Académique Documents
Professionnel Documents
Culture Documents
List of contents
S.No
Title
Page no.
i.
List of figures
ii.
List of tables
1.
1.1. Introduction
1.3.1. Paraffins
2.
3.
4.
10
10
1.3.4.1. Thermal
11
1.3.4.2. Chemical
11
1.3.4.3. Mechanical
12
Literature Survey
15
15
16
17
Experimental Work
21
21
22
23
25
25
26
35
2
List of figures
Fig.No.
1.1.
Title
Page no.
1.2.
1.3.
2.1.
16
3.1.
24
3.2.
25
3.3.
26
3.4.
27
3.5.
28
3.6.
28
3.7
29
3.8.
29
3.9.
30
3.10.
30
3.11.
31
3.12.
31
3.13.
32
List of tables
Table.No.
3.1.
3.2.
Title
Thickness of wax deposited in Pipes 1 and 2 at different temperatures
and flow rates
26
1.3.
Page no.
32
33
1.1.
Introduction
Fig 1.1. A schematic of the change from onshore to offshore in petroleum production in the
late twentieth century. (From Huang, Z. et al., AIChE J. 57, 841851, 2011.)
Taking the United States as an example, large offshore reservoirs that are mainly by the
coastlines of Louisiana, Texas, California, and Alaska have quickly become one of the
most crucial elements to the United States strategic development of energy resources
(Economic analysis methodology for the 5-year OCS Oil and Gas Leasing Program for 2012
2017, 2011). While 20 million bbl of oils were produced from offshore in the Gulf of Mexico
in 1995, this number has risen to 1400 million bbl in 2007 (Bai & Bai, 2012). The offshore
petroleum fluids are usually transported in long-distance pipelines, which range from tens
to hundreds of kilometers before they eventually reach onshore processing facilities
(Golczynski & Kempton, 2006). The oil typically comes out of the reservoir at a
temperature around 160F and is cooled significantly as it is transported through the pipes on
the ocean floor, where the water temperature is around 40F. This temperature difference
between the oil in the pipeline and the surrounding water on the ocean floor (160F to 40F)
becomes the driving force that causes the oil in the pipeline to cool down. As the oil
temperature decreases, the waxy components can precipitate out of the oil and form deposits
on the pipe wall. The problem of wax deposition in the subsea pipeline has caused a series of
problems for the flow assurance industry, including increased pressure drop needed for oil
transportation and potential blockage of the pipeline. An example of a plugged pipeline due
to wax deposition reported by Singh, Venkatesan, Fogler, and Nagarajan (2000) is shown in
Figure 2.
Figure 1.2. An example of a pipeline being plugged by wax deposits on the wall. (From
Singh, P. et al., AIChE J., 46, 10591074, 2000.)
The problem of wax deposition has become such a flow assurance concern that its
severity must be assessed in the design of nearly every subsea development across
the world, including the Gulf of Mexico (Kleinhans, Niesen, & Brown, 2000), the North
Slope (Ashford, Blount, Marcou, & Ralph, 1990), the North Sea (Labes-Carrier,
Rnningsen, Kolnes, & Leporcher, 2002; Rnningsen, 2012), North Africa (Barry, 1971),
Northeast Asia (Bokin, Febrianti, Khabibullin, & Perez, 2010; Ding, Zhang, Li, Zhang, &
Yang, 2006), Southern Asia (Agrawal, Khan, Surianarayanan, & Joshi, 1990; Suppiah et al.,
2010), and South America (Garcia, 2001). The locations of these oil fields that have been
reported to have concerns of wax deposition are highlighted in Figure 1.3.
Figure 1.3 Areas reported to have wax deposition problems across the world
Significant operational hazards due to wax deposition have been reported over the past few
decades. The U.S. Minerals Management Service reported 51 occurrences of severe waxrelated pipeline plugging in the Gulf of Mexico between the years 1992 and 2002 (Zhu,
Walker, & Liang, 2008). One of the most severe cases was reported by Elf Aquitaine in
which a removal of a wax-related pipeline blockage cost as much as $5 million. The
remediation of this blockage resulted in a 40-day shutdown of the pipeline, which added an
additional loss of $25 million of deferred revenue (Venkatesan, 2004). The arguably most
notorious incidence might be from the Staffa Field, Block 3/8b, UK North Sea, in which the
problem of wax deposition, after several unsuccessful attempts for remediation, eventually
led to the abandonment of the field and its platform (Gluyas & Underhill, 2003), leading to an
estimated loss of as much as $1 billion (Singh, 2000).
One of the main approaches to prevent wax deposition in subsea operations is pipeline
insulation. However, this solution could greatly increase the the pipe is subjected to wax
deposition risk, the most frequently used remediation method is called pigging, which
uses an inspection gauge with brushes or blades on its surface to scrape off the wax
deposits on the wall (Golczynski & Kempton, 2006). Normal production is usually
interrupted during the pigging operations, adding to the cost of production. The
frequency of pigging can greatly influence the production cost. An estimate of deferred
revenue based on a 29-km production pipeline and a production rate of 30,000 bbl/day
with an oil price of $20/bbl at the time of the study is shown in Figure 1.4 (Niesen, 2002). It
should be noted that the oil price nowadays has increased and thus, the production costs
related to pigging will be much higher.
As we can see from the above analysis, it is extremely important to have a sufficient and
rigorous understanding of the physics and chemistry of wax precipitation/deposition in the
pipeline in order to develop economically viable prevention/mitigation strategies. The
establishment of such an understanding can be achieved through a series of laboratory
characterizations as well as predictive modeling that incorporates the fundamentals of
thermodynamics and transport phenomena.
Wax precipitation-induced viscosity increases and wax deposition on pipes are the primary
causes of high flowline pressure drops. In turn, these pressure losses lead to low flow rates
that make conditions for wax deposition more favorable. In extreme cases, pumping pressure
8
can exceed the limits of the system and stop flow entirely. A related problem is the high-yield
stress for restarting flow. When oil is allowed to stand in a pipeline at temperatures below its
pour point, a certain pressure is required to break the gel and resume flow. Again, this
pressure may be higher than the pressure limits of the pumps and pipelines.
Reduction of the internal diameter of the pipelines, which restricts and can ultimately
block flow.
Increased surface roughness on the pipe wall which causes increased backpressure and reduced throughput.
Accumulations that fill process vessels and storage tanks, leading to system
upsets and labor/OPEX-intensive cleanup and disposal problems.
Interference with valve and instrumentation operation.
9
Increased risk of sticking pigs in the line and interference with the in-line inspection
of flowlines and export lines by tools such as gauge pigs, caliper pigs and intelligent
pigs.
All of these problems may result in production shutdowns, hazardous conditions, and damage
to equipment.
Paraffin wax mitigation/prevention can be either preventive or corrective. Preventive
practices take steps to avoid paraffin deposits and growth. Corrective practices require the
periodic removal of any deposits. A cost/benefit analysis of these solutions should be
conducted before the final selection of a paraffin management strategy is made, where a
combination of these approaches may be required in order to provide an optimized wax
control strategy.
Thermal
Chemical
Mechanical
10
1.4.1. Thermal
Because wax precipitation is highly temperature dependent, thermal methods can be highly
effective both for preventing and removing wax precipitation problems. Prevention methods
include steam- and electrical-heat tracing of flowlines, in conjunction with thermal insulation.
Thermal methods for removing wax deposition include:
Hot oiling
Hot watering
Hot water treatments cannot provide the solvency effects that hot oiling can, so surfactants
are often added to aid in dispersion of wax in the water phase. Surfactants are discussed
under chemical methods.
Hot oiling is one of the most popular methods of deposited wax removal. Wax is melted and
dissolved by hot oil, which allows it to be circulated from the well and the surface producing
system. Hot oil is normally pumped down the casing and up the tubing; however, in flowing
wells, the oil may be circulated down the tubing and up the casing. There is evidence that hot
oiling can cause permeability damage if melted wax enters the formation.
Higher molecular-weight waxes tend to deposit at the high-temperature bottom end of the
well. Lower molecular-weight fractions deposit as the temperature decreases up the wellbore.
The upper parts of the well receive the most heat during hot oiling. As the oil proceeds down
the well, its temperature decreases and the carrying capacity for wax is diminished. Thus,
sufficient oil must be used to dissolve and melt the wax at the necessary depths.
1.4.2. Chemical
The types of chemicals available for paraffin treatment include:
Solvents
Wax crystal modifiers
Dispersants
Surfactants
Solvents can be used to treat deposition in production strings and also may be applied to
remediate formation damage. Although chlorinated hydrocarbons are excellent solvents for
waxes, they generally are not used because of safety and processing difficulties they create in
the produced fluid. Hydrocarbon fluids consisting primarily of normal alkanes such as
condensate and diesel oil can be used, provided the deposits have low asphaltene content.
Aromatic solvents such as toluene and xylene are good solvents for both waxes and
asphaltenes. Solvents are mostly used in large batch treatments.
Wax crystal modifiers act at the molecular level to reduce the tendency of wax molecules to
network and form lattice structures within the oil. Wax crystal modifiers which are used to
prevent wax deposition, reduce oil viscosity and lower the wax gel strength are only effective
when used continuously. Since they work at the molecular level they are effective in
concentrations of parts per million, as opposed to hot oil or solvents, which must be applied
in large volumes. Wax crystal modifiers have a high-molecular-weight and as a result they
have high pour points, so their use can be limited in cold climates.
11
Dispersants are a type of surfactants that helps disperse the wax crystals into the produced oil
or water. This dispersing of the wax crystals into the produce oil or water helps prevents
deposition of the wax and also have a positive effect on the viscosity and gel strength.
Dispersants can help break up deposited wax into particles small enough to be carried in the
oil stream. To prevent wax deposition dispersants must be used continuously. To remediate
deposited wax, dispersants can be used continuously or in batch treatments. Dispersants
generally have a very low pour point making their use suitable for cold climates. These
chemicals are used in low concentrations and can be formulated in both aqueous and
hydrocarbon solutions, making them relatively safe and inexpensive.
Surfactants are a general class of chemicals that are most often used to clean vessels, tanks,
pipes, machinery or any place where wax may deposit. Surfactants or dispersants can also be
used in combination with hot oil and water treatments.
1.4.3. Mechanical
12
References
1. Reistle, C. E. (1928). Methods of dealing with paraffin troubles encountered in
producing crude oil.
2. Lee, H. S. (2008). Computational and rheological study of wax deposition and
gelation in subsea pipelines (Ph.D. thesis). University of Michigan.
3. Berne-Allen, A., Jr., & Work, L. T. (1938). Solubility of refined paraffin waxes in
petroleum fractions. Industrial and Engineering Chemistry, 30, 806812.
4. Reistle, C. E. (1932). Paraffin and gongealing-oil problems.
5. Bilderback, C. A., & McDougall, L. A. (1969). Complete paraffin control in
petroleum production. Journal of Petroleum Technology, 21, 11511156.
6. Han, S., Huang, Z., Senra, M., Hoffmann, R., & Fogler, H. S. (2010). Method to
determine the wax solubility curve in crude oil from centrifugation and high
temperature gas chromatography measurements. Energy & Fuels, 24, 17531761.
7. Economic analysis methodology for the 5-year OCS Oil and Gas Leasing Program for
20122017. (2011). Washington, DC.
8. Bai, Y., & Bai, Q. (2012). Subsea engineering handbook (1st ed.). Houston,
TX: Gulf Professional Publishing.
9. Golczynski, T. S., & Kempton, E. (2006). Understanding wax problems leads to
deepwater flow assurance solutions. World Oil, D7D10.
10. Singh, P., Venkatesan, R., Fogler, H. S., & Nagarajan, N. (2000). Formation and
aging of incipient thin film wax-oil gels. AIChE Journal, 46, 10591074.
11. Ashford, J. D., Blount, C.G., Marcou, J. A., & Ralph, J. M.(1990). Annular
packer fluids for paraffin control: Model study and successful field application. SPE
Production Engineering, 5, 351355.
12. Kleinhans, J., Niesen, V., & Brown, T. (2000). Pompano paraffin calibration field
trials. In SPE Annual Technical Conference and Exhibition (pp. 115). Dallas, TX:
Society of Petroleum Engineers.
13. Labes-Carrier, C., Rnningsen, H. P., Kolnes, J., & Leporcher, E. (2002). Wax
deposition in North Sea gas condensate and oil systems: Comparison between
operational experience and model prediction. In SPE Annual Technical Conference
and Exhibition. San Antonio, TX.
14. Barry, E. G. (1971). Pumping non-Newtonian waxy crude oils. Journal of the Institute
of Petroleum, 57, 7485.
15. Bokin, E., Febrianti, F., Khabibullin, E., & Perez, C. E. S. (2010). Flow assurance and
sour gas in natural gas production.
16. Agrawal, K. M., Khan, H. U., Surianarayanan, M., & Joshi, G. C. (1990). Wax
deposition of Bombay high crude oil under flowing conditions. Fuel, 69, 794796.
17. Suppiah, S., Ahmad, A., Alderson, C., Akbarzadeh, K., Gao, J., Shorthouse, J.,
Jamaluddin, A. (2010). Waxy crude production management in a deepwater subsea
environment. In SPE Annual Technical Conference and Exhibition (pp. 118).
Florence, Italy: Society of Petroleum Engineers.
13
14
2. LITERATURE SURVEY
2.1. Wax deposition
During the early years of the oil industry, easy profits meant that pipeline operators could
afford to be ambivalent about wax deposition and there was little incentive to analyse the
phenomena. Although the cooling of oil was, self-evidently, the cause of wax deposition,
there were few studies of the various parameters that control deposition rate and severity until
mitigation of these deposits started to become prohibitively expensive, largely due to the
move towards offshore oil recovery.
Most of the theoretical models underpinning studies of wax deposition are based on oil-wax
equilibria and equations-of-state. Essentially, these models are semi-empirical and require
experimental measurements of WAT (Wax Appearance Temperature) to allow their
application to specific crude oils. Won[1989] considered wax to be a solid solution of
hydrocarbons into which all components of the crude oil could enter. He based oil-wax phase
equilibria on the cooling curves of simple hydrocarbon mixtures. Subsequent studies have
shown this model to over predict wax deposition when tested against 'real' crude oil samples,
Pedersen et al [1991]. Also, WAT obtained from stock tank oils (STO's) has been shown to
vary considerably depending on measurement method, Hammami [1997]. This raises the
possible danger of an over-predictive model calibrated using inaccurate WAT values.
Faroozibadi [1995] proposed that a more accurate model of wax deposition would take into
account the range of solidification temperatures for different molecular weight waxes and
suggested that they do not form a solid solution, but rather de-mix on solidification. This
'multi-solid' model for wax deposition was tested against the more traditional solid-solution
model by Coutinho [2002]. Although Coutinho acknowledged that a 'multi-solid' model was
more realistic, the de-mixing of wax on solidification is supported by experimental evidence,
he concluded that the solid solution model's simplicity outweighed any limitations imposed
by idealisation.
Regardless of how idealized solutions are based on phase equilibria, they cannot accurately
predict deposition without considering the dynamic environment in which these phase
changes occur. Not only must the thermodynamics of deposition be understood but also the
kinetics of the process. To this end, experimental studies have analysed mechanisms of wax
deposition in flowing pipelines. In a study by Burger et al[1981] a laboratory flow circuit
was set up to allow cooling of oil as it was circulated through ~inch pipes. From his
observations and measurements of deposition rate Burger proposed mechanisms for
deposition and identified controlling factors. The mechanisms for wax deposition he
proposed were molecular diffusion, Brownian diffusion, gravity settling and shear dispersion.
The controlling factors identified were radial temperature flux, the oil's WAT and the flow
velocity and regime.
Burger's observations and theoretical predictions are confirmed by later experimental studies
by, amongst others, Hamouda and Davidsen [1995] and Creek et al [1998]. All of these
experimental studies observed that in addition to the controlling factors affecting deposition
15
rate, they also affected the deposit's physical structure. In terms of removing wax, knowledge
of the physical structure of the deposit is equally as important as predicting its deposition rate.
The mechanical properties of wax deposits are a function of the distribution of different
molecular weight hydrocarbons and the amount of oil entrained within the wax's crystalline
structure. Once a deposit establishes itself on a pipe wall these parameters change over time
and age hardening takes place. This phenomenon is of particular interest, as imposing time
dependency on the deposit's mechanical properties can have a profound impact on
remediation issues such as pigging frequency.
Singh [2000, 2001] has performed a series of laboratory experiments to develop a model
describing the aging and morphological changes in wax deposits. He proposed the existence
of a critical carbon number within the wax-oil system above which wax molecules diffuse
into the deposit and below which oil diffuses out into the bulk flow. The rate of this diffusion
process is controlled by the radial temperature gradient within the deposit and the flow
regime in the pipe. Also, in an experimental study, Cordoba and Schall [2001] provided
confirmation of this theory, concluding from their own experiments that hardening of the wax
deposit occurs due to solvent migration. Again, it is proposed that this solvent migration (or
diffusion) occurs due to a temperature gradient between the cool pipe wall and the flowing oil.
2.2. Wax crystallization and Wax-Oil Gel Formation
Ararimeh et al.(2011) have provided a critical review on the issue of wax formation in oil
pipelines. The characteristics of wax-oil gels depend on the crystal morphology and
structures of the crystal networks, which are strong functions of both thermal and shear
histories (Singh et al., 2000). The crystallization of wax molecules below the cloud point
temperature incurs formation of gels with a complex morphology. As shown in Figure 2.1.,
the structure of the wax-oil gel is an interlocking of various wax forms such as needles, plates
and orthorhombic wax crystals, dependent on the cooling rate (thermal history), wax
concentration and shear history (Dirand et al., 1998; Singh et al., 2000).
Fig. 2.1 Cross Polarized microscope photo of wax oil gel (Lee et al., 2007)
16
Cazaux et al. (1998) investigated the gel structure using X-ray diffraction (XRD), Smallangle X-ray scattering (SAXS), a cross-polarized microscopy (CPM) and a controlled stress
rheometer (CSR). They reported that the key parameters that determine the structure of waxoil gel are the crystal shape (aspect ratio) and number density of wax crystals, both of which
depend on the temperature and cooling rate. Chang et al. (1999) reported that the morphology
of the paraffin crystals strongly depends on both the cooling rate and the shear stress applied
to the mixture (Kane et al., 2003; Venkatesan et al., 2005). Recently Visintin et al. (2005) and
Vignati et al. (2005) reported that waxy gels have the characteristics of colloidal gels and the
radius of gyration of the wax-oil gel changes with cooling rate.
A variety of chemicals are available to pipeline operators that are generally referred to as
Flow Improvers. One group of chemicals that fit into this category are wax inhibitors or Pour
Point Depressants (PPDs). Inhibitors must be matched to the composition of the crude oil,
and as composition may vary from one well to another (even from the same reservoir) and
will also vary over time, periodic sampling and testing is necessary to ensure the chemical's
effectiveness. The problem is exacerbated where a number of wellheads feed into a common
riser and process facility, as is often the case in offshore production. Laboratory studies of
the effectiveness of chemical inhibitors by the California Institute of Technology and
Chevron Texaco revealed even greater concerns [Wang et al, 2003]. They found that in some
instances the deposition of low molecular weight paraffins (>C34) was reduced but the
amount of high molecular weight paraffins actually increased. Given the general correlation
between molecular weight and strength, this is a most undesirable outcome.
PPDs have been used which contain oil soluble long chain alkyl group and a polar moiety in
the molecular structure. The long chain alkyl group insert into wax crystal and polar moiety
exist on the wax surface and reduces wax crystal size.(El-Gamal et al.,1998; Holder and
Winkler,1965). They contain crystal modifiers that prevent the formation of large wax
molecules by bonding to the wax crystal and hindering further growth. These polymers need
to be added to the crude oil before the wax begins to crystallize but are not universally
effective, Garcia (1998, 2000), Chanda et al (1998). Inhibitors must be matched to the
composition of the crude oil, and as composition may vary from one well to another (even
from the same reservoir) and will also vary over time, periodic sampling and testing is
necessary to ensure the chemical's effectiveness. The problem is exacerbated where a number
of wellheads feed into a common riser and process facility, as is often the case in offshore
production. Many theoretical and experimental studies have been put forward to explain the
action mechanism of PPD for the control of wax crystallization.
17
The most extensively used flow improver for fuel oils are ethylene-vinyl acetate
copolymer (M.G. Botros (1997), J.C. Chen, (1985), N.A. Kidd (1982), S. IInyckyj, B.
Charles (1962), M.J. Wisotsky, H.N. Miller (1972).) alkyl ester of unsaturated carboxylic
acid-olefin copolymer(M.G. Botros (1997), H. Pieter, H. Rodolf (1973)), maleic anhydride
alkyl ester of unsaturated carboxylic acid copolymer(L.M. Dong, S.W.Xie (1996), K. Liao, Y.
Zhai (1999)).
The crystalline lattice structure of wax gels with and without PPD had been studied by
Srivastava et al. using XRD It was suggested that parafn crystallized with a predominantly
orthorhombic structure in isolated petroleum waxes. When forming gels in solvents, the
lattice structure of wax changed to the hexagonal form. The pour point depressant additive
hastened the development of hexagonal planes, the additive molecules seemed to provide the
necessary energy to parafn molecules to crystallize in this high energy form. The similar
phenomenon was found by Zhang fusheng when he studied the interactions between
wax and PPD using the infrared spectrometric (Vignati et al.(2005)).
In general, inhibition of wax crystallization has been considered to occur in the presence of
PPD by nucleation, co-crystallization or adsorption. It is generally believed that the PPD
function by disrupting or preventing the formation of three-dimensional wax networks,
leaving the amount of crystalline wax unaffected. However, based on the study of
Srivastava(1992) and Zhang fusheng (1995) as well as the relation between the wax crystal
structure and its thermodynamic properties, it can be concluded that the PPD can have an
effect on the amount of crystallized wax. The paper dealt with high speed centrifuge and gas
chromatography methods to study the effect of PPD on the amount and composition of wax
precipitated from solutions. Differential scanning calorimetry and X-ray diffraction were
used to study the blends of pour point depressant with parafn wax to gain a better
understanding of their interactions.
S. IInyckyj and C. O. Cole (1976) thought that the response of fuels to flow
improvers could be substantially improved by utilizing a dual functioning flow
improver's composition, which is a combination of two different wax modifying
compounds. One of these functions acts as a wax growth arrester while another acts as
nucleating agent. In the past years, works have been directed to the combination of two or
three compounds as flow improvers (N. Feldman (1980), N. Feldman, J.J. Habeeb (1992),
S. IInyckyj (1979)) These additives were a combination of the conventional flow improvers
and wax dispersants. The structure and composition of wax dispersants is similar to
conventional flow improver in some feature, but different in others. They often possess
highly polar functional groups. This polarity may reach a surfactant character, which is
considered as the basic prerequisite for the dispersant potential. Polar nitrogen containing
polymers can function as wax dispersants and flow improvers simultaneously in one
component additive.
Pour point is widely used to evaluate the low temperature owability of crude oil, there are
many factors affecting the owability behavior of crude oil such as its chemical composition,
temperature and the current, as well as previous thermal history.
18
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19
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Tang,Yongchun. Evaluation of effects of selected wax inhibitors on paraffin
deposition, Petroleum Science and Technology, Volume 21, Issue 4 (2003).
27. M.G. Botros (1997). U.S. Patent 5,681,359, October 28, 1997.
28. J.C. Chen, (1985). U.S. Patent 4,512,775, April 23, 1985.
29. N.A. Kidd (1982). U.S. Patent 4,362,533, December 7, 1982.
30. S. IInyckyj, B. Charles (1962). U.S. Patent 3,048,479, August 7, 1962.
31. S. IInyckyj, C.O. Cole (1976). U.S. Patent 3,961,916, June 8, 1976.
32. M.J. Wisotsky, H.N. Miller (1972). U.S. Patent 3,638,349, February 1, 1972.
33. H. Pieter, H. Rodolf (1973). U.S. Patent 3,726,653, April 10, 1973.
34. L.-M. Dong, S.-W. Xie, Acta Petroeli Sinica Chinese (Petroleum Processing
Section) 12 (4) (1996) 66.
35. K. Liao, Y. Zhai Pet, Sci. Technol. 17 (1&2) (1999) 51.
36. J. Zhang, Ch. Wu, W. Li, Y. Wang, H. Cao, DFT and MM calculation: the
performance mechanism of pour point depressants study, Fuel 83 (2004) 315326.
37. Srivastava SP, Tandon RS, Verma PS, Saxena AK, Joshi GC, Phatak SD.
Crystallization behavior of n-parafns in Bombay-High middle-distribution
wax/gel. Fuel 1992;71:5337.
38. S. IInyckyj, C.O. Cole (1976). U.S. Patent 3,961,916, June 8, 1976.
39. S. IInyckyj (1979). U.S. Patent 4,147,520, April 3, 1979
40. N. Feldman, J.J. Habeeb (1992). U.S. Patent 5,094,666, March 10, 1992.
20
3. EXPERIMENTAL WORK
In this study, the effects of various parameters on pressure drop reduction and ultimately wax
deposition thickness achieved by addition of 200-1000 ppm PPD has been investigated. In
order to make a comprehensive analysis of various operating parameters such as temperature,
oil flow rate, pipe diameter and concentration of PPD, some experiments have been carried
out with several concentrations of PPD at four different operating temperatures.
A flow loop apparatus was designed to determine the effect of temperature, flow rate and
PPD addition on wax deposition. The apparatus is shown schematically in figure 3.1.
21
p = 4 d
4 2
(d2 ) .............................(3.1)
where
p is the pressure drop
L is the length of the pipe section
D is the hydraulic diameter or effective inside diameter
Q is the volumetric flow rate
is the fluid density
f is the fanning factor
A waxy crude oil often behave as a non- Newtonian fluid when temperature becomes lower
than the cloud point and wax crystals are present in the crude oil. However, when the wax
content is low, e.g. less than 5% by weight, this non-Newtonian behavior is not appreciated
and the crude oil can be treated as Newtonian fluid. But in this case the wax content of the
crude oil in study is 11.3 which is very high and will contain good amount of asphaltenes and
wax crystals.
The friction factor in Equation 4.1 can be estimated from Equation 3.2 with the help of
Equation 3.3.
n
= N
NRe =
..................................(4.2)
.................................(4.3)
where
is the apparent viscosity of the crude oil c=16, n=1 for laminar flow and c = 0.046, n = 0.2
for turbulent flow. Laminar flow exists when NRe <2000. Substitution of Equation 7.2 into
Equation 4.1 yields Equation 3.4
2
4 2
= d5 () ( )
.........................(4.4)
Differentiating equation 4.4 with respect to the effective inside diameter and dividing the
resulting equation by equation 4.4 yields Equation 3.5.
22
(p f )
Pf
.............................(3.5)
(5 n)
d
d
This equation clearly shows that a small reduction of the effective inside diameter of the pipe
causes a significant increase in the frictional pressure drop across the pipe section. For
example, the frictional pressure drop can increase by 31.5% for laminar flow and 37.8% for
smooth pipe turbulent flow, respectively, if a wax layer with a uniform thickness of 0.0787 in.
(2mm) deposited in a pipe section with an inside diameter of 2in. (50.8mm). Once the
frictional pressure drop across a pipe section is measured and the flow rate, density, and
viscosity of the crude oil in the pipe section are determined, the wax thickness present in the
pipe wall can be calculated accurately from Equation 3.6.
n
(di 2 w )
5 n
2c L 4Q
Pf
2 n
.....................(3.6)
The pressure drop method is an on-line wax measurement technique that does not require
depressurization and restart in order to obtain the measurements. Neither does it impose any
influence on the in-situ and overall heat transfer.
23
Flow rate
At high flow rates the drag forces are high and the waxes do not deposit on the pipeline walls.
It is also seen in literature that at low diameter pipes, drag reduction was lesser that in high
diameter pipes. The flow rate was varied from 80 LPM to 120 LPM. After achieving the
desired flow rates, the system was allowed to reach equilibrium, i.e., it was made sure that the
flow rate did not fluctuate. Then the readings were taken.
Flowmeter
Pressure transducer
Water Jacket
Crude out
Pipe 2
Valve
Crude in
Water Jacket
Crude out
Pipe 1
Crude in
Water inlet
Water Jacket
Water outlet
Oil Bath
Water Bath
Gear pump
3.0
30C
35C
40C
45C
2.5
2.0
1.5
1.0
70
80
90
100
110
120
130
25
4.5
30C
35C
40C
45C
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
70
80
90
100
110
120
130
Table 3.1. Thickness of wax deposited in Pipes 1 and 2 at different temperatures and flow
rates
30C
35C
40C
45C
Pipe 1
Pipe 2
Pipe 1
Pipe 2
Pipe 1
Pipe 2
Pipe 1
Pipe 2
Q, LPM
w, mm w, mm
w, mm w, mm
w, mm w, mm
w, mm w, mm
80
2.43702 4.067585 2.52666 4.007913 2.65412 3.886016 2.37501 3.760565
90
2.11454 3.368641 2.20754 3.243101 2.33973 3.113901 2.05019 2.912803
100
1.78265 2.651731 1.88028 2.519083 2.01893 2.382474 1.71505 2.169655
110
1.46767 1.897909 1.56995 1.827437 1.71505 1.609485 1.3968 1.38107
120
1.14823 1.161697 1.25603 1.009725 1.40877 0.852866 1.07346 0.607773
Concentration of PPD in the waxy crude oil is an important factor in reducing thickness of
deposited wax. In the following experiments, the effect of increasing concentration on PPD
on wax deposition thickness has been studied. The concentrations of PPD used were 200 ppm,
400 ppm, 600 ppm, 800 ppm and 1000 ppm.
The analysis of the crude oil with the PPD shows that PPD produced a great reduction in
thickness on deposited wax. Figure 4.4-4.8 shows that the inhibitor reduced the wax thickness
at flow rate 80LPM, 90LPM, 100 LPM, 110LPM and 120 LPM respectively for Pipe 1. The
26
results are tabulated in Table 3.2. Similar data has been shown in figures 4.9-4.12, for pipe 2
at same flow rates (80,90,100,110,120 LPM), and corresponding results for pipe 2 have been
shown in table 3.3. Maximum reduction in wax deposition thickness was at 120 LPM and
45 C when 1000 ppm PPD was used. The reduction went up to 47%. The PPD has been used
in the current work are based on polymers which are normally used as pour point depressant.
The reduction in the pour point and the crude oil viscosity had been making the transportation
of the crude oil easier. This PPD was reducing the wax deposition process by interfering with
wax crystallization and growth process. However, this interfering mechanism has not yet
been fully understood.
2.7
2.6
2.5
2.4
2.3
2.2
Pure crude
Crude + 200 ppm PPD
2.1
2.0
1.9
25
30
35
40
45
50
Temperature, C
27
2.50
2.25
2.00
Pure crude
Pure crude + 200 ppm PPD
1.75
1.50
25
30
35
40
45
50
Temperature, C
2.2
2.0
1.8
1.6
1.4
Pure crude
Pure crude + 200 ppm PPD
Pure crude + 400 ppm PPD
1.2
1.0
25
30
35
40
45
50
Temperature,C
Figure 3.6 Effect of PPD concentration on wax deposition at Q = 100 LPM (Pipe 1)
28
1.8
1.5
1.2
Pure crude
Crude + 200 ppm PPD
Crude + 400 ppm PPD
Crude + 600 ppm PPD
Crude + 800 ppm PPD
Crude + 1000 ppm PPD
0.9
25
30
35
40
45
50
Temperature, C
Figure 3.7 Effect of PPD concentration on wax deposition at Q = 110 LPM (Pipe 1)
1.50
1.25
1.00
Pure crude
Crude + 200 ppm PPD
0.75
0.50
25
30
35
40
45
50
Temperature, C
Figure 3.8 Effect of PPD concentration on wax deposition at Q = 120 LPM (Pipe 1)
29
4.2
4.0
3.8
3.6
3.4
Pure crude
3.2
3.0
2.8
25
30
35
40
45
50
Temperature,C
3.8
3.6
3.4
3.2
3.0
2.8
2.6
Pure crude
2.4
2.2
2.0
1.8
25
30
35
40
45
50
Temperature, C
30
2.8
2.4
2.0
Pure crude
1.6
1.2
25
30
35
40
45
50
Temperature, C
Figure 3.11 Effect of PPD concentration on wax deposition at Q = 100 LPM (Pipe 2)
2.1
1.8
1.5
1.2
0.9
Pure crude
Crude + 200 ppm PPD
0.6
0.3
25
30
35
40
45
50
Temperature, C
Figure 3.12 Effect of PPD concentration on wax deposition at Q = 110 LPM (Pipe 2)
31
1.25
Pure crude
1.00
0.75
0.50
0.25
0.00
25
30
35
40
45
50
Temperature, C
Figure 3.13 Effect of PPD concentration on wax deposition at Q = 120 LPM (Pipe 2)
Table 3.2 Effect of PPD on wax deposition thickness at different temperatures for Pipe 1
Pipe
1
30C
35C
40C
45C
Q,
LPM
80
90
100
110
120
80
90
100
110
120
80
90
100
110
120
80
90
100
110
120
Pure
crude
w, mm
2.65412
2.33973
2.01893
1.71505
1.40877
2.52666
2.20754
1.88028
1.56995
1.25603
2.43702
2.11454
1.78265
1.46767
1.14823
2.37501
2.05019
1.71505
1.3968
1.07346
200 ppm
PPD
w, mm
2.61252
2.29659
1.9737
1.66773
1.35899
2.48234
2.16155
1.83201
1.51939
1.20276
2.39069
2.06646
1.73215
1.41473
1.09238
2.32724
2.00062
1.66294
1.34215
1.01575
400 ppm
PPD
w, mm
2.55569
2.23765
1.91187
1.60302
1.29087
2.42169
2.09864
1.76594
1.45016
1.12976
2.32724
2.00062
1.66294
1.34215
1.01575
2.2618
1.93268
1.5915
1.26718
0.93654
600 ppm
PPD
w, mm
2.49722
2.177
1.84822
1.53637
1.22066
2.35921
2.03379
1.69782
1.37873
1.05438
2.2618
1.93268
1.5915
1.26718
0.93654
2.19423
1.86253
1.51769
1.18966
0.85455
800 ppm
PPD
w, mm
2.37501
2.05019
1.71505
1.3968
1.07346
2.22829
1.89789
1.5549
1.22875
0.8959
2.12442
1.79003
1.44135
1.10944
0.76964
2.05223
1.71505
1.36234
1.02635
0.68158
1000 ppm
PPD
w, mm
2.29478
1.96692
1.62751
1.30497
0.97648
2.14209
1.80839
1.46068
1.12976
0.79115
2.03379
1.69589
1.34215
1.00511
0.65906
1.95841
1.61757
1.25954
0.91815
0.56678
32
Table 2.3 Effect of PPD on wax deposition thickness at different temperatures for Pipe 2
Pipe
2
30C
35C
40C
45C
Q,
LPM
80
90
100
110
120
80
90
100
110
120
80
90
100
110
120
80
90
100
110
120
Pure
crude
w, mm
4.067585
3.368641
2.651731
1.897909
1.161697
4.007913
3.243101
2.519083
1.827437
1.009725
3.886016
3.113901
2.382474
1.609485
0.852866
3.760565
2.912803
2.169655
1.38107
0.607773
200 ppm
PPD
w, mm
3.947395
3.243099
2.519081
1.755893
1.009722
3.886014
3.113899
2.382472
1.683253
0.852864
3.760562
2.980841
2.241685
1.458425
0.690828
3.631366
2.773554
2.022151
1.222519
0.437367
400 ppm
PPD
w, mm
3.728622
3.014479
2.277286
1.49664
0.74
3.664027
2.87839
2.133213
1.419902
0.565714
3.531888
2.738062
1.984535
1.182054
0.39384
3.395631
2.519081
1.752288
0.931922
0.124435
600 ppm
PPD
w, mm
3.5653
2.843715
2.096485
1.302445
0.523298
3.498218
2.702289
1.946616
1.222519
0.349931
3.360896
2.556316
1.791799
0.974512
0.170349
3.219158
2.328231
1.549632
0.71324
0.0781
800 ppm
PPD
w, mm
3.430094
2.702289
1.946616
1.141249
0.349931
3.360896
2.556316
1.791799
1.058594
0.170349
3.219158
2.405524
1.631735
0.801883
0.0781
3.072742
2.169652
1.381068
0.668314
0.031337
1000 ppm
PPD
w, mm
3.255021
2.519081
1.752288
0.931922
0.124435
3.183004
2.367039
1.59086
0.845613
0.031337
3.035374
2.209809
1.423768
0.668314
0.0781
2.882706
1.963507
1.250644
0.622976
0.003071
33
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34
35