IPTC 16401

Vital Role of Nanotechnology and Nanomaterials in the Field of Oilfield

Chemistry
Long Li, Xubo Yuan, Jinsheng Sun, Xianguang Xu, Shuang Li, Lihui Wang, CNPC Drilling Research Institute

Copyright 2013, International Petroleum Technology Conference

This paper was prepared for presentation at the International Petroleum Technology Conference held in Beijing, China, 26–28 March 2013.

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Abstract
Nanotechnology has the potential to introduce revolutionary change in the energy industries such as exploration, development
and production. Nanotechnology can revolutionalise the additive properties by tuning particle characteristics to meet certain
environmental, operational and technical requirements. Nanotechnology produces nanomaterials that are ultra fines in nature,
usually smaller than ordinary micro particles and thus has very high specific surface area with enormous area of interactions.

Recent research has indicated that nanomaterials have unique properties for a broad range of applications in the field of oilfield
chemistry, where fluid loss control, borehole stability, cementing quality of a well, remediation of damaged reservoirs,
hydrocarbon recovery efficiency, oilfield wastewater treatment are of interest.

This paper presents an extensive literature review of assessing the applications of nanotechnology and nanomaterials in the
field of oilfield chemistry, investigating the existing problems in the application of nanomaterials in oilfield chemistry, and
evaluating the potential technical and economic benefits that nanotechnology and nanomaterials might provide to petroleum
development and production.

Introduction

Nanotechnology is one of the most active research areas with both novel science and useful applications. Because of its
significant application in future, petroleum scientists are putting their heads together, and targeting what promises to be a new
energy industrial revolution. Nanotechnology can offer many potential solutions to resolve industry problems for upstream
sector that cannot be solved with traditional approaches (Singh et al. 2010; Nabhani et al. 2011; Abdo et al. 2012).

Nanotechnology generates nanomaterials with at least one dimension in the range of 1~100 nm. Nanomaterials are being
considered for various uses in hydrocarbon development and production (Del Gaudio et al. 2007; Amanullah et al. 2009; Kong
et al. 2010). The ability of nanotechnology to produce tailored made nanomaterials with specific properties is expected to play
a leading role in overcoming the technical and environmental challenges faced during petroleum development and production
(Jimenez et al. 2002; Evdokimov et al. 2006).

Nanotechnology has already contributed significantly to technological advances in the energy industries. Recent research has
indicated that nanomaterials have special characteristics for a broad range of application in the field of oilfield chemistry. With
the combination of nanotechnology and oilfield chemistry technology, it will be beneficial to maintain borehole stability,
enhance oil and gas recovery, raise the success rate and economical benefit of petroleum development and production, and
protect the environment (Li et al. 2012).

Nanotechnology has the potential to introduce revolutionary change in the field of oilfield chemistry (Krishnamoorti et al.
2006; Mokhatab et al. 2006; Sensoy et al. 2009). Currently, nanomaterials are considered to be the most promising matter of
choice for designing and development of novel oilfield chemistry additives, and may offer a better solution to petroleum
industry problems that cannot be solved with traditional methods, so they have a bright prospect in hydrocarbon development
and production.
2 IPTC 16401

This paper reviews important nanomaterials developed so far in the field of oilfield chemistry, including drilling fluids,
completion fluids, workover fluids, stimulation fluids, profile control agents, heavy oil thinner, and wastewater treatment
materials, which may offer a wide range of benefits for petroleum industry.

Nanometer Additives for Drilling Fluids

Nano-Sized Shale Inhibitor for Drilling Fluid

Maintaining wellbore stability is the most critical aspect of petroleum drilling operations. But most of conventional water-
based mud can easily generate fluid invasion into shale formations, and subsequent cause swelling and sloughing of wellbore.
The basic reason is that conventional filtration additives do not form mud cakes to plug nano-sized pore throats in shales, and
thus do not stop fluid invasion. Six brands of commercial and non-treated silica nanoparticles with sizes varying from 5 nm to
22 nm were added to the drilling fluids, and water-based inhibitive drilling fluids were formulated for the first time (Cai et al.
2011). The experimental results demonstrated that all 6 non-modified nanoparticles could reduce the Atoka shale permeability
by a significant amount, and thus stop fluid invasion and increase wellbore stability. In addition, these nanoparticles with size
varying from 7 nm to 15 nm had better plugging performance than those with size greater than 20 nm, so they were more
effective plugging agents. The reason for this was that these nanoparticles were small enough to enter and plug the pore throat
in shales, and built an effective mud cake on shale surface, therefore, minimized fluid invasion into shales.

Using these water-based inhibitive mud containing non-modified nanoparticles to seal the shale was a very powerful and
economical approach to address borehole instability problems in troublesome shale formations. As a result, these water-based
fluids were suitable for the drilling of long sections of horizontal laterals. In the future, these non-modified nanoparticles based
drilling fluids might hold great promise to resolve shale instability problems.

Nano-Sized Fluid Loss Agent

The filtrate invasion into formations may cause formation damage and increase the difficulty of filter cake removal, resulting
in the reduction of oil well productivity. Hence, the filtrate losses to the formation should be properly controlled. Sized silica
nanoparticles were added to drilling fluids, and their fluid loss properties were tested (Srivatsa et al. 2012). The experimental
results showed that the nanoparticles had better reduction in fluid loss in comparison with the standard polymer-based fluid
loss additive, because the nanoparticles could seal the pores and form an effective filter cake than the internal filter cake
formed by the polymer. Moreover, the addition of nanoparticles did not raise the mud weight, so they could be used as a new
class of bridging agent that did not increase the solid content of drilling fluids, which could play an important role in drilling in
high angle wells, horizontal and directional wells. Therefore, the application of nanoparticles in drilling fluids was mainly to
form a thin and impermeable membrane on the borehole wall, which could plug the pores of the shale formation, minimize
filtrate-induced damage, strengthen borehole stability, and maximum well conductivity.

Nanometer Drilling Fluid System

Nanoparticle-Based Drilling Fluid

Novel oil-based drilling fluid system was formulated for the first time by adding in-house prepared nanoparticles (NPs) to
commercial oil-based drilling fluid (Zakaria et al. 2012). The experimental results indicated that there was no effect on the
viscosity of commercial drilling fluid, and the oil-based drilling mud containing NPs could maintain its stability for more than
6 weeks. The NP-based drilling fluid produced an ultra-thin, tight and relatively impenetrable mud cake deposited on the
borehole wall, which could reduce filtrate invasion into formations and hence minimized fluid-induced damage. In addition,
NPs could also possess the small sized pores to block throats and interact with the clay particles, and consequently provided an
excellent sealing effect and hence increased borehole stability. As a result, the application of NP-based drilling fluid might
offer high potential for reducing the differential pipe sticking in highly permeable formations, formation damage and
contamination while drilling, and also could enhance ROP in hard rock formations greatly, and thus lower drilling costs
significantly.

Nano-Enhanced Drilling Fluids

Abdo et al. (2012) reported an approach to overcome drilling problems by controlling the rheological properties of drilling
fluids by using nanoparticles. New nanomaterial ATR was added to drilling fluids, and the rheology of drilling fluids was
investigated. The results demonstrated that ATR could reduce viscosity without compromising the requirement of density.
Additionally, the obtained drilling fluids had high gel strength, which was very essential for eliminating severe drilling
problems such as poor hole cleaning, high torque and drag, pipe sticking, wellbore instability and formation damage.
IPTC 16401 3

Compared with regular bentonite, ATR nanoparticles could offer better functionality. In order to improve the functionality of
bentonite, a certain number of ATR nanoparticles were added to bentonite-based drilling fluid system. The results showed that
the obtained drilling fluid system had excellent properties and shear thinning behavior mainly due to the combination of the
characteristics of high density of bentonite and low viscosity and high gel strength of nanosized ATR, which could not be
achieved by bentonite or ATR alone. Therefore, the use of ATR could play an important role in developing versatile drilling
fluid recipes to suit particular drilling conditions.

Nanometer Materials for Completion Fluids

New Nano-Cement Slurry

The nano-sized particles such as SiO2, 2CaO·SiO2, 3CaO·SiO2, Al2O3, and phosphorous/calcium were selected as additives to
improve the properties of the resulting cement (Mercado et al, 2010). The experimental results showed that these nano-
additives could enter the interstitial areas and other areas of high porosity in the cement. Therefore, a much less permeable
structure could be formed, and the strength and other desirable characteristics of the cement could be improved.

In addition, these nano-particles could raise the mechanical, thermal and chemical properties of the resulting cement, which
was particularly useful in solving such problems as low mechanical property, gas and fluid migration of oil and gas well
cement system, and reducing the erosion of sour gas.

New Nano-Spacer Fluids

Nano-emulsions, the droplet size of which was between 20 and 500 nm, were obtained by a low energy cost method, so they
could be prepared readily in great amounts (Maserati et al, 2010). In addition, the nano-emulsions could be directly obtained in
the field or transported on site. Due to their small droplet size, they had a high surface area, very particular characteristics, and
high stability, and thus had potential applications in oil and gas industry.

With the help of nano-emulsion technology, a new nano-spacer was prepared by adding commercial gelling and weighting
agents to the nano-emulsions. Compared with the traditional spacers, the nano-spacer had better performances in mud
removal, reverse wettability, and casing-bore adhesion of the concrete. Moreover, the experimental results demonstrated that
the fresh and aged nano-spacers had the same effect, so the nano-spacer could be applied at complex field conditions. The
innovative spacer fluid had very high cleaning properties, was totally compatible with drilling fluid as well as slurry systems,
and could improve the cement sheath bonding, so it would have a broad prospect in well cementing operations.

Nanoscale Workover Fluids

Low permeability oil and gas well reservoirs are commonly characterized by high content of argillaceous cements, small pore
throats, poor permeability, severe heterogeneity, and large oil and gas flow resistance. The reservoirs
are extremely sensitive to working fluids such as drilling fluids, completion fluids, stimulation fluids, and so on. Therefore, the
fines invasion into reservoirs can result in pore throat blockage, and thus create severe formation damage and produce
impairment (Davies et al, 2009). As a result, novel workover fluids should be developed to repair the damaged reservoirs.

A new workover fluid had been developed by a unique blend of biodegradable solvent, surfactant, co-solvent and water
(Penny et al, 2005). The experimental results demonstrated that this workover fluid was efficient in remediating damage and
promoting well cleanup following stimulation. The workover fluid could result in lower pressures to displace fracfluids from
propped fractures resulting in lower damage and higher production rate. Field applications indicated that the addition of the
workover fluids to drilling fluids could result in greater fluid recoveries and higher production rates, the addition of the
workover fluids to fracturing treatments could result in improved load recoveries and enhanced gas and oil production, and the
squeeze jobs with the workover fluids had restored productivity to wells damaged by fracfluids, water blocks and heavy oils.
Meantime, the workover fluid system was naturally occurring, nonsynthetic, non-hazardous, non-carcinogenic, and contained
no volatile organic solvents. The workover fluid was effective in remediating damaged wells, and was highly effective in fluid
recovery and relative permeability enhancement when used in drilling and stimulation treatments, and thus it would have a
wide application future in workover operations

Nanoparticles-Associated VES-Stimulation Fluids

Viscoelastic surfactant (VES) fluids have been widely used as stimulation fluids, including gravel-packing fluids, fracture-
packing fluids, and fracturing fluids. But they may easily produce low viscosities and high fluid leakoff from the fracture at
high temperature, which limit their applications to hydraulic fracturing and fracture-packing treatments.
4 IPTC 16401

To maintain viscosity at high temperature and control the fluid loss of VES stimulation fluid, a nanometer particle was added
to a VES solution (Huang et al, 2008; 2009). The experimental results demonstrated that these nanoparticles could stabilize
VES fluid viscosity at high temperature, reduce the rate of fluid loss significantly, and improve fluid efficiency for hydraulic
fracturing, because these nanoparticles could associate with VES micelles through surface-charge attraction and surface
adsorption, and produce a pseudofilter cake of viscous VES fluid.

When an internal breaker was used to break the VES micelles, the viscosity of VES fluid would reduce significantly, and the
pseudofilter cake would break into brine with nanoparticles, which were small enough to pass through the pore throats of
producing formations, and they could be flowed back with the producing fluids, and thus no formation damage would be
formed.

New Profile Control Agents

CO2 channeling is a serious problem for enhanced oi1 recovery with CO2, which has serious influence upon
oil displacement efficiency of CO2, and thus it will reduce oil recovery dramatically. Therefore, to control CO2 channeling
during CO2 injection process is an important part in oil displacement process. It is particularly necessary for petroleum
scientist to develop an environmental friendly and highly efective CO2 plugging agent.

Utilizing sodium silicate as starting materials, acrylamide as initiator and crosslinking agent, Hou et al. (2010) prepared a new
type of organic-inorganic nanocomposite gel at high-pressure acid environment generated by CO2. The experimental results
demonstrated that the high-pressure acid environment generated by CO2 injection could not only accelerate the formation of
composite gel, but also have positive influence on gel properties. The composite gel system had good resistance to high
temperature and high pressure, and high elasticity. The core plugging tests showed the plugging rate of the composite gel
could reach up to 95%. Additionally, the gel system flowed freely, and could be pumped into the formation easily. As a result,
the new nanocomposite gel was a kind of environmental-friendly CO2 plugging agent, and it would have good potential for
plugging CO2 channeling.

Using diesel oil, sorbitan monooleate, polyethylene glycol sorbitan monostearate, acrylamide, N, N’-methylenebisacrylamide
as raw materials, Wang et al. (2010) synthesized a new kind of polyacrylamide microgel nanosphere by inverse
microemulsion polymerization method. The experimental results demonstrated that the nanospheres after water absorption
could expand from the original 50 nm to several microns in diameter, which showed that they had good water absorbing
capacity and excellent swelling property. Meantime, the nanospheres had good elasticity and deformability, too. The microgel
nanospheres were not water soluble, and they had high stability in water. The core flood tests demonstrated that the
nanospheres could enlarge the sweep efficiency, so they were suitable for deep profile control. The sandpacks tests showed
that the nanospheres could improve enhanced oil recovery (EOR) with incremental oil recovery over 20% OOIP after primary
recovery. Therefore, the nanospheres had great potential in profile control and oil displacement.

Nanometer Stimulants for Heavy Oil Recovery

With the increasing consumption of world oil market and scarcity of the fast decrease of conventional oil reserves,
more attention is paid to huge unconventional oil resources such as heavy oil, mainly due to their enormous volume and
worldwide distribution. However, the viscosity of heavy oil is very high, and it is difficult to be produced from the wellbore,
so a suitable heating technique to reduce its viscosity and decrease the cost of energy should be developed. In other words, the
reduction of heavy oil viscosity should be achieved in an economic way.

Pramana et al. (2010) proposed nano-ferrofluid and graphite fluid as stimulants for heavy oil recovery processes using
electromagnetic induction heating. The heat generation in the stimulants would be used for reducing the viscosity of heavy oil.
The results showed that the temperature of the stimulants increased with the presence of electromagnetic induction, and thus
they could transfer the heat to the heavy oil, so the viscosity of heavy oil decreased significantly, and large quantities of heavy
oil could be extracted at low pressures. Compared with graphite fluid and brine, nano-ferrofluid was more rapidly heated, so it
had more efficiency improvement of electromagnetic induction heating for heavy oil recovery. The combination of the
electromagnetic induction heating and nanometer stimulant fluids was economically and practically optimum.

Shokrlu et al. (2010) investigated the effect of different metal types with different sizes on heavy oil viscosity in the absence
of electromagnetic fields. The viscosity of oil samples added by these metal particles was measured, and the effect of the metal
particles on heat transfer enhancement was tested. The experimental results indicated that heavy oil viscosity could be reduced
even at room temperature or without steam stimulation. Additionally, due to the stronger effect of the aquathermolysis
IPTC 16401 5

reactions catalyzed by metal particles, the efficiency of heavy oil viscosity reduction would be more with applying steam
stimulation. More importantly, nano-sized particles caused an improvement in heavy oil recovery, mainly due to the
combination of viscosity reduction effect and heat transfer enhancement of nanoparticles, so they had a remarkable effect on
heavy oil viscosity, which was very useful in further studies and applications as to the efficiency improvement of the thermal
applications for heavy oil recovery.

Treatment of Oily Wastewater by Nanomembranes

A substantial amount of oily wastewater has been generated from oil and gas exploration and production activities, and it
contains a great number of harmful substances such as suspended solids, organics, heavy metal ions, and so on, which will
cause severe environmental pollution when discharged arbitrarily without any treatment (Wen et al. 2008). Therefore, it is
necessary to purify this wastewater so that it can be reused to save water resources. However, conventional oily wastewater
treatment methods have several disadvantages, including low efficiency, high cost, corrosion and recontamination problems.
Additionally, they are not effective in removing smaller oil droplets and emulsions (Mondal et al. 2008). So a new technique
for wastewater treatment should be developed.

A tubular UF module equipped with polyvinylidene fluoride membranes modified by inorganic nano-sized alumina particles
was used to purify oily wastewater, and the membrane water permeations of the UF process were analyzed (Li et al. 2006;
Yan et al. 2009). The experimental results showed that the oil content was reduced to less than 1 mg/L, suspended solids
content was reduced to less than 1 mg/L, and the median diameters of solid particle were less than 2 µm, which indicated that
the quality of the permeation water could meet the requirement for oilfield injection or drainage. The retentions of chemical
oxygen demand were more than 90%, and the total organic carbon was more than 98%. The SEM images showed that the
nanometer alumina particles could improve the performance of membrane antifouling, and the modified membrane flux
recovery ratio reached 100% when washing with 1% of OP-10 solution (pH 10), which indicated that the modified membrane
had a better antifouling performance, better flux recovery and less contaminant adsorption in comparison with unmodified
membrane. As a result, this modified nanomembrane had excellent permeation performance, and it would have a broad
application in oily wastewater treatment.

Discussion

With the rapid development of nanotechnology, nanomaterials have been gradually infiltrating to every respect of oilfield
chemistry, and they will play an essential role in the preparation of new oilfield chemistry agents. Unfortunately, there are
many problems in the applications of nanotechnology and nanomaterials in the field of oilfield chemistry.
(1) It is very easy to generate agglomerates for nanomaterials during use, and the grain sizes will increase greatly. Only
by stirring can hardly disperse these agglomerated particles into nanometer scale again, so these nanomaterials will lose their
unique properties, even resulting in failure of preparation of novel oilfield chemistry agents. Therefore, the agglomerate
problem of nanomaterials remains to be solved in future, and the stability of nanomaterials should be improved.
(2) There are few researches on the mechanism of nanomaterials in oilfield chemistry, and some aspects are seldom
involved. A breakthrough in their application can not be made until the fundamental research of nanomaterials is appreciated.
(3) Nowadays, the cost effectiveness of most nanomaterials is too low. In the field application, the desired results can not
be achieved with only a little dosage of nanomaterials, but excessive dosage will raise the cost. So low cost and industrial
production are the key factors for extensive application of nanomaterials in the field of oilfield chemistry.

With the development of nanotechnology, many potential solutions will emerge for the above problems, and nanomaterials
will be applied in broader field of oilfield chemistry. Meanwhile, further development of nanotechnology and oilfield
chemistry technique will be promoted.

Conclusions

Nanotechnology has essential application value and broad application prospect in oilfield chemistry, and it has been attracting
considerable attention. Many applications of nanotechnology in oilfield chemistry have been emerging such as drilling fluids,
completion fluids, workover fluids, environmentally friendly stimulation fluids, profile control agents, heavy oil thinner, oily
wastewater treatment materials, etc. So it shows great promise for upstream sectors of petroleum industry.

Due to nano-scale particle dimension, nanomaterials have many attractive properties, which can play an essential role in
maintaining borehole stability, improving the cementing quality of a well, remediating damaged reservoirs, enhancing oil and
6 IPTC 16401

gas recovery efficiency, and purifying oilfield wastewater, so it has the potential to introduce revolutionary change in
hydrocarbon production and development.

Nanotechnology offers many potential solutions to resolving industry problems that can not be solved with traditional
methods, and it can enable to push the limits of the existing petroleum development and production technology, and endow
with economically and technically viable petroleum development and production processes. The application of
nanotechnology in oilfield chemistry will make a new breakthrough in enhancing the efficiency of petroleum development and
production, and improve the overall competitiveness of the oil and gas industry.

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