Paraffin and Asphaltenes in Crude Oil

There are three main groups of compounds:

1) Saturated hydrocarbon of paraffin
2) Aromatic hydrocarbons
3) Resins and asphaltenes

The table above shows the composition of crude oil, tars and bitumens obtained from various
sources. This proven that crude oils contain substantial proportions of saturated and aromatic
hydrocarbons with relatively small percentages of resins and asphaltenes. To the degraded
crudes, including tars and bitumens, contain substantially larger proportions of resins and
asphaltenes.

Paraffin Deposition
Paraffins are high-molecular-weight alkanes (C20+) that can build up as deposits in the wellbore,
in feed lines, etc. These organic deposits can act as chokes within the wellbore, resulting in a
gradual decrease in production with time as the deposits increase in thickness. This can result
in producing problems unless some remedial action is taken on a systematic and periodic basis.
Deposits vary in consistency from soft accumulations to hard, brittle deposits. Usually the
deposits are firmer and harder as the molecular weight of the paraffin deposits increases.
Sometimes paraffin and asphaltenes occur together in organic deposits.

Loss in solubility in the crude oil is the primary cause of wax or paraffin deposition. The changes
in temperature, pressure or composition of the crude oil as a result of loss of dissolved gases in
which this resulted to the loss of solubility. Paraffins that have the highest melting point and
molecular weight are usually the first to separate from solution, with lower-molecular-weight
paraffins separating as the temperature decreases further. For example, a C60 alkane with a
melting point of about 215F will deposit at a much higher temperature than a C 20 alkane with a
melting point of 98F.
The ability of the crude oil to hold the paraffin in solution is generally quantified with two
indicators:

Pour point

Cloud point

The procedure for measuring the pour point and cloud point may be found in ASTM manuals
(D2500-66 for cloud points and D97-66 for pour points). The cloud point is defined as the
temperature at which paraffins begin to come out of solution and a clear solution of
hydrocarbons turns cloudy. Obviously, it is difficult to measure the cloud point for dark crude oil,
because cloudiness is not visible. In such cases, the presence of paraffin crystals may have to
be detected with a polarizing light microscope. The pour point is defined as the temperature at
which the crude oil no longer flows from its container. As the temperature is lowered, wax
crystals form an interlocking network that supports the hydrocarbon liquid within it. This network
of paraffin crystals is quite shear sensitive and loose when first formed but can harden and
become extremely rigid as fluid is lost from it. Pour points are relatively easy to measure in the

field and provide a good indication of conditions under which large quantities of paraffin will fall
out of solution in crude oils.
The most common cause of loss of solubility of the paraffin in the crude oil is a decrease in
temperature, which may occur for a variety of reasons:
1) Cooling produced by the crude oil and associated gas expanding through the
perforations
2) Gas expansion while lifting fluids to the surface
3) Radiation of heat from the tubing to the surrounding formation induced by intrusion of
water into or around the wellbore
4) Loss of lighter constituents in the crude oil because of vaporization
Several other possible reasons for a decrease in temperature can be envisioned. In offshore
installations, for example, paraffin problems are usually associated with the rapid change in
temperature as the crude oil from the wellbore enters subsea pipelines that are immersed in
seawater at 4C. Large volumes of paraffins can be deposited on the surfaces of the pipelines,
which requires periodic pigging.
Pressure itself has little or no influence on the solubility of paraffin in crude oil. However, it does
have a significant impact on the composition of the crude oil. Reductions in pressure usually
lead to loss of volatiles from the crude oil and can induce the precipitation of paraffins. This is
the primary reason why paraffin problems are more common in the more mature regions of the
world. As the reservoir pressure is depleted and the lighter components of the crude oil are
produced in preference to the heavier fractions, the likelihood of paraffin precipitation is
significantly increased.
For paraffin deposition to be a significant problem, the paraffin must deposit on the pore walls or
the tubing surface. If the paraffin remains entrained in the crude oil, it usually offers few
production problems. Several factors influence the ability of paraffin to deposit on the pipe walls:

Presence of water wetting the surfaces of the pipe tends to inhibit paraffin deposition. In
addition, water has a higher specific heat than oil, which increases flowing temperatures.

Pipe quality plays an important role. Rusty pipes with large surface area and numerous
sites for paraffin crystal formation offer an ideal location for paraffin deposition. Paraffin
adheres to rough surfaces better than smooth surfaces.

Temperature profile in the near-wellbore region or within the pipe plays an important role
in determining whether the paraffin will deposit on the walls or will continue to be
entrained with the fluid.

Removal of Paraffin Deposits

Paraffin accumulation are removed by methods that can be categories into three:
1) Mechanical removal of paraffin deposits
2) Use of solvents to remove paraffin deposits
3) Use of heat to melt and remove the wax
Mechanical methods means we used scrapers, knives and other tools are most commonly used
to remove paraffin deposits in the wellbore. They can be very effective and are relatively
inexpensive.
The most common solvent used to remove paraffin from tubulars and the near-wellbore region
is crude oil. Hot oiling is the least expensive method, commonly used on stripper wells to
remove paraffin deposits. Lease crude taken from stock-tank bottoms is heated to temperatures
of 300F or more. This heated oil is then injected or gravity fed into the tubing or annulus (more
common). The high temperature induces solubilization of the paraffin deposits in the injected
crude, which is then produced back to the surface. Hot oiling has been used successfully to
remove paraffin deposition, but can result in formation damage. The use of hot salt water to melt
the paraffin may be a safer approach.
Solvents, both organic and inorganic, have been used in the past. These include crude oil,
kerosene, diesel, and surfactant formulations that can solubilize the paraffin. Organic solvents
that consist of a blend of aromatics are usually used to remove mixtures of paraffin and
asphaltene deposits. However, the cost of such treatments can be significantly higher than that
of hot oil or water treatments.
Steam has been used in a number of cases in which severe paraffin problems have resulted in
plugged tubulars. The lack of solubility of paraffin in hot water necessitates the use of
surfactants with steam or hot water so that the melted paraffin can be removed.

Crystal modifiers
Paraffin-crystal modifiers are chemicals that interact with the growing crude-oil waxes by
cocrystallizing with the native paraffin waxes in the crude oil that is being treated. These
interactions result in the deformation of the crystal morphology of the crude-oil wax. Once
deformed, these crystals cannot undergo the normal series of aggregation steps. Types of
paraffin-crystal modifiers include:

Maleic acid esters

Polymeric acrylate and methacrylate esters

Ethylene vinyl acetate polymers and copolymers

Dispersants
Dispersants act to keep the wax nuclei from agglomerating. Dispersants are generally
surfactants and may also keep the pipe surface water wet, minimizing the tendency of the wax
to adhere. Some water production is required, of course. High levels of water alone may
maintain the system in a water-wet state. As with scale prevention, a smooth surface tends to
decrease wax adherence. However, the operational problem is to maintain such a surface for an
extended period of time. Various forms of erosion are highly detrimental.
Obviously, these inhibitors must be delivered into the crude oil at temperatures above the WAT.
This need not cause a problem for surface equipment, but it could cause a problem for wellbore
treatment, if the bottomhole temperatures are low.

Methods for preventing paraffin deposition

Several mechanical adjustments can be made in the production string that can minimize the
likelihood of paraffin deposition. In general, these steps are designed to minimize the cooling of
the crude oil as it is produced to the surface. This can be accomplished by designing pumping
wells or tubing sizes and gas lift systems that maximize the flow of oil to the surface and
minimize the heat lost to the surrounding formations. Use of more expensive methods such as
plastic coatings on tubulars and electrical heaters is severely limited by economics.
Paraffin inhibitors are a class of compounds that consist of crystal modifiers that prevent the
deposition of paraffin onto pipe surfaces. These surface-active materials retard paraffin
deposition by inhibiting the adhesion of paraffin to sites on the tubing walls. Surfactants used in
these applications include wetting agents, dispersants, and crystal modifiers. Each of these
chemicals needs to be tested for a specific crude oil to evaluate its effectiveness.
Asphaltene precipitation
High-molecular-weight constituents of crude oil containing nitrogen, sulfur, and oxygen (N, S,
and O) compounds are referred to as asphaltenes. This broad class of compounds is clearly not
hydrocarbon because these compounds contain a large portion of heteroatoms in their
structure. Lower-molecular-weight NSO compounds are referred to as resins. The separation of
crude oil into resins and asphaltenes and other constituents is based primarily on solubility.
Asphaltenes and resins are generally defined as the pentane-insoluble fraction of the crude oil.
The average molecular structure of an example asphaltene fraction from a crude oil from
Venezuela is shown in Fig. 1.

Fig. 1Cross-sectional view of an asphaltene model based on X-ray diffraction. Zigzag

line represents configuration of a saturated carbon chain or loose net of naphthenic
rings; straight line represents the edge of flat sheets of condensed aromatic rings.

It consists primarily of condensed aromatic rings associated with aliphatic tails. The polynuclear
aromatic rings associate with each other through their electron systems to form clusters of
stacked rings, as shown in the figure. In crude oils, these asphaltene structures are dispersed
and maintained in suspension by the action of resins. If sufficient quantities of resin molecules
are present in the crude oil, the asphaltenes remain dispersed and in solution. However, the
addition of large quantities of alkanes or removal of the resin fraction can result in a loss of
solubility because the asphaltene molecules associate with each other, forming large
aggregates or micelles, and precipitate out. These micelles or aggregates are visible under
optical microscopes as dark, solid aggregates. Precipitation of asphaltenes occurs through the
formation of such aggregates. The solubility of asphaltenes is therefore a function of
temperature, pressure, and the composition of the crude oil. Any action that affects the
compositional balance of the crude oil can affect the ability of the oil to maintain the asphaltenes
in solution.
A very common example of the change in composition of a crude oil is what occurs during
pressure depletion in a reservoir. As shown in Fig. 2, the solubility of asphaltene is a minimum
at the bubblepoint pressure. This has important consequences for predicting where asphaltene
precipitation will occur in a reservoir. As the reservoir is depleted and the bubblepoint pressure
is achieved lower in the tubing or even in the formation itself, the possibility of asphaltene
deposition occurs at these locations. Indeed, in studies published in the literature, the location of
asphaltene deposition is observed to move from the top of the tubing to the bottom and into the
reservoir over a period of time as the reservoir pressure is depleted and the location where the
bubblepoint pressure is reached moves further out toward the reservoir.

Fig. 2Pressure dependence of asphalt solubility for a North Sea crude oil showing the
possibility of asphalt deposition in the well tubing.
Asphaltene deposition can also be induced by changes in composition of the crude oil through
injection of fluids such as CO2 or lean gas. Several studies have documented the possibility of
asphaltene precipitation during lean gas and CO 2 injection. Large changes in temperature can
also induce asphaltene deposition. In such cases, deposits of paraffin and asphaltene are
commonly observed together. The asphaltene particles frequently act as nucleation sites for
paraffin crystals.
Removal of asphaltene deposits
Removal of asphaltene deposits also requires the use of solvents or mechanical devices.
However, the solvents used for asphaltene removal are quite different from those used for
paraffins. Because asphaltenes are soluble in aromatic solvents, mixtures of aromatic solvents
such as xylene have been used to remove asphaltene deposits. It should be noted that solvents
such as diesel and kerosene that are primarily straight-chain alkanes should not be used
because they may induce asphaltene precipitation.