INVESTIGATION OF EFFECT OF POUR POINT

DEPRESSANT ON WAX DEPOSITION AND

CRUDE FLOW BEHAVIOUR
INTERIM PROJECT REPORT
SUBMITTED IN PARTIAL REQUIREMENT FOR
THE DEGREE OF
MASTERS IN PETROLEUM ENGINEERING
(2015-2017)
BY

M Afzal Akthar (15MT000306)

Under the guidance of

Dr. Tarun Kumar Naiya

to

THE DEPARTMENT OF PETROLEUM ENGINEERING

INDIAN INSTITUTE OF TECHNOLOGY
(INDIAN SCHOOL OF MINES), DHANBAD-826004
1

List of contents
S.No

Title

Page no.

i.

List of figures

ii.

List of tables

1.

Introduction & Background

1.1. Introduction

1.2. Effect of wax deposition in pipes

1.3. Introduction to Paraffins

1.3.1. Paraffins

1.3.2. Paraffin Wax Management

2.

3.

4.

1.3.3. Paraffin Wax Mitigation & Prevention Techniques

10

1.3.4. Methods of wax prevention and removal

10

1.3.4.1. Thermal

11

1.3.4.2. Chemical

11

1.3.4.3. Mechanical

12

Literature Survey

15

2.1. Wax deposition

15

2.2. Wax crystallization and Wax-Oil Gel Formation

16

2.3. Pour Point Depressants

17

Experimental Work

21

3.1. Experimental Apparatus

21

3.2. Wax deposition calculations

22

3.3. Pipeline study

23

3.4. Results and discussion

25

3.4.1. Effect of flow rate and temperature on wax deposition

25

3.4.2. Effect of PPD on wax deposition thickness

26

Future work to be done

35
2

List of figures

Fig.No.
no.
1.1.

Title

Page

A schematic of the change from onshore to offshore in petroleum

production in the late twentieth century

1.2.

An example of a pipeline being plugged by wax deposits on the wall

1.3.

Areas reported to have wax deposition problems across the world

2.1.

Cross Polarized microscope photo of wax oil gel

16

3.1.

Schematic of experimental set-up

24

3.2.

Effect of flow rate on wax deposition in Pipe 1

25

3.3.

Effect of flow rate on wax deposition in Pipe 2

26

3.4.

Effect of PPD concentration on wax deposition at Q = 80 LPM (Pipe 1)

27

3.5.

Effect of PPD concentration on wax deposition at Q = 90 LPM (Pipe 1)

28

3.6.

Effect of PPD concentration on wax deposition at Q = 100 LPM (Pipe 1)

28

3.7

Effect of PPD concentration on wax deposition at Q = 110 LPM (Pipe 1)

29

3.8.

Effect of PPD concentration on wax deposition at Q = 120 LPM (Pipe 1)

29

3.9.

Effect of PPD concentration on wax deposition at Q = 80 LPM (Pipe 2)

30

3.10.

Effect of PPD concentration on wax deposition at Q = 90 LPM (Pipe 2)

30

3.11.

Effect of PPD concentration on wax deposition at Q = 100 LPM (Pipe 2)

31

3.12.

Effect of PPD concentration on wax deposition at Q = 110 LPM (Pipe 2)

31

3.13.

Effect of PPD concentration on wax deposition at Q = 120 LPM (Pipe 2)

32

List of tables

Table.No.
no.
3.1.

3.2.

Title
Thickness of wax deposited in Pipes 1 and 2 at different temperatures
and flow rates

26

Effect of PPD on wax deposition thickness at different temperatures

for Pipe 1

1.3.

Page

32

Effect of PPD on wax deposition thickness at different temperatures

for Pipe 2

33

1. INTRODUCTION & BACKGROUND

1.1.

Introduction

Crude oil is a complex mixture of hydrocarbons, consisting of waxes, asphaltenes, resins,

aromatics, and naphthenes. Wax deposition has become one of the most common flow
assurance problems in the petroleum industry. This phenomenon can result in many problems
such as decreased production rates, increased power requirements and failure of facilities.
As petroleum resources shift from onshore reservoirs toward offshore subsea production, the
industry is currently facing unprecedented challenges to maintain flow assurance for
petroleum production, in which the strategy to prevent or mitigate wax deposition has
become increasingly costly and complicated.
Wax deposition is a critical operational challenge to the oil and gas industry. As early as
1928, wax deposition was reported as an issue that presents many difficult problems
while being produced, transported, and stored (Reistle, 1932). Wax deposition
problems occur in a wide range of locations in the petroleum production chain,
including flow lines, surface equipment, and topside facilities, and downstream refineries.
In some of the extreme cases, it can also occur in well tubings.
The waxy components of crude oils, also known as n-paraffins, represent a group of nalkanes with carbon numbers that are usually greater than 20 (Lee, 2008). These components
are normally dissolved in the oil at reservoir conditions where the temperature is relatively
high. However, as the crude oil leaves the reservoir and travels toward processing facilities,
its temperature can decrease substantially and potentially fall below the wax appearance
temperature (WAT) (Berne-Allen & Work, 1938). When the waxy components can precipitate
out of the oil and form solids, resulting in slurries in the oil flow that require higher pressure
drop for transportation. More importantly, the precipitation of these components on the inner
surface of the pipe wall can lead to the formation of wax deposits, which often occurs on the
tubing, the pipelines, and the process equipment (Reistle, 1932).
In early- to mid-1990s, the problem of wax deposition usually occurred during
petroleum production on land or onshore resources (Reistle, 1932). In 1969, it was reported
that the cost for wax control in U.S. domestic production amounted annually to $4.5$5
million (Bilderback & McDougall, 1969). Because of easy access and management for these
resources, the problem of onshore wax deposition can be addressed by relatively simple
methods, including the optimization of the operating conditions (pipeline size, pressure, etc.).
Heating of the pipeline or mechanical removal of the wax deposit was used occasionally
and was generally not as prohibitive. It is during the late twentieth century that the
problem of wax deposition has become increasingly challenging, as the production of
petroleum fluids shifted from onshore resources toward offshore reservoirs around the
world. A schematic of this shift is shown in Figure 1.1 (Huang, Senra, Kapoor, & Fogler,
2010).
5

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.

1.2.Effect of wax deposition in pipes

Crystallization of waxes in crude oils leads to non-Newtonian flow characteristics, including
very high yield stresses that are dependent on time and the shear and temperature histories of
the fluid. This crystallization may cause three problems:

High viscosity, which leads to pressure losses

High-yield stress for restarting flow

Deposition of wax crystals on surfaces

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
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.

1.3. Introduction to Paraffins

1.3.1. Paraffins
Paraffin precipitation and deposition in flowlines and pipelines is an issue impacting
the development of deep-water subsea hydrocarbon reservoirs. The buildup of paraffin
deposits decreases the pipeline cross-sectional area, restricts operating capacities, and places
additional strain on pumping equipment. Hence it becomes necessary to understand paraffins.
Waxes are typically long, linear or branched n-paraffin chains within produced
hydrocarbons and primarily consist of paraffin hydrocarbons (C18-C36) and naphthenic
hydrocarbons (C30 - C60).
Hydrocarbon components of wax can exist in various states of matter (gas, liquid or solid)
depending on their temperature and pressure. When the wax freezes, it forms crystals referred
to as macrocrystalline wax.Those formed from naphthenes are known as microcrystalline
wax. The solid forms of paraffin, called paraffin wax, are from the heaviest molecules from
phytane (C20H42 ) to lycopane (C40H82 ).
Paraffin wax is a white, odorless solid with a typical melting point between about 115F and
154F (46 and 68C) having a density of around 0.9 g/cm 3.Waxes have low thermal
conductivity, a high heat capacity, and are insoluble in water. While constant deposition of
wax can block production lines, it can also act as insulation due to its low thermal
conductivity and high heat capacity, resulting in higher arrival temperatures during steady
flowing conditions and longer cooldown times during shutdowns. Paraffin wax is soluble in
ether, benzene and certain esters, while being unaffected by most common chemical
reagents.

1.3.2. Paraffin Wax Management

Paraffin deposition can cause a multitude of operational challenges including:

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.
9

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.
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.

1.3.3. Paraffin Wax Mitigation & Prevention Techniques

Some common wax mitigation/prevention techniques are:

1.4.

Optimized pipeline sizing and layout.

Insulating the line to prevent heat loss and maintain flowing temperatures above the
WAT.
Injection of paraffin inhibitors, dispersants or solvents. Inhibitors need be injected
above the WAT to be effective. Solvents can be used on existing wax deposits and
dispersants when it is not possible to inject above the WAT.
Controlled production of wax deposits by carefully monitoring the wax layer
thickness.
Use of non-metallic pipe linings and coatings to reduce the frictional drag and
thereby reduce the effects of shear dispersion and molecular diffusion.
Selection and use of a suitable pig design and periodic pigging of the line.

Methods of wax prevention and removal

Wax can deposit on surfaces in the production system and in the formation. Wax deposition
can be prevented or removed by a number of different methods. These methods fall into three
main categories:
1. Thermal
2. Chemical

10

3. Mechanical

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.
11

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.
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

Mechanical removal by using progressive pigging programs to remove

accumulated deposits while ensuring that the use of an overly-aggressive pig will
not result in the pig becoming stuck behind the wax accumulation.

Scrapers and cutters are used extensively to remove wax deposits from tubing
because they can be economical and result in minimal formation damage. Scrapers
may be attached to wireline units, or they may be attached to sucker rods to
remove wax as the well is pumped. Deposits in surface pipelines can be removed
by forcing soluble or insoluble pigs through the lines. Soluble pigs may be
composed of naphthalene or microcrystalline wax. Insoluble pigs are made of
plastic or hard rubber.
Another method of mechanical intervention to prevent deposition is the use of
plastic or coated pipe. Low-friction surfaces make it more difficult for wax crystals
to adhere to the pipe walls. Deposition will still occur if conditions are highly
favorable for wax precipitation, and deposits will grow at the same rate as for other
pipes once an initial layer of material has been laid down; therefore, the pipe and
coating system must be capable of withstanding one of the other methods of wax
removal.

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

13

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.
18. Garcia, M. C. (2001). Paraffin deposition in oil production. In SPE International
Symposium on Oilfield Chemistry (pp. 17). Houston, TX: Society of Petroleum
Engineers.
19. Zhu, T., Walker, J. A., & Liang, J. (2008). Evaluation of wax deposition and its
control during production of Alaska North Slope OilsFinal Report.
20. Venkatesan, R. (2004). The deposition and rheology of organic gels (Ph.D.
thesis). University of Michigan.
21. Gluyas, J. G., & Underhill, J. R. (2003). The Staffa Field, Block 3/8b, UK North Sea.
Geological Society, London, Memoirs, 20, 327333.
22. Singh, P. (2000). Gel deposition on cold surfaces (Ph.D. thesis). University of
Michigan.
23. Erickson, D. D., Niesen, V. G., & Brown, T. S. (1993). Thermodynamic measurement
and prediction of paraffin precipitation in crude oil. In SPE Annual Technical
Conference and Exhibition (pp. 353368). Houston, TX: Society of Petroleum
Engineers.

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
15

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
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).

16

Fig. 2.1 Cross Polarized microscope photo of wax oil gel (Lee et al., 2007)

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.

2.3. Pour Point Depressants

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.
17

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.
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
18

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.
References
1. Won, K W. Thermodynamic calculation of cloud point temperatures and wax phase
compositions of refined hydrocarbon mixtures, Fluid Phase Equilibria Volume 53,
December, Pages 377-396 (1989).
2. Pedersen, K S, Skovborg, P and Ronningsen, H P. Wax precipitation from North Sea
crude oils. 4. Thermodynamic modelling, Energy & Fuels, 5, 924 (1991).
3. Hammami, Ahmed. Paraffin Deposition from crude oils: Comparison of laboratory
results to field data, Paper presented at SPE Annual Technical Conference and
Exhibition, San Antonio, Texas, 5th- 8th October, Paper No. SPE 38776 (1997).
4. Coutinho, Joao A P; Edmonds, Beryl; Moorwood, Tony; Szczepanski, Richard and
5. Zhang, Xiaohong. Reliable wax predictions for Flow Assurance, Presented at the SPE
13th European Petroleum Conference, Aberdeen, UK 29-31 October (2002).
6. Burger, ED; Perkins, T K; Streigler, J H. Studies of Wax Deposition in the Trans
Alaska Pipeline, Journal of Petroleum Technology, June, 1075-1086 (1981).
7. Hamouda and Davidsen. An approach for simulation of paraffin deposition in
pipelines as a function of flow characteristics with a reference to Tees ide Oil
Pipeline, Paper presented at the Society of Petroleum Engineers' International
Symposium on Oilfield Chemistry, San Antonio, TX, U.S.A., 14-17 February 1995
(1995).
8. Creek, J L; Hans, Jacob Lund; Brill, James P; Volk, Mike. Wax deposition in single
phase flow, Fluid Phase Equilibria, Vol 158-160, Elsevier, 801-811 (1999).
9. Singh, Probjot; Venkatesan, Ramachandran; Fogler, H Scott; Nagarajan N R.
Morphological Evolution of Thick Wax Deposits, AIChE Journal, Vol47, No 1,
January, 6- 18 (2001 ).
10. Cordoba, A J and Schall, C A. Application of a heat transfer method to determine wax
deposition in a hydrocarbon binary mixture, Fuel Vol. 80, 1285-1291 (200 1 ).
11. Cordoba, A J and Schall, C A. Solvent migration in a paraffin deposit, Fuel Vol. 80,
1279-1284 (2001).

19

12. Ararimeh , D P Chakrabarti, Angelus Pilgrim, M.K.S. Sastry. Wax Formation in oil
pipelines: A critical review, International Journal of Multiphase Flow 37 (2011) 671694.
13. Dirand, M., V. Chevallier, E. Provost, M. Bouroukba, and D. Petitjean,
Multicomponent Paraffin Waxes and Petroleum Solid Deposits: Structural and
Thermodynamic State, Fuel 77, 1253 (1998).
14. Singh, P., R. Venkatesan, H.S. Fogler, and N.R. Nagarajan, Formation and Aging of
Incipient Thin Film Wax-Oil Gels, AIChE J. 46, 1059 (2000)
15. Lee, H.S., P. Singh, W.H. Thomason, and H.S. Fogler, Waxy Oil Gel Breaking
Mechanisms: Adhesive versus Cohesive Failure, Energy and Fuel, (2007)
16. Cazaux, G., L. Barre, and F. Brucy, 1998 SPE Annual Technical Conference and
Exhibition, New Orleans, 27 (1998).
17. Chang, C., D.V. Boger, and Q.D. Nguyen, Yielding of Waxy Crude Oils, Ind. Eng.
Chem. Res. 37, 1551 (1998)
18. Kane, M., M. Djabourov, J.L. Volle, J.P. Lechaire, and G. Frebourg, Morphology of
Paraffin Crystals in Waxy Crude Oils Cooled in Quiescent Conditions and under
Flow, Fuel 82(2), 127 (2003)
19. Venkatesan, R., N.R. Nagarajan, K. Paso, Y.B. Yi, A.M. Sastry, and H.S. Fogler, The
Strength of Paraffin Gels Formed under Static and Flow Conditions, Chem. Eng. Sci.
60(13), 3587-3598 (2005)
20. Visintin, R.F.G., R. Lapasin, E. Vignati, P. D'Antona, and T.P. Lockhart, Rheological
Behavior and Structural Interpretation of Waxy Crude Oil Gels, Langmuir 21(14),
6240-6249 (2005)
21. Vignati, E., R. Piazza, R.F.G. Visintin, R. Lapasin, P. D'Antona, and T.P. Lockhart,
Wax Crystallization and Aggregation in a Model Crude Oil, J. of Phys.: Condens.
Matter 17(45), 3651-3660 (2005)
22. Holder, G.A., Winkler, J., 1965. Wax crystallization from distillate fuels. J. Inst.
Petrol.51, 228252.
23. I.E. El-Gamal, A.M. Atta, A.M. Al-Sabbagh, Fuel 76 (14/15) (1997) 14711478.
24. Garcia, Maria del Carmen; Carbognani, Lante; Urbina, Argelia; Orea, Miguel.
Paraffin deposition in oil production. Oil composition and paraffin inhibitors activity,
Journal of Petroleum Science and Technology, Vol. 16, Issue 9-10, Oct/Nov, 10011021 (1998).
25. Chanda, D et al. Combined effect of asphaltenes and flow improvers on the
rheological behaviour of Indian waxy crude oil, Fuel, vol.77, No. 11, 1163-1167
(1998).
26. Wang, Kang-Shi; Wu, Chien-Hou; Creek, Jefferson L;
Shuler, Patrick J;
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.
20

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.

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.

3.1. Experimental Apparatus

Experimental Setup: The experimental setup consists of a oil bath with 30L capacity
which is equipped with temperature control system and mechanical stirrer, a stainless steel
double-pipe heater, a chilling/ heating circulator, a centrifuge pump variable drive, valves
for regulating the flow of crude oil, and thermocouples for temperature reading and a
pipeline.
Test section: The test section consists of two horizontal independent stainless steel pipes
(SS-304) of 0.0508 m (2 inches) and 0.0254 m (1 inch) diameter and 2.5 meters length.
The whole length of the pipeline and exposed surfaces are completely insulated to
minimise heat loss. Pressure transducers were fitted at both the ends of the pipeline to
measure the pressure drop. Flow meters were placed at the outlet of each pipeline. Valves
were operated for varying flow rates in the test section. Both, oil flow and water in oil as
dispersed flow were kept in circulated mode until the loop reached its stabilization
condition for a particular flow rate and temperature.
Data acquisition: The data acquisition section consists of pressure transducers, flow
meters, temperature sensors connected to a control panel where the input data can be
controlled as per requirement.
Gear pump was used to circulate waxy crude oil from the oil bath through the pipeline test
sections. Waxy crude oil and the coolant (water) temperatures were adjusted at the desired

21

values by controlling the bath and the chilling circulator temperatures. Volumetric flow
meters were used to measure flow rates of waxy crude oil.
The water bath was heated and the water was flowed through the jackets of the two test
sections to liquefy remove all the fluid that remains in the pipe after termination of an
experiment.

3.2. Wax deposition calculations

The method of calculating wax deposition is based on the concept that wax deposition in a
pipe section reduces the hydraulic diameter of the flowing fluid inside the pipe, resulting in
an increase in friction pressure drop over the pipe section.
The friction pressure drop across a section of pipe with wax deposited inside can be
calculated using the Equation 3.1
L 4Q 2
pf =4 f
d 2 d 2 .............................(3.1)

( )

where
pf

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

f =c N

..................................(4.2)

22

N =

4 Q
d

.................................(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
N
for turbulent flow. Laminar flow exists when
<2000. Substitution of Equation 7.2 into
Equation 4.1 yields Equation 3.4
Pf =

2 cL
d 5n

2n

4Q

( )( )

.........................(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.

( p f )
Pf
(5 n)
d
d

.............................(3.5)

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

2n

.....................(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.

3.3. Pipeline study

Pressure drop
During the experiments, the measured pressure drop in the pipelines increased. When the
temperature of crude oil inside the pipelines was raised above its WAT by circulating hot
23

water through the jackets, the wax liquefied and the pressure drop reduced back to the initial
amount. If paraffin wax deposits on the pipeline wall the pipeline diameter will decrease. We
can see in Equation 4.4 that frictional pressure drop is inversely proportional to the pipeline
diameter to a power of five. This means that a change in pipe diameter will have a great
impact on pressure drop.
Temperature
Temperature has a strong effect on wax precipitation and deposition. In the experiments four
temperatures were fixed to study wax deposition. Two temperatures were below the pour
point of the crude oil in question, i.e., 30C and 35C while two temperatures were above
pour point, i.e., 40C and 45C. The effect of temperature on wax deposition thickness was
measured at different flow rates.

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
Water Bath

Oil Bath
24

Gear pump

Pipe 1: length (test section) = 2.5 m

diameter = 0.0254 m
relative roughness = 0.00059
Pipe 2: length (test section) = 2.5 m
diameter = 0.0508 m
relative roughness = 0.000295
Figure 3.1. Schematic of experimental set-up

4.4. Results and discussion

3.4.1. Effect of flow rate and temperature on wax deposition
The change in wax deposition thickness in pipe 1 and pipe 2 with different flow rates at 30C
- 45C is shown in Figure 3.2. and Figure 3.3 and the data is tabulated in Table 3.1. In this
experimental study, five flow rates of crude oil are studied i.e., 80, 90, 100, 110 and 120
L/min. It is deduced from the figures that the flow rate of crude oil has an influence on the
wax deposition thickness inside the pipelines. The reduction in thickness of the deposited
wax is 71.44 % in Pipe 2 when flow rate is increased from 80 to 120 LPM at 30C. At the
same temperature the wax deposition thickness reduced from 2.43 mm to 1.14 mm (53%) for
Pipe 1. It can be seen in Figure 3.3 that an increase in the bulk crude oil flow rate results in
lower deposition amount. At high flow rates, due to high velocities of crude oil flow, the
deposition decreases due to turbulence in the walls. This trend is in agreement with
previously reported trends where the mass deposit decreases with an increase in crude oil
flow rate or Reynolds number (Singh et al., 2000; Parthasarathi et al., 2005; Fong and
Mehrotra, 2007)

25

Wax deposition thickness, mm

3.0

30C
35C
40C
45C

2.5

2.0

1.5

1.0
70

80

90

100

110

120

130

Flow rate, LPM (Pipe dia. = 1 inch)

Figure 3.2. Effect of flow rate on wax deposition in Pipe 1

4.5

30C
35C
40C
45C

Wax deposition thickness, mm

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

Flow rate, LPM (Pipe dia. = 2 inches)

Figure 3.3. Effect of flow rate on wax deposition in Pipe 2

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 4.06758 2.52666 4.00791 2.65412 3.88601 2.37501 3.760565
26

90
2.11454
100
1.78265
110
1.46767
120
1.14823

5
3.36864
1
2.65173
1
1.89790
9
1.16169
7

2.20754
1.88028
1.56995
1.25603

3
3.24310
1
2.51908
3
1.82743
7
1.00972
5

6
2.33973 3.113901
2.38247
2.01893 4
1.60948
1.71505 5
0.85286
1.40877 6

2.05019 2.912803
1.71505 2.169655
1.3968

1.38107

1.07346 0.607773

3.4.2. Effect of PPD on wax deposition thickness

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
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.

27

2.7

Wax deposition thickness,mm

2.6
2.5
2.4
2.3
2.2
P ure crude
Crude + 200 ppm P PD

2.1

Crude + 400 ppm P PD

Crude + 600 ppm P PD

2.0

Crude + 800 ppm P PD

Crude + 1000 ppm P PD

1.9
25

30

35

40

45

50

Temperature, C

Figure 3.4 Effect of PPD concentration on wax deposition at Q = 80 LPM (Pipe 1)

Wax deposition thickness, mm

2.50

2.25

2.00

P ure crude
P ure crude + 200 ppm P P D

1.75

P ure crude + 400 ppm P P D

P ure crude + 600 ppm P P D
P ure crude + 800 ppm P P D
P ure crude + 1000 ppm P P D

1.50
25

30

35

40

45

50

Temperature, C

Figure 3.5 Effect of PPD concentration on wax deposition at Q = 90 LPM (Pipe 1)

28

2.2

Wax deposition thickness, mm

2.0

1.8

1.6

1.4

P ure crude
P ure crude + 200 ppm P P D
P ure crude + 400 ppm P P D

1.2

P ure crude + 600 ppm P P D

P ure crude + 800 ppm P P D
P ure crude + 1000 ppm P P D

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)

Wax deposition thickness, mm

1.8

1.5

1.2

P ure crude
Crude + 200 ppm P P D
Crude + 400 ppm P P D
Crude + 600 ppm P P D
Crude + 800 ppm P P D
Crude + 1000 ppm P P D

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)

29

Wax deposition thickness, mm

1.50

1.25

1.00

P ure crude
Crude + 200 ppm P P D

0.75

Crude + 400 ppm P P D

Crude + 600 ppm P P D
Crude + 800 ppm P P D
Crude + 1000 ppm P P D

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)

4.2

Wax deposition thickness, mm

4.0

3.8

3.6

3.4
P ure crude

3.2

Crude + 200 ppm P P D

Crude + 400 ppm P P D
Crude + 600 ppm P P D

3.0

Crude + 800 ppm P P D

Crude + 1000 ppm P P D

2.8
25

30

35

40

45

50

Temperature,C

Figure 3.9 Effect of PPD concentration on wax deposition at Q = 80 LPM (Pipe 2)

30

3.8

Wax deposition thickness, mm

3.6
3.4
3.2
3.0
2.8
2.6
P ure crude

2.4

Crude + 200 ppm P P D

2.2

Crude + 400 ppm P P D

Crude + 600 ppm P P D

2.0

Crude + 800 ppm P P D

Crude + 1000 ppm P P D

1.8
25

30

35

40

45

50

Temperature, C

Figure 3.10 Effect of PPD concentration on wax deposition at Q = 90 LPM (Pipe 2)

Wax deposition thickness, mm

2.8

2.4

2.0

P ure crude

1.6

Crude + 200 ppm P P D

Crude + 400 ppm P P D
Crude + 600 ppm P P D
Crude + 800 ppm P P D

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)

31

2.1

Wax deposition thickness, mm

1.8

1.5

1.2

0.9
P ure crude
Crude + 200 ppm P P D

0.6

Crude + 400 ppm P P D

Crude + 600 ppm P P D
Crude + 800 ppm P P D

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)

1.25
P ure crude

Wax deposition thickness, mm

Crude + 200 ppm P P D

Crude + 400 ppm P P D

1.00

Crude + 600 ppm P P D

Crude + 800 ppm P P D

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)

32

Table 3.2 Effect of PPD on wax deposition thickness at different temperatures for Pipe 1
Pipe
1

30
C

35
C

40
C

45
C

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

Table 2.3 Effect of PPD on wax deposition thickness at different temperatures for Pipe 2
Pipe
2

30
C

35
C

40
C

Q,
LPM
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

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

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

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

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

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
33

45
C

80
90
100
110
120

3.760565
2.912803
2.169655
1.38107
0.607773

3.631366
2.773554
2.022151
1.222519
0.437367

3.395631 3.219158
2.519081 2.328231
1.752288 1.549632
0.931922 0.71324
0.124435
0.0781

3.072742
2.169652
1.381068
0.668314
0.031337

2.882706
1.963507
1.250644
0.622976
0.003071

References
1. Singh P, Venkatesan R, Fogler HS, Nagarajan N. Formation and aging of incipient
thin film waxoil gels. AIChE J 2000;46:105974.
2. Parthasarathi P, Mehrotra AK. Solids deposition from multicomponent wax solvent
mixtures in a bench scale flow-loop apparatus with heat transfer. Energy Fuels
2005;19:138798.
3. Fong N, Mehrotra AK. Deposition under turbulent flow of wax solvent mixtures in a
bench-scale flow-loop apparatus with heat transfer. Energy Fuels 2007;21:126376.

34

4. FUTURE WORK TO BE DONE

As explained in chapter 4 on experimental work, in this session, experiments were conducted
to study the effect of a pour point depressant in lowering the pressure drop of flow of the
waxy crude which is characterized by drag reduction.
In the next phase of the research (semester 4 : 2015-2017 session) , it is intended to study
more on the role of pour point depressant in improving flow. Also it is looked to study the
role the PPD plays in wax deposition behavior. This is intended to be achieved through more
pipeline study experiments with different PPDs. Also it is thought to perform more
experiments like differential scanning calorimetry, to study the the wax precipitation curve
and find wax appearance temperature; X- ray diffraction and microscopy to study the wax
crystal morphology in presence of PPD.

35