Oilfield Paraffin /Asphaltene

Paraffin Asphaltenes and Inhibitors

Paraffin control products prevent crude oil precipitation of paraffin wax deposits in production risers,
subsea tie-backs, or any other production tubular or transportation pipeline.
Some formulation products are wax crystal modifiers that prevent paraffin formation by interfering with
the bonding of aliphatic wax molecules. Composed of branched chain polymers, these modifiers bond to
the wax crystal lattice at an active growing site but prevent further growth and interfere with deposition
by disrupting the lattice structure.
Although the paraffins remain unstable in solution, they are prevented from growing crystals of
adequate size to block production lines; hence production is not impeded even for temperatures below
the wax appearance temperature (WAT).
Wax crystal modifiers are applied continuously in the production stream for uninterrupted paraffin
control. In pumping wells with low to moderate fluid levels, frequent batch treatments can approximate
a continuous injection treatment. Similarly, a continuous supply of chemical can be provided by
feedback from a formation squeeze treatment.

Paraffin Deposition...
Crude oil is a complex substance formed under high pressure and temperature from vegetable and/or
animal organic materials. A broad spectrum of organic chemical components exist in light, paraffinic
and heavy oils. These include wax up to C60, esters, organic acids, asphaltenes and napthalenes.
Depending on the makeup of these components, the crude oil will have its own characteristics, including
specific gravity, wax content, pour point, color, etc.

Crude oil can cause a series of problems:

Wax deposition
Viscous gels at low temperatures (from heavy oils)
Deposition of asphaltenes

North Sea oil Texas oil Utah oil

Paraffin consists of straight and branched chain hydrocarbons of varying lengths; they are part of the
chemical family called alkanes. Paraffin wax molecules contain between 20 to 80 or more carbon atoms
in their chain and have a definite melting point. Paraffin waxes often make up 60-90% of a wax deposit.
Soft deposits are composed of molecules containing from CI, to C,5 carbon atoms, their melting points
are below 150F. The high molecular weight waxes are referred as microcrystalline waxes and are similar
in chemical structure to the normal paraffin waxes but have a much higher melting point. (150 to 212F).
Paraffins are aliphatic hydrocarbon waxes that are present in most crude oils. They precipitate from a
crude oil at the point where the temperature falls below the WAT.
These deposits reduce the internal diameter of tubulars and pipelines, restrict or block valves, and
impede other production equipment to reduce capacity and, in the worst case, stop production.

Factors Influencing Paraffin Deposition:

Paraffin wax is primarily a solid liquid phase equilibrium phenomenon; the lowering of temperature
is the significant driving force for precipitation. Crude oil is made up of many different properties and
freeze points. As the temperature falls below the freeze point of a hydrocarbon, it falls out of solution.
The harder waxes deposit first, followed by the softer waxes as the temperature drops.
Hydrocarbon density - paraffin waxes are increasingly soluble in lighter gravity, low molecular weight
hydrocarbons.
Solution gas - as oil losses light ends it becomes more dense, and paraffin solubility decreases. The
light end losses usually occur at pressure drops, which cause the release of the volatile hydrocarbons,
which are good solvents for paraffin wax.
Rough surfaces provide sharp edges, which promote the deposition and agglomeration of wax.
Suspended solids also provide surfaces for wax to adhere to and start accumulating.
Water cut - as the water cut increases in a system it affects the temperature, water carries and retains
more heat than oil does. The water reduces the tendency for wax to deposit by increased velocity and
water wetting surfaces.

Asphaltene Deposition
Asphaltenes are probably the least understood deposits occurring in the oilfield. They are a complex
organic material that are thought to be arranged in stacked, multi-ring structures. They contain
nitrogen, oxygen' and sulfur atoms within the repeating unit.

Asphaltenes have a wide variety of potential structures and vary from reservoir to reservoir.
Asphaltenes are not truly soluble in most crude oils. They exist as 35 to 40 micron sized platelets
and are maintained in suspension by materials called maltenes and resins. These smaller similar
suspending molecules are soluble and act in what has been described as a micelle-type
arrangement to keep the asphaltic products in suspension. When stabilizing influences are
removed the asphaltic particles coalesce into larger groups, called flocs, which separate from
the oil. Asphaltene precipitation will occur with the addition of low molecular weight alkanes,
like pentane, hexane, and heptane, and are soluble in aromatic hydrocarbons, like xylene and toluene.

Typical molecule structure of an asphaltene molecule.

Factors Influencing Asphaltene Deposition
Rich gas flooding causes destabilization by lowering the carbon to hydrogen ratio. Stripping gas from
the oil has been shown to improve the solubility of the asphaltenes.
The lowering of pH interrupts solution equilibrium and can cause a destabilization of the asphaltene.
This may be caused by CO mineral acid or naturally occurring organic acid. This can cause asphaltene to
deposit in the well bore and pumps.
Mixing of crude and/or condensate streams can cause a shift in pH or change the ratio of light
hydrocarbons. Another example is the mixing of a paraffinic oil or condensate with an asphaltenic one.
Incompatible organic chemicals, like isopropyl alcohol, methyl alcohol, acetone, and even some glycol,
alcohol or surfactant based mutual solvents that do not have an aromatic component can selectively
wet or attract maltenes and resins and cause the precipitation of asphaltenes.
The effect of pressure drop and shear on asphaltene behavior may be to shift the tendency to
precipitate asphaltene, similar to a change in equilibrium. Turbulence also has impact on increasing
asphaltene precipitation. Asphaltene deposits are frequently found downstream of chokes, liner
slots, valves, and vessels.
Temperature drop - this may have more to do with indirect destabilization of the solubility of
maltenes and resins or may cause paraffin precipitation, which traps some asphaltenes as it solidifies.
Temperature can also be affected by pressure drop.

Paraffin / Asphaltene Comparison

Paraffin
Straight and branched chains
Definite melting point
Cloud point indicates crystal initiation
Soluble in crude oil
Pour Point - no flow of oil due to wax
Carbon number's C12 to C66+
Asphaltene
Friable solids
No definite melting point
Swell and pop when heated
Aromatic rings
Decompose to coke material
Stabilized by resins and maltenes
Not soluble in crude oil
Contain nitrogen, oxygen and sulphur

Impact of Paraffin / Asphaltene Deposition

The impact of paraffin/asphaltene deposition is very severe and it can increase operating costs as well as
reduce well and system productivity. Examples of the impact are as follows:
Plugging of perforations and near well bore damage resulting in a decline in reservoir
productivity.
Increased lifting costs from down hole pump maintenance, etc.
Pressure increases in flow lines and wells resulting in higher operating costs.
 Deposition and plugging of production tanks resulting in a difficulty of meeting BS &W
requirements.
Pipeline blockage and increased transmission costs.

Wax is present in most crude oils, usually in quantities of less than 5%, but even this much can still cause
problems. Wax can be detected by normal analytical methods (IP) and usually represents that fraction of
the oil with a carbon number higher than 18. Wax is formed when the oil is cooled as a result of being
produced from the well.
Subsea pipelines
Heat exchange
Joule effect
Gas lift (change in solubility)

The wax crystals are formed at a specific temperature (wax appearance point), and then they become so
big that they deposit on the surface and block the pipes or process equipment.

Deposit Identification
Paraffin
If it melts above l22'F
If it floats on water
If it dissolves in hot xylene
Asphaltene
If it doesn't melt but dissolves in
hot xylene.
Solids (scale, iron sulfide, sand,
mud, etc.)
Solids
If it doesn't melt
If it doesn't dissolve in hot xylene
If it sinks in water

If the above testing shows that the sample is a solid sample - not a hydrocarbon, place the deposit in a
hydrochloric acid solution and observe for the following:
If acid bubbles or effervesces without sour odor and remains colorless, it is probably
calcium carbonate.
If it turns yellow, it is probable iron carbonate or iron oxide (rust). In pure form, iron
carbonate is grey and iron oxide is red-brown to black.
If acid bubbles or effervesces with sour odor and remains colorless, it is probably lead or
zinc sulfide.
If it turns yellow, it is probably iron sulfide

If there is no reaction in hydrochloric acid, break up a new scale sample and cover with calcium sulfate
converter.
If sample swells and becomes fluffy, it is probably calcium sulfate.
If there is no reaction, the scale is either, barium sulfate, strontium sulfate, sand, dirt, clay, mud,
bacteria, slime, or colloidal sulfur.

Customized Response

Proper treating recommendations for cost-effective paraffin control are complicated by differences in
produced oil characteristics, variations in system operating conditions and the wide variety of treatment
chemicals available for use.
Selection of the proper chemical and treating method, particularly for continuous injection or squeeze
applications with crystal modifiers, should be based on laboratory and field-testing.
Equally important is expert analysis to quickly determine the key treatment parameters and select the
appropriate paraffin control formulation. Once selected and applied, representatives monitor the
treatment program to maintain effectiveness and avoid reoccurring problems.
Many chemical industry-leading capabilities in tailored field service and project-specific product
formulation make these types of products a highly effective, economic solution for prevention of
paraffin wax deposits.

Paraffin and Asphaltene Dispersants and Solvents

Products for Paraffin and Asphaltene Control in the Oilfield

Paraffins and asphaltenes are commonly-occurring components of crude oils, which have the potential
to seriously interfere with production and in many cases, shut it down entirely. Asphaltenes are large
aromatic agglomerates composed primarily of heterocyclic rings. Held in solution in crude oil by
naturally occurring petroleum resins that adhere to the outer surface of the asphaltene agglomerate,
they will precipitate and deposit in your production system in locations where pressure drops allow the
resins to desorb. Paraffins are saturated hydrocarbon waxes that will precipitate and deposit in areas
where your production systems temperature falls below the solubility temperature of the paraffins,
known as the Wax Appearance Temperature (WAT). Like asphaltenes, paraffins can block a production
system and completely stop production.
In locations where paraffins or asphaltenes have already deposited in a system, remedial treatment is
necessary for their removal. Many lines of paraffin and asphaltene dispersants and solvents offer the
capability to remove these deposits and restore a production system to its designed capacity. Some
solvents remove paraffin and asphaltene deposits when used in batch treatments by simply dissolving
the deposits, while dispersants contain oil soluble surfactants that break up the paraffin or asphaltene
deposit and disperse it in the oil.
While many products can be used in continuous injection applications to control deposition of waxes
and asphaltenes, the normal procedure is to remove existing deposits through batch treatment. The
volume of chemical and frequency of treatment required for batch treatments will depend primarily on
the severity of the problem. Once existing paraffin and asphaltene deposits are removed, continuous
injection treatment provides a cost-effective approach to maintaining a system with no production-
inhibiting deposits.
Proper treating recommendations for cost-effective control of paraffins and asphaltenes are
complicated by the differences in characteristics of the produced oil, variations in system operating
conditions and the wide variety of chemicals available for use. Selection of the proper chemical and
treating method should be based on laboratory and field-testing. Focus on custom-tailored product
formulation and project-specific field service make these types of products the go-to tool for removal
of paraffin and asphaltene deposits, restoring the production capacity of the customers assets and
enhancing their bottom line.

Wax inhibitors modify the structure on the growing wax crystal, either by co-crystallization or by
absorption to the surface of the crystal. Further growth will then be stopped.