Wax Deposition and Characterization

using combined scientific

measurements along with its
prevention and removal
Muskaan Kothari, Rajdip Soni, Ayush Nair

Keywords: Wax deposition, Wax treatment, Wax Prevention, Oil pipelines and tanks, Wax
Characterization

ABSTRACT

A review on the deposition of wax, its treatment, and preventive measures. Utilizing different models
available to detect deposition as well as to characterize the wax depositing on the inner side of pipelines
used for crude transportation from oil wells and reserves to refineries, as well the tanks used for crude
storage. Several methods of wax characterization are compared along with available data. Besides,
various types of chemical inhibitors are highlighted, based on how significantly they lower the Wax
Appearance Temperature (WAT) and soften the deposited wax as a means to degrade it.
The approach to detecting wax deposition includes EM Wave utilization under coupled scientific
measurements. An assessment of the C-S measurements is done by listing the pros and cons followed
by modeling the rate of deposition. Subsequent models provide theoretical information on different
parameters of wax that is deposited. Chemical inhibitors used to eliminate wax depositions range from
ionic salts to co-polymeric compounds. A detailed comparison is presented on the ability of each
compound to reduce the WAT and soften the hardened wax. To reduce the pour point greatly, different
surfaces and chemicals are suggested for coating the inner pipes to prevent wax deposition. However,
considering the limitations, industrial methods of wax removal are discussed.

1. INTRODUCTION

WPT is the temperature at which the wax in the crude separates itself from the liquid form via
precipitation making its appearance waxy or cloudy. After being separated from crude, when the
temperature begins to fall, an interlocking network of paraffin particles is formed due to the attraction
of precipitated matter. This leads to the thickness of the crude at a temperature also known as PP. At
this point, the thick and slimy crude loses its ability to flow. Naturally, this causes problems in
transportation and reduces the quality of the crude and it becomes very urgent for engineers to remove
its presence or strive to prevent its formation.
 2. CHARACTERIZATION

There are several factors under which wax can be characterized that have been discussed below.
However, it is important to know why this classification is done. It is necessary to do a thorough study of
the wax that is being dealt with to decide the treatment process. For example, if the wax is
microcrystalline then the melting range is wider owing to the complexity of the wax. Similarly, different
environments lead to the formation of different types of wax which require different types of prevention
mechanisms.

2.1 WAX APPEARANCE TEMPERATURE

Wax mainly constitutes the paraffinic content of crude oil. It is highly viscous and tends to get deposited
over the inner surfaces of pipelines that are used to transport raw crude from reservoirs to refineries.
One of the most important characteristics is the paraffin’s Wax Appearance Temperature (WAT). It is
defined as the cloud point of the waxy fluid at which the wax particles first start to crystallize when the
system is subjected to cooling. The cooling phenomenon may be natural, while hot crude is being pumped
through the network due to atmospheric temperature difference, or forced when it is passed through heat
exchangers.
It gives an accurate estimate of possible wax precipitation. WAT is popularly found by the scientific,
experimental technique of DSC. It is a thermos-analytic technique that measures heat flow from or to the
sample when the sample is either heated or cooled. When the material precipitates on cooling (in this case,
paraffinic wax), it shows up on the curve of DSC as an exothermic peak.

2.2 POUR POINT

Pour point is yet another standard way of assessing the extent of wax deposition. It is the lowest temperature
at which the crude is just able to flow under the gravitational pull. The primary point of differentiating
WAT and PP is that WAT measures the freezing point of paraffinic wax alone whereas PP determines the
flow-stopping temperature of the raw crude.
PP is helpful because it helps determine the kind of PPD to be used to lower the pour point. This discourages
the solidification of crude while being transported hence reducing the chances of deposition. In addition to
being used in crude transportation, PPDs are also used in engines to stop gasoline from freezing in colder
regions and also in aviation jet fuel.
Some typical examples are alkyl-aromatic and aliphatic polymers and non-polymer materials such as
phenyltristearyloxysilane.
 2.3 LATENT THERMAL ENERGY STORAGE

The phase change corresponding to melting and freezing gives rise to the storage of thermal energy in
Latent Thermal Energy Storage systems. Added heat gets stored as latent heat of fusion for melting and for
freezing, this latent heat gets liberated into the surrounding. During the phase change, circulating fluids like
air or water stores the dissipated heat and cause the phase change.

2.4 CUMULATIVE THERMAL ENERGY STORAGE

Cumulative Thermal Energy is also an important characterization of wax. It has been defined as the thermal
energy stored in wax by raising the temperature from a reference temperature to a higher temperature by
also considering all the composition effects of the hydrocarbons present in the wax. The sensible heat stored
in wax is due to the difference between latent heat and cumulative heat stored at different temperatures.

2.5 OTHER CHARACTERIZATIONS

The paraffin wax formed from the crude oil is a complex mixture of hydrocarbons which are non-reactive,
non - toxic, clean fuel, colorless, good water barrier. The physical characteristics of the wax crystals show
that they are hard and brittle with the melting point ranging from 120°F to 160°F based on the amount and
type of hydrocarbons present. These wax crystals are mainly divided into two major categories namely
Microcrystallines and Macrocrystallines where the microcrystalline consists of high portions of naphthene
and paraffin and are made as a combination of lube distillates and residual oil. On the other hand,
macrocrystalline are straight-chain hydrocarbons ranging from C20 – C50 with structures visible to naked
eyes unlike the case with microcrystalline which are microscopic.

3. TREATMENT AND PREVENTION METHODOLOGY

Before the methods of prevention and treatment of paraffin are discussed, it is vital to know the need.
The wax crystals can get deposited at the bottom of tanks which affect the quality of crude oil is stored.
The chemistry behind is that stable emulsions are formed when this happens and complex is formed
with the precipitated asphaltene. This complex becomes responsible for the blockage of pipelines. As
mentioned before, obstruct the flow of oil through pipelines can be very inconvenient as it is essential
for transportation from one point of the industry to another. Pipeline operations are severely affected
as the properties of crude change from that of Newtonian Fluids to Non-Newtonian Fluids.
 3.1 EM WAVE UTILISATION

Removal of wax deposits can be achieved by several techniques like dehydration of pumped gas, breaking
down of pressure at both ends of the pipeline, exciting the molecular matter by laser radiations, usage of
toxic chemicals, etc. But these methods are significantly expensive and also compromise with the safety
aspects, so the usage of High Frequency, Super High Frequency, and Electromagnetic Fields was seen to
be an efficient, economical, and safe method to remove the oil with high viscosity and ARPM content.

A High-Frequency emission generator is used to raise the temperature of the plug up to the melting point
of the paraffin wax and based on the deposit of wax, the power and frequency of the generator can be
monitored.

The walls of the pipe are designed as tubing and casing strings along with imperfectly conducting walls
with an annular space that is filled with a dielectric to absorb the EMF and convert it into thermal energy
which in turn melts the wax deposits.

The ARPM deposits can be found by the following equation

Where; - Real and imaginary parts of the dielectric constant;

- Cyclic frequency - Linear frequency;

- Temperature and Pressure

With the increasing duty cycle, for constant power of a High-Frequency generator emission, the time
required for melting the wax increases nonlinearly.

Heat Conduction equation assuming a completely clogged pipeline is given as follows

Where;

- Density, Thermal capacity, and Heat Conductivity of the medium

 3.2 AN ASSESSMENT OF THE C-S MEASUREMENTS

The effects of a thermal driving force, turbulence, and shear force were experimentally analyzed using
sample crude oil from the Gulf of Mexico. Under a wide range of Reynolds number and shear stress, 15
experiments were conducted with varying operating conditions.

It is the temperature gradient between the pipeline wall and crude oil which drives the n-paraffin contents
for the wax deposition. The current model to predict the wax-deposition is highly efficient for low or zero
shear stress, but highly uncertain in case of high shear stress. Oil System, Test Section, and Glycol System
collectively formed the experimental facility.

The equation derived to find:

The viscosity of oil:

Where;

Deposit mass:

Where;

is the wax mass deposited on the pipe; is the wax content obtained;

is the deposit thickness; is the initial pipe diameter

Based on the experimental shreds of evidence the following conclusions were drawn:

1. There will be an increase in pressure drop with the increase of deposition thickness.
2. Both shear stress and Reynolds Number are a responsible factor for the wax deposition.

Wax content increases linearly with the increase in shear stress while the deposit mass shows a decreasing
trend.
 3.3 CHEMICAL INHIBITORS

WAT is an important characteristic of the wax deposited on the inner surfaces of pipelines. Closely related
to the pour point, WAT is indispensable and needs to be lowered so that solidification of wax or the rate
of increase in its viscosity can be lowered. This is the job of chemical inhibitors. Chemicals that modify
WAT are called Wax Inhibitors. On the other hand, those which modify pour point are called Pour Point
Depressants (PPDs). Some chemical inhibitors modify the surface of pipelines by decreasing adhesive
forces between waxy liquid and pipe surface.

3.3.1 Sodium hypochloride and calcium chloride dihydrates

Sodium hypochloride is essentially used to soften wax by dissolution in water. A solution is pumped into
the pipe along with water. This produces enough heat to melt the solidified wax. The calcium chloride is
then added to break the molten wax into smaller pieces to improve the dissolution. It is to be noted that
the concentration of sodium hypochloride is kept small since it releases a small amount of chlorine that
can tend to damage the inner surfaces. However, while dissolving in water, it releases nascent oxygen
which is responsible for softening the wax.

3.3.2 Polymeric inhibitors

Polymeric materials may also be used extensively to reduce and treat wax deposition. Ethylene
copolymers and PEs are greatly used to and are still being studied for their contribution to reducing wax
deposition. However, is it known that polar polymers such as VA and MMA help reduce the crystalline
nature of wax and prevent its deposition. In addition to the existing industrially used polymers, comb
polymers are being studied and it is found that a matching average length of a comb polymer chain with
that paraffin distribution of crude provides the greatest PPD.

3.4 SURFACES AND CHEMICALS FOR COATING THE INNER PIPES SURFACES

Once treated, it is of utmost importance to prevent wax deposition since it impedes a good flow of crude
through the pipeline from the oil reservoir. Rather than going for several, regular checks and treatments
every month or year, it is a wiser option to modify the inner surface of the pipeline.

Polymeric materials such as polyvinyl can be coated on the inner surface. The polar nature of the polymer
reduces the adhesive forces between the wax particles and the material of pipe by increasing the magnitude
of cohesion within the wax itself. Hence, the wax does not stick to the pipeline.
Moreover, the material of the pipe chosen should have a minimum RR per feet. This is because the lesser
the roughness, the lesser is the friction factor. The low friction ensures a smooth flow of crude with lesser
chances of waxy fluid interacting with the surface.

With this knowledge, a creative approach would be to utilize PVC pipes. With the combination of polar
polymeric nature and bearing extremely less RR, PVC proves to be a great deal to help cut down on
treatment costs by reducing wax deposition to a great extent. However, due to strength and durability
reasons, PVC may be used at some locations throughout the pipeline network. In case this application is
insignificantly practical, proper insulation such as ceramic coating can be installed on the outer surface.
This reduces heat transfer to the atmosphere from the pipe and prevents wax particles from agglomerating
and solidifying on the surface.

3.5 DEGRADATION OF PARAFFIN WAX USING MAGNETIC FIELD: USE OF MAGNETIC

FLUID CONDITIONING

Crude oil in its liquid state can get supersaturated to a solid waxy form. It is required to create maximum
wax precipitation sites in the oil bulk. A magnetic field will help this formation by creating a greater
number of potential nucleation sites. For charged species in crude oil to become neutral, there are two
processes namely solvation and association into molecules.

The applied Magnetic field will favor the equilibrium direction towards solvation when the existing
equilibrium gets dissolved. Let Pbe be the population of solvated ions before equilibrium and Pae the
population of solvated ions after equilibrium then z

Pae > Pbee

An MFC reduces the conversion of liquid into solid by simply inhibiting the process of crystallization.
One reason why the solution gets converted to solid is because of the adhesion of the sticky paraffin
molecules with one another. This can be reduced if the surface tension is reduced. MFC reduces the cloud
point as well as the viscosity which lowers the rate of paraffin deposition as wax.

3.6 DEGRADATION OF PARAFFIN WAX USING MICROBIAL SUBSTANCES

As it has been discussed during this paper that chemical as well as mechanical possibilities exist to either
prevent or treat paraffinic wax. These may be however inefficient and a newer microbial approach is
proposed. Anaerobic thermophilic microorganisms can exist at lower oxygen levels and survive in
extremely high temperatures as well. Studies have been made with Geobacillus type TERI NSM and these
have proved to be extremely useful. The following degradation was observed:
 Component Percentage
Eicosane 97
Pentacosane 85
Triacontane 77

4. NOVELTY

1. The wax deposition is dominated by molecular diffusion, instead of Brownian diffusion. An

alternative to measuring the wax content in crude oil is by dissolving 2g crude oil sample in 50g
of hexane and separating the asphaltene content by using conc. sulfuric acid. After leaving this
solution for 2 hours, Ammonium Sulphate solution is used to remove the acid and wash the
solution with deionized water. Finally, by cooling the solution to -30 degrees with methylene
chloride and dry ice, it is sent into a vacuum filter. This filtered wax is dissolved in hexane and
then evaporated and dried to give wax crystals.

2. A combination of less relative roughness and polar polymeric nature makes substances like PVC a
great deal to be used for coating the inner surfaces of pipelines that transport crude from oil
reservoirs. Although it is highly impossible to construct the entire network length out of PVC, it is
very much possible to coat the inner surface at locations where the heat transfer rate is much
significant and higher. The polar nature reduces the adhesive forces between wax particles and pipe
surface and prevents it from sticking whereas greater smoothness ensures greater flow assurance
so that no waxy fluid’s flow is obstructed by the pipe surface.

3. This paper proposes a theoretical approach to the use of Thermobrachium celere. What makes
this class of anaerobic thermophilic bacteria fit for our purpose is the distinguishing
characteristics it shows. It can double its population within 10 minutes and is ideal for a pH above
9. This is highly suitable for crude which has a pH between 9 and 11. Strains of this bacteria can
withstand high temperatures as well. Strains of paraffinic wax degrading under the presence of
this bacteria will be compared and studied. The analysis will be made about their degradation
graphs.

4. Apart from wax removal, EM waves play a crucial role in enhanced oil recovery from the
reservoir. The heat energy generated from the EM waves is utilized to decrease the viscosity of
the oil and hence improve its mobility. Using EM waves with Gas Injection showed 45% more oil
recovery than the usual recovery technique.
 5. RESULTS

Chemical methods are experimentally proven to give better results than the conventional mechanical
processes. Solvents dissolve paraffin deposits, dispersants helps in breakdown of wax , and surfactants
solubilize the kinds of paraffin in oil. Significant results were obtained on treating crude oil with
inhibitors like diethanylamine to bring down the WAT to 10°C from 30°C without affecting the
viscosity of crude oil. Other inhibitors like methyl methacrylate, ethylene vinyl acetate have also
shown promising results. Another breakthrough result was obtained when Sodium Hypochloride and
Calcium Chloride Dihydrates were used as inhibitors. The dilution of Calcium Chloride releases heat
and when added along with Sodium Hypochloride will make the wax soft and with constant
stirring, the wax gets removed. Experiments prove that the chlorine and hypochlorous acid released
by the presence of sodium hypochloride is largely insignificant to cause corrosion in the pipeline.
Microbial organisms can be used to degrade the wax deposited and a magnetic field can be created for
degradation as well.

6. CONCLUSION

1. The heat energy released from the High-Frequency EMF has significant potential to melt the wax
deposits inside the walls of the pipeline.
2. The conducting walls have an annular space that is filled with a dielectric to absorb the EMF.
3. The time required for melting increases non linearly with an increase in the duty cycle for a constant
power EMF generator.
4. An increase in deposition thickness leads to an increase in pressure drop.
5. Wax deposition is affected by both Sheer Stress and Reynolds Number.
6. Usage of Sodium Hypochloride and Calcium Chlorite can efficiently soften the deposited wax.
7. Polymers such as Ethylene copolymers, polar polymers like VA, and MMA can essentially prevent
the deposition of wax.
8. PVC coatings on the inner walls of the pipeline have also found an application to prevent the
formation of wax on its walls during recovery.
9. The usage of a magnetic field maximizes the wax precipitation sites in oil bulk and also reduces the
surface tension of the crude oil.
10. Microbial substances like Geobacillus type TERI NSM have been extremely efficient to remove wax
deposition.
11. EM waves with Gas Injection shows 45% higher oil recovery than conventional recovery.
12. The wax deposition is dominated by molecular diffusion rather than Brownian diffusion.
13. Thermobrachium Celere has been consistent with the rapid rate of degradation of the wax deposition.
 7. NOMENCLATURE

ARPM Asphalt, Resin and Paraffin Matter

DSC Differential Scanning Calorimetry
MFC Magnetic Fluid Conditioning
MMA Methyl Methacrylate
PP Pour Point
PPD Polyvinyl Chloride
RR Relative Roughness
VA Vinyl Acetate
WAT Wax Appearance Temperature
WPT Wax Precipitation Temperature

REFERENCES

1. Sousa, A.L., Matos, H.A. & Guerreiro, L.P. Preventing and removing wax deposition inside
vertical wells: a review. J Petrol Explor Prod Technol 9, 2091–2107 (2019).
https://doi.org/10.1007/s13202-019-0609-x

2. Mohd Mustaffa, Norseri. (2010). Oil pipeline wax deposition inhibition using chemical methods.

3. Wax formation in oil pipelines: A critical review Ararimeh Aiyejina, Dhurjati Prasad
Chakrabarti, Angelus Pilgrim, M.K.S. Sastry b
http://dx.doi.org/10.1016/j.ijmultiphaseflow.2011.02.007

4. Wax Deposition and prediction in petroleum pipelines Fadi Alnaimat, Mohammed Ziauddin
https://doi.org/10.1016/j.petrol.2019.106385

5. DOI: 10.15593/2224-9923/2018.2.5 Cleaning the well from wax deposition by high-frequency

and ultra-high-frequency electromagnetic exposure Lenart M. Fatykhov

6. Experimental Study on Wax-Deposition Characteristics of a Waxy Crude Oil Under Single-Phase

Turbulent-Flow Conditions DOI: https://doi.org/10.2118/163076-PA Priyank Dwivedi, Cem
Sarica, and Wei Shang

7. Removal of Paraffin wax deposition by magnetic field Hasbullah, Nura thirah

8. SYUKRI HIMRAN, ARYADI SUWONO & G. ALI MANSOORI (1994) Characterization of
Alkanes and Paraffin Waxes for Application as Phase Change Energy Storage Medium, Energy
Sources, 16:1, 117-128, DOI: https://doi.org/10.1080/00908319408909065
9. Wax appearance temperature (WAT) determinations of different origin crude oils by differential
scanning calorimetry Mustafa VerşanKöka Mikhail A.Varfolomeevb Danis K.Nurgaliev

10. Determination of Wax Appearance Temperature (WAT) for Crude Oil and Petroleum Products
Using Differential Scanning Calorimetry (DSC)
https://www.tainstruments.com/pdf/literature/TA429.pdf

11. Shirsendu Banerjee, Ravindra Kumar, Afzal Akhtar, Rajesh Bairagi, Ajay Mandal & Tarun
Kumar Naiya (2017) Effect of pour point depressant on wax deposition and drag reduction in
horizontal pipelines, Petroleum Science and Technology, 35:6, 561-
569, DOI: https://doi.org/10.1080/10916466.2016.1269128