Introduction
For many years fossil fuels were the main, well-satisfying and reliable source of power, until recently threats of
the depletion became evident. Although it is commonly accepted that all the fossil fuels are diminishing, in fact
it is only the ones that are easy to extract are in danger. [1] Apart others these include light crude oil which is
relatively easy to extract and transport as it is of low viscosity. Meanwhile there are also other materials from
which we could create energy, heavy waxy hydrocarbons. Since heavy waxy crude oil accompanies large
portion of the crudes in the world, better techniques for its extraction and transportation are in particular interest
today.
Heavy hydrocarbon with long chains at room temperature possesses an extremely high viscosity ranging from
1000 to 100,000 cst. [2] Heavy hydrocarbons are difficult to work with due to their high pour points as well as
presence of hydrocarbon solids (such as asphaltenes, wax, and hydrate) that deposit in the flow systems and
block the other hydrocarbon. [3] Flow assurance analysis allows predicting, assessing and preventing deposition
of these solids which in turn averts this big obstacle to the success of oil production companies. [4, 5] This has
been a big challenge especially for the petroleum companies that extract waxy viscous oils from the
underground of the ocean, such as ONGC from India. Crude oil from India with characteristic viscosities of
8000 cst was used in this case study. Extraction type for this particular oil requires pumping system, which in
turn needs viscosities not exceeding 1000 cps. Moreover, temperatures of the ocean bottoms drop below the
pour points of the oils, making them solid and almost impossible to get. Even bigger problems are faced during
the transportation phase of the heavy crudes which is usually done through the pipelines requiring only 200 cst.
[6]

For this reason different strategies already exist for the heavy crude recovery and transportation. However each
of these strategies has its own disadvantage either pricewise, technically, logistically or they pollute the
environment. [6] Nevertheless, to this day the most promising solution is chemically engineered strategy with
the applications of physic-chemical advancements. Surface active agents (surfactant), provide us with an
elegant, non-toxic, effective, easy and cheap solution by significantly decreasing the interfacial tension between
aqueous medium and hydrocarbon, emulsifying oil-in-water and increasing water wettability of the wellhead.
[6]
This paper aims to find the most optimum concentrations and volumes of the green product, water- based
surfactant formulation – Bio-Surfactant Solution, BSS. This agent consists of water and naturally-derived
surfactants which do not harm the environment or have a flash point, is not toxic, flammable, corrosive or
volatile and which is safe and easy to use. Herein the pour points of waxy crudes before the application of BSS
and after were studied. The effectiveness of BSS on the dilution of waxy, viscous crude oils was also recorded.
Methods and Materials

The case study for waxy crude oil samples were carried out consisted of two parts: first, the effect of BSS on the
viscosities was tested, and second, different pour points were observed upon application of BSS to waxy crudes.
Reducing the viscosities of crude oil

All oil is different and reacts differently, thus prior to any experimentation it was characterized with reference to
the American Petroleum Institute gravity (API Gravity), as a measure. For the subjected, its API Gravity was
36.5°. Thus, since the value was above 10°, tested hydrocarbon was light. (Appendix P-1: Table 1.2) [7] The
analysis also showed that crude oil contained light asphaltenes content (0.8%), resins content (11.98%), and
wax content (8%).
BSS was diluted to 2.5%, 5%, 10%, and 15% concentration. Densities of the samples were measured at SGS
Port Klang, Malaysia. 24 samples of crude oil of 50 ml volume were prepared in 100 ml beaker by stirring for 5
minutes and the viscosity measurements of raw oils were obtained at room temperature, 27 °C. Then 1 ml of
2.5%, 5%, 10% and 15% concentrations of BSS were added to the crude oil samples, followed by stirring the
solutions for 5 minutes and measuring the viscosities. The same steps were carried out for 2.5 ml, 5 ml, 10 ml,
20 ml, 29.4 ml, 40 ml, 50 ml of BSS. Next, the procedure was repeated for every concentration and volume at
40°C, and only for best concentrations the procedure was repeated at 20 °C and 30 °C.
Lowering the pour point of crude oil

Firstly, to carry out the flow assurance test for raw crude oil 50 ml of heavy hydrocarbon were placed into 100
ml beaker. The beaker was heated up to 50 °C, after what the oil was poured to another 100 ml beaker. The flow
ability was observed. Finally, the beaker was cooled down to 45
°C, 40 °C, 39 °C, until the flow rate reached 0 and the crude could not flow anymore. The temperature and time
for the sample to solidify were recorded. The procedure was repeated for the samples with application of
various volumes (10 ml, 20 ml, 29.4 ml) of 5%, 10%, and 15% concentrations of BSS.
Reducing the viscosities of crude oil

At room temperature, as depicted on Figure 1.1 below, all concentrations except 2.5% showed the highest
decrease in viscosities ( > 92%) at the maximum of applied BSS volume – 50 ml.

Viscosity of Crude Oil VS Volume of BSS of Different

Concentration
2500
2000
1500
1000
500
0 1 2 3 4 5 6 7 8 9 10
Amount of BSS
2.50% Room Temperature 5% Room Temperature
10% Room Temperature 15% Room Temperature
Figure 1.1: Viscosity of the crude oil graph at the room temperature
Since the purpose of this part of the study was to find the most optimum concentration and volume for better
pumping of oil from the bottom of an ocean - 5% concentration of BSS reduced viscosity of the crude to the
sufficient values for pumping – 1064.5 cst, already after addition of only 2.5 ml, which shows 50% efficiency at
such a small volume. Explanation to this could serve critical micelle concentration (CMC) which is a required
concentration of surfactants in order for them to start forming micelles in the solution. CMC depends on the
type of surfactants and solvent used, however since the solvent and surfactants remain constant, the
concentration of them is the only playing factor. At insufficient surfactant concentrations, addition of bigger
volumes is required to initiate micelle formation which is unfavourable for the oil companies due to extended
expenses. This is clearly demonstrated by the difference of effectiveness of 2.5%, which is the only
concentration that reduced the viscosity by just 6% after addition of 1 ml of BSS (compared to 31%, 27% and
28% efficiency at 5%, 10% and 15% respectively after addition of 1 ml). Such good effectiveness of 5 %
solution must mean that it is the closest to or reaching the CMC but not exceeding. [8] This way, when the oil
medium is added, the surfactants readily form micelles around it. The results demonstrate that 2.5%
concentration is below CMC and only after addition of high volumes micelles effectively form creating a less
viscous oil-in-water emulsion. In contrast, at the higher concentrations like 10% and 15% it was observed that
the viscosity decreased by only 25% and 37% after addition of 2.5 ml of solution, meaning that both of these
concentrations are less effective than 5% which is justified by higher attraction forces between smaller
dispersed particles in the emulsion. Similar observations have been published by Zaki et al (1997), Ahmed et al
(1999), Parkinson et al (1970) and many others in the past: the higher the concentration of surfactants present in
the solution, the lower the interfacial tension between water and oil, the more small dispersed particles there are
and the more viscous the liquid emulsion. [9, 10, 11] This Parkinson et al (1970) proposed to be due to the fact

that for the same fraction of volume due to finer particles and higher interfacial area, these droplets interact with
each other over a bigger surface area creating higher emulsion viscosities. [11]
At high temperatures like 40 °C, the viscosity of oil decreases a lot due to the amount of energy molecules gain
upon heating up. After reaching their activation energy the liquid molecules are able to move and exchange
places with the neighbouring molecules reducing the viscosities and causing oil to flow. [12] Consequently all
the viscosity measurements of raw crude are already lower by thousands cst without addition of BSS. However,
this test showed the opposite results where viscosity was increasing upon addition of surfactants. Mahmood and
Al-Koofee (2013) had noted before that the CMC significantly decreases with increasing temperature. [13]
They explained this phenomenon by the observation of surfactant surrounding water molecules that get start
actively moving and disrupt the structure reducing the hydration of the hydrophilic groups that cause
micellization. [13] This could be possible explanation to the fact that the effect was adverse for each
concentration of BSS applied in larger volumes, i.e. with more surrounding water molecules. Similarly, in
smaller volumes but higher concentrations, i.e. when less water molecules are present the efficiency was
improved in each case which could be observed from the Figure 1.2.
Viscosity of Crude Oil VS Volume of BSS of Different

Concentration
60
50
40
30
20
0 1 2 3 4 5 6 7 8 9 10
Amount of BSS
2.50% 40°C 5% 40°C 10% 40°C 15% 40°C
Figure 1.2 Graph of the viscosity of the crude oil at 40°C
The most optimum concentration was found to be at 5% of BSS. Thus, further experiments were performed on
it at different temperatures: 20 °C and 30 °C, the results of these experiments are depicted on the graph below,
Figure 1.3. At 20 °C temperature the viscosity of the crudes significantly increases (7138.08 cst) inhibiting the
flow of it, while at 30 °C the viscosity is only slightly less viscous than at room temperature. After application
of minimum volume of 5 % BSS (1 ml: 1000 ppm solution, 50 ppm BSS) the viscosity of the waxy crude oil
decreased by 9% (6476.201 cst). Waxy crude oil viscosity was decreased as the volume of BSS increased
reaching 99% reduction from 50 ml of the solution. The most optimum volume for the pumping systems (~
1000 cst) on the bottoms of the ocean was found to be in between 10 ml and 20 ml (observed viscosities are
1286.439 cst and 801.648 cst respectively). Meanwhile 30 °C operational temperature could be used in the

pipelines for the transportation uses. In order for the crudes to flow through pipelines, they have to possess
viscosity not more than 200 cst. Therefore, for this purpose the most optimum volume was found to be 40 ml,
while for pumping – 10 ml. At the same time, 5 % concentration demonstrated that viscosities can be easily
reduced to 200 cst at room temperature too: only 29.4 ml required for this purpose.
Viscosity of Crude Oil VS Volume of 5% BSS Solution

8000
7000
6000
5000
4000
3000
2000
20°C 27°C 30°C 40°C
Figure 1.3: Viscosity of crude oil after added 5% concentration of BSS at different temperatures
Lastly, the viscosities of the crude oil were measured at different temperatures without and with application of
BSS. The effect on viscosities was recorded and illustrated on the Figure 1.4, where the advantage of using BSS
is clearly noticeable, especially at low temperatures like 20°C and 27
°C.
Viscosity of Crude Oil Vs Temperature
8000
7000
6000
5000
4000
3000
15 20 25 30 35 40 45
Temperature (°C)
Viscosity Without BSS (cst) Viscosity With BSS (cst)

Figure 1.4: Viscosity of crude oil at different temperature
Lowering the pour point of crude oil

Pour point is an important factor in the oil industry that affects the production majorly. This is the temperature
below which the oil solidifies and does not flow. Pour point can be reduced by applying surfactants to the oil
that minimizes the interfacial tension between oil and water and creating an emulsion with embedded water
molecules that have a very low solidification temperature (below 0 °C). By mixing these two liquids with
different solidification temperatures the temperature of the whole mixture lowers too. Figure 2.1 and Figure 2.2
exhibit the times and temperatures at which oil samples solidified after using various concentrations and
volumes of BSS.
Pour Point of the India Crude Oil VS Amount of BSS

42
40
38
36
34
32
Raw 10ml 20ml 29.4ml
Amount of BSS
5% 10% 15%
Figure 2.1: Crude Oil Pour Point Graph
It is clear from the Figure 2.1 that after pouring 15% solution to the waxy crude oil samples they solidify at the
minimum temperature – 34 °C, which corresponds to 6 °C pour point reduction comparing to the pour point of
waxy crude oil alone. Meanwhile 5% and 10% resulted in only
1.5 °C and 2 °C difference, respectively. However, clear pattern can be noticed that with an increasing
concentration of surfactants present in the solution the pour points are significantly decreasing. This could be
because more concentrated solutions are exceeding the CMC resulting in the formation of more micelles with
the higher amount of surfactants present. With creation of more micelles, more water molecules are able to
surround the oil droplets as a consequence of attraction of polar water to hydrophilic parts of surfactants. As
more water molecules are present in the emulsion, lower the temperature and longer the times are needed for
solidification. Interestingly enough volume of the solutions does not affect so much the pour point meaning that
for the sake of saving the costs minimum amount of BSS could be used – 10 ml. However, further
investigations on higher concentrations might be useful in order to see whether more reduction of the pour
points is possible and at what point it reaches the maximum.

Time Taken for Indian Crude Oil to Solidify (min) Vs

Amount of BSS
16
15
14
13
12
Raw 10ml 20ml 29.4ml
Amount of BSS(ml)
5% 10% 15%
Figure 2.2: Crude Oil Solidification Time Graph
Figure 2.2 demonstrates that it took the longest time for oil to solidify at 34°C after applying only 10 ml of
15% BSS. Gaining more time for oil to flow is very beneficial for petroleum companies as it provides an
opportunity for better and easier extraction as well as transportation of crude oil which are the most problematic
aspects of heavy hydrocarbons. An explanation to this could be the same as for the temperature – more water
molecules are attracted to the oil droplets through hydrophilic surfactant heads longer time it takes for
solidification. In case of 5% concentration, less water molecules as well as surfactants are present in 10 ml, but
upon increasing the volume the amount of both increases resulting in longer times reaching its maximum at 15
minutes. The reason for not improving the times after putting more than 10 ml of 15% and 10% solutions could
be that it already reached the maximum capacity of possible elongated time and addition of more water does not
affect the oil anymore. Further research is required again on higher concentrations and their influence on flow
rate.
Conclusion
In conclusion of this case study BSS proved its absolute advantageous properties in various applications.
Depending on different combination of concentrations and volumes used BSS was able to greatly reduce the
viscosities and pour points of the waxy crude oil that has been studied. The determining factor for the choice of
concentrations for viscosity reduction varies from case to case and depends on CMC of the solution, where the
concentration is preferable to be close to or reaching the CMC, while too low concentration required bigger
volumes to be beneficial. Moreover, 5% concentration indicated high effectiveness in reducing the viscosity at
the lower temperature like 20 °C suggesting a possibility of using it for improved extraction of oil from the
bottom of the ocean. In contrast, 15 % of any volume performed best in reducing the pour point of oil and
extending the flow rate for longer time which could be due to higher attraction between more concentrated
hydrophilic surfactants and polar water. Finally, for the purpose of further improvement of the flow at lower
costs more research could be conducted on the relation between higher concentrations and flow rate.

Recommendations
Recommendations on reducing the viscosities of crude oil with using 5% BSS
We recommend to use 5% concentration of BSS of 2.5 ml volume (2500 ppm solution, 500 ppm BSS) for better
extraction of heavy crudes through pumping at room temperature. To ensure the flow of the crude oil in the
pipeline it is better to use between 10 ml (10,000 ppm solution, 500 ppm BSS) to 29.4ml (29,400 ppm solution,
1470 ppm BSS) at room temperature.
Recommendations for lowering the pour point of crude oil

We recommend to use 15 % concentration of BSS of 10 ml volume (10,000 ppm solution, 1500 ppm BSS) for
the most efficient reduction of the pour point and elongation of the times until the solidification of the Indian
crude oil occurs.
Acknowledgement
We acknowledge and thanking the kind support from Mr Christopher Do and Mr Rajiv Savara of IEV
Technologies (India) Pte Ltd for making the kind arrangements for which the successful and smooth execution
of this meaningful study. Also to Ms Tomiris Nabiyev for excellent coordinations and compilations as well as to
ECT Lab team for the full dedications.
References
[1] Plegue, T. H., Frank, S. G., Fruman, D. H. & Zakin, J. L. Studies of Water-Continuous Emulsions of
Heavy Crude Oils Prepared by Alkali Treatment. SPE-18516-PA 4, 181-183, doi:10.2118/18516-PA (1989).
[2] Schumacher, M. M. Enhanced recovery of residual and heavy oils. (Noyes Data Corp., 1980).
[3] Tarek, A. Flow Assurance. Equations of State and PVT Analysis. 457-533,
https://doi.org/10.1016/B978-1-933762-03-6.50011-3 (2007)
[4] Bai Y., Bai, Q., Subsea System Engineering. Subsea Pipelines and Risers, Elsevier Science Ltd, 263-
276, https://doi.org/10.1016/B978-008044566-3.50019-1. (2005)
[5] Guo, B., Song S., Ghalambor, A., Ran Lin, T., Flow Assurance. Offshore Pipelines (Second Edition).
179-231, https://doi.org/10.1016/B978-0-12-397949-0.00015-7. (2014)
[6] Ashrafizadeh, S. N. & Kamran, M. Emulsification of heavy crude oil in water for pipeline
transportation. Journal of Petroleum Science and Engineering 71, 205-211,
doi:https://doi.org/10.1016/j.petrol.2010.02.005 (2010).
[7] Demirbas, A., Alidrisi, H., Balubaid, M. A. API Gravity, Sulfur Content, and Desulfurization of Crude
Oil. Petroleum Science and Technology, 33:1, 93-101, DOI: 10.1080/10916466.2014.950383 (2015)
[8] Sheng, J. J. in Modern Chemical Enhanced Oil Recovery. (ed James J. Sheng), 239-335, (Gulf
Professional Publishing, 2011).
[9] Zaki, N. N. Surfactant stabilized crude oil-in-water emulsions for pipeline transportation of viscous
crude oils. Colloids and Surfaces A: Physicochemical and Engineering Aspects 125, 19- 25,
doi:https://doi.org/10.1016/S0927-7757(96)03768-5 (1997).
[10] Ahmed, N. S., Nassar, A. M., Zaki, N. N. & Gharieb, H. K. STABILITY AND RHEOLOGY OF
HEAVY CRUDE OIL-IN-WATER EMULSION STABILIZED BY AN ANIONIC- NONIONIC
SURFACTANT MIXTURE. Petroleum Science and Technology 17, 553-576,
doi:10.1080/10916469908949734 (1999).
[11] Parkinson, C., Matsumoto, S. & Sherman, P. The influence of particle-size distribution on the apparent
viscosity of non-newtonian dispersed systems. Journal of Colloid and Interface Science 33, 150-160,
doi:https://doi.org/10.1016/0021-9797(70)90082-2 (1970).

[12] Khan, M. R. Rheological Properties of Heavy Oils and Heavy Oil Emulsions. Energy Sources
18, 385-391, doi:10.1080/00908319608908777 (1996).
[13] Al-Koofee, Dhafer. Effect of Temperature Changes on Critical Micelle Concentration for Tween Series
Surfactant. Global Journal of Science Frontier Research Chemistry. 13. (2013)

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Conference Proceedings (IOGCA 2019), Ahmadabad

Content (List of Full Papers Submitted)

Paper No. Title Page No.

IOGCA(2019)/1 Title: “Importance of Controlling Fluid Loss & Settling Behavior 4

Organized By MatCorr Page 1

Paper No. Title Page No.

IOGCA(2019)/12 Title: “Linear and Poly Alpha Olefins: Precursors to Synthetic 89

Organized By MatCorr Page 2

Paper No. Title Page No.

IOGCA(2019)/23 Title: “Drilling Fluid Design As A Relacement Of Kcl” 185

Organized By MatCorr Page 3

Paper No. IOGCA (2019)/1

Organized By MatCorr Page 4

• Loss/ of carrying capacity results on barite settling

Organized By MatCorr Page 5

• Fluids intermixing and potential cement slurry contamination

API fluid loss test

Stability tests of spacer

Organized By MatCorr Page 6

Fig 1. Dynamic Settling paddle compared with HPHT consistometer paddle

Compatibility tests of spacer

Organized By MatCorr Page 7

Definition of R-Index Value

RESULTS & DISCUSSIONS

Table 1 Cement slurry design, BHCT-900C, pressure-5000psi (Sp.gr -1.94)

Cement Water S.Flour FLA Dispersant Retarder Defoamer

Water Defo Spac FL ASA Barytes Fluid Thermal Remarks

Cement Spacer Fluid loss(ml) At 880C after

Organized By MatCorr Page 8

Table5 Cement slurry design, BHCT-1500C, pressure-10000psi,Sp.gr - 2.20

Cement Wat S.Flour FLA Micro Dispers Retarder Co Defoamer

Wat Defoa Spacer FL AS Baryte Fluid Thermal Remarks

Organized By MatCorr Page 9

(a) (b) (c)

Cement Spacer Fluid loss(ml) at 880C after conditioning in HPHT

Cement Spacer Fluid loss(ml) at 880C after conditioning in

Organized By MatCorr Page 10

Table 9 Cement slurry design, BHCT-2000C, pressure-16500 psi, sp.gr -2.35

Water Defoamer HPHT FLA ASA Barytes Fluid Thermal Remarks

Cement proportions Spacer Fluid loss(ml) at 880C after conditioning

Cement proportions Spacer Fluid loss(ml) at 880C after conditioning

Organized By MatCorr Page 12

Organized By MatCorr Page 13

Paper No. IOGCA(2019)/2

Title: “Robust design for Cement degradation in CO 2 under HPHT Environment.”

Organized By MatCorr Page 14

Organized By MatCorr Page 15

Experimental Work & Procedure

Preparation of Cement Slurry & molds

Modification of existing equipment

c) At a temperature of 170C & a pressure differential of 700psi was continuously applied to

Organized By MatCorr Page 16

Results & Discussions

Table 1 Composition of Cement Sample 1

Table 2 Composition of Cement Sample 2

Table 3: Before exposure to CO2

Organized By MatCorr Page 17

Fig1- Sample 1 before exposure to static CO2 gas

Fig2- Sample 2 after exposure to static CO2 gas

Organized By MatCorr Page 18

Fig3- Sample 1 before exposure to static CO2 gas

Fig 4- Sample 2 after exposure to static CO2 gas

After exposure to CO2