OILFIELD CHEMICALS

TRAINING MANUAL
PART 7

7.

ASPHALTENES

7.1

Problem

While both paraffin and asphaltenes are often referred to as wax, they are actually quite
different. When asphaltenes are present in crude oil, they can cause severe processing
problems at any point - from the formation to the refinery.

Downhole
In addition to plugging pumps and tubing, precipitation of asphaltenes can result in
restricted flow in the well bore or even the formation itself. Depending on where they
form, the black, sometimes coal-like deposits can plug tubing or cause considerable
formation damage.

Surface Equipment
Once oil is produced, the asphaltene problem can continue. By collecting at the oilwater interface of surface equipment, such as free-water knockouts and heater
treaters, asphaltenes contribute to the formation of stable, ragged emulsions that make
oil-water separation extremely difficult. Asphaltenes sometimes fall to the bottom of
treaters, contaminating discharged water. This contaminated water may pose a
difficult disposal or injection problem. Asphaltene deposition in stock tanks lowers
volume capacity and sometimes builds to a level which can compromise the discharge
line.

Pipelines
Asphaltene deposits can also restrict flow or cause plugging in pipelines carrying high
asphaltene crudes. Though easier to reach than tubing strings, pipelines are still
difficult and expensive to clean.

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Asphaltenes

7.2

Asphaltene Composition

Petroleum asphaltenes are best defined as a solubility class of the heavy components in crude
oil that are insoluble in a none polar solvent such as pentane. Paraffin, saturates and
aromatics are soluble in pentane.
Both the structure and chemistry of asphaltenes differ from paraffins:

7.3

Asphaltenes are large complex aromatic structures with no exact composition.

Although the exact structure of asphaltenes is unknown, experimental data provides
possible structures (Figure 7A-1).

Asphaltenes have molecular weights up to several thousand.

They are complex polar macro-cyclic molecules that contain carbon, oxygen, sulfur
and possibly metals.

Asphaltenes are present in crudes as colloidal micelles, that is, clusters of asphaltene
molecules (Figure 7A-3).

Resins (Figure 7A-2), which are the lower molecular weight precursors to
asphaltenes, act to stabilize the asphaltene micelles. Crudes with high resin content
are more stable.

Under stable reservoir conditions the asphaltenes, resins, maltenes and the oil are in a
thermodynamic equilibrium (Figure 7A-3). When this equilibrium is disturbed and
the resins are disassociated from the asphaltenes, flocculation of the asphaltenes often
occurs (Figure 7A-4). It is the flocculated asphaltenes that cause the production
problems.

Mechanism of Flocculation and Deposition

Like asphaltene structure, the mechanism of asphaltene deposition is complex and difficult to
define. Asphaltene precipitation is strongly influenced by the interaction between
asphaltenes and other components of the oil. Asphaltenes are most commonly thought to
occur in the form of a colloidal dispersion, however, they tend to cluster into aggregates.
Asphaltenes form by a different mechanism than paraffinic deposits. Chemical, mechanical
or electrical action can depolarize asphaltene micelles.
7.3.1 Chemical
The peptized asphaltenes exist in an equilibrium. This equilibrium can be shifted when the
chemical composition of the crude changes. The depeptized micelles flocculate, causing
precipitation of asphaltene deposits.
The chemical composition of the crude oil can change when:

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Asphaltenes

Crudes are Mixed - This can upset the delicate balance between the resin/asphaltene
ratio or the polar to non-polar ratio.

Miscible Floods - Miscible solvents tend to be non-polar (CO2, C4 - C6). These nonpolar solvents strip the stabilizing agents from the asphaltene causing asphaltene
precipitation.

Pressure Falls Below the Bubble Point - When the pressure falls below the bubble
point, the gases that were in solution are now in a separate phase. This change will
effect the equilibrium of the stabilized asphaltenes.

Acid - Acid and asphaltic crude are incompatible. Great care must be given on
asphaltic crudes during well completion and stimulation.

7.3.2 Mechanical
Shear can cause physical change in the crude composition in two ways:

Since the resin or peptizing components of the crude are in a loosely associated
equilibrium with the asphaltenes in the crude, they can be physically stripped from the
asphaltene causing flocculation, or the asphaltenes can be stripped from the peptizing
agents where they contact each other and coalesce.

Under certain conditions shear/turbulent flow can cause micro-location pressure

drops. This can have the same effect on asphaltene stability as a bulk pressure drop.
Even though the pressure drops are temporary, problems can still occur because the
process of asphaltene flocculation is generally irreversible.

Pressure and temperature changes can also change the delicate equilibrium of the peptizing
agents and asphaltenes.
7.3.3 Streaming Potential (Electrical)
Asphaltenes are polar and generally are weakly charged. These charges act as stabilizing
forces. As the charged asphaltic particles flow over a surface a streaming potential can be set
up, disturbing the electrical forces and causing aggregation and flocculation of the
asphaltenes. The streaming potential can occur in the formation, flow lines, pipelines, etc. It
is expected that surface type plays a role in streaming potential.
It is generally believed that streaming potential is a function of the flow regime, pipe wall,
conductivity, physical properties of the crude, and electrical properties of the asphaltene.
Temperature also plays a major role. The streaming potential is directly affected by the
diffusivity of the asphaltene particles to the surface, so flow can also play a major role.
Pipe surface plays a major role. A very rough surface may be sufficient to initiate the
deposition process and trigger simultaneously the effect of other phenomena. Wax also plays
a role on the surface. Wax crystals on a pipe surface can act as a nuclei about which
asphaltene particles deposit.

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Asphaltenes

7.4

Treatment Methods

Asphaltene deposits are hard, brittle, dark black, dry solids which have a tendency to adhere
to metal. Heat does not melt them; they must be removed by mechanical cutting and/or by an
aromatic soak.
7.4.1 Physical Removal
Asphaltene deposits can be physically removed by:
1. wireline cutting
2. pigging
3. hydroblasting
4. drilling
7.4.2 Solvents
Solvents effective in asphaltene treatment are aromatic like toluene, xylene, heavy aromatic
naptha, and others including aromatic aliphatic blends.
For downhole asphaltene deposits, solvent soaks are done using aromatic solvents and/or
aromatic solvents blended with dispersants. Also these solvents and/or solvent dispersants
can be recirculated in the well.
Solvent soaks can also be used in asphaltene remediation in tanks and other surface
equipment.
Solvents used in conjunction with pigging operations are an effective method of removing
asphaltene deposits in pipelines.
7.4.3 Dispersants
Dispersants can be applied using batch or continuous methods. Dispersants help the
flocculated asphaltene remain dispersed in the oil.
7.4.4 Asphaltene Inhibitors
Because asphaltene deposition does not occur until after flocculation, a new class of
polymeric dispersants was developed that act as asphaltene inhibitors, stabilizing the
aspahltenes and preventing flocculation. It is widely believed that these asphaltene inhibitors
act in the same manner as the resins and maltenes; interacting with the asphaltenes and
stabilizing the asphaltene micelles in the crude oil. These asphaltene inhibitors have a
stronger association with the asphaltenes than the natural resins and maltenes and are able to
stabilize the asphaltenes through greater changes in pressure, temperature, shear and chemical
environment. It is important that these asphaltene inhibitors are added to the crude oil before
the asphaltenes become destabilized and flocculation occurs.

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Asphaltenes

Conventional asphaltene inhibitor treatment techniques involve continuous treatment by

means of a chemical pump at the wellhead either downhole through capillary tubing, or by a
slip-stream. Although these methods are effective at preventing flocculation and deposition
of the asphaltenes in the tubing, flowlines and in surface equipment, they do nothing to
prevent deposition of asphaltenes in the near-wellbore area. The reason for this is that the
chemical is spotted in the oil after the oil leaves the formation and is not placed in the
formation where it can stabilize the asphaltenes before they deposit and damage the nearwellbore area. In a similar manner, the bottom hole pump is often not protected because
there is not enough mixing of the chemical into the crude oil to stabilize the asphaltenes
before the crude is lifted, thus allowing the asphaltenes to deposit in the pump. In order to
solve the inefficiencies in these chemical treatment methods, the chemical needs to be placed
in the crude before the point of flocculation. This requires adding the chemical to the crude
while it is still in the formation. This can be accomplished by squeezing the asphaltene
inhibitor into the formation.

7.5

Asphaltene Test Methods

Asphaltene inhibitors can be screened using the Asphaltene Dispersant Test (ADT).
The ADT procedure is shown on the following page.

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Asphaltenes

Asphaltene Dispersant Test (ADT)

The following ADT procedure will allow the OFC Sales Representative to perform a field
screening of asphaltene content and efficacy of asphaltene dispersants, and demonstrate this
performance to customers. It is intended as a general procedure to probe the presence of
asphaltenes and their tendency to precipitate (asphaltene screening), and the relative efficacy of
various dispersants and solvents (ADT). It may be most useful in determining at what point in a
system asphaltenes become destabilized, particularly with combinations of crude streams, and the
best relative application for the asphaltene dispersant.
Asphaltene content (%) is not the only factor affecting deposition in the application, as crudes
may vary greatly in the natural stability of colloidal asphaltenes by resins. System parameters
such as temperature and pressure cannot be addressed in this method. Similarly, observed
volumes of sediment in this test do not directly relate to % asphaltenes in the crude and effective
dosages of product, as the appearance is also affected by particle size of precipitated asphaltenes.
This method is intended as a qualitative tool to indicate relative tendencies for precipitation or
dispersancy, more than absolute values.
Several methods exist where asphaltenes are precipitated from the crude before testing. Research
indicates, however, that the characteristics of the asphaltene/resin properties may by altered by
isolation. Therefore, crude oil samples diluted 50/50 in toluene (asphaltenes are soluble) are
preferred. Deposits may be dissolved as 10% solutions in toluene.
Equipment
12.5 ml centrifuge (grindout) tubes
Centrifuge tube rack
Eppendorf or Drummond pipette (100 l)
Solvents: hexane, toluene
Timer
Sample Preparation
Crude: Prepare a sample of dry oil in toluene (50/50). Residual emulsion must be broken. In
many cases it will be sufficient to dilute the crude 50/50 with toluene and let stand before
centrifuging, separating water and solids from the crude solution to be used for testing. Heat and
emulsion breaker can be applied if necessary.
Deposits: Soak the deposit in a sufficient volume of toluene to give a 10% solution. Paraffins
and asphaltenes should dissolve; inorganic solids remain.

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Asphaltenes

Asphaltene Screening (Blank)

1. Add 12.5 ml of hexane to each of our centrifuge tubes (fill to 100% mark).
2. Dose the hexane with the desired amount of crude oil/stock solution. Typically, the
following dosages are chosen: 50, 100, 200 and 300 l. Use an Eppendorf or Drummond
pipette to accurately measure the crude oil solution.
3. Shake vigorously for 60 seconds.
4. Allow the tubes to stand for one hour. Observe and record percent sedimentation due to
gravity. Notice that as the amount of crude oil in the hexane increases, the amount of
precipitate also increases, and the supernatant solution gets darker.
To determine the volume of crude for dispersant screening, observe the volume of untreated
crude solution that gives between 4 and 10% sediment.
Note: If more than 300 l of crude solution are required to give 4% precipitate, this indicates
that asphaltenes are not present, or that they are naturally well stabilized in the crude.
ADT Procedure
1. Add the desired amount of dispersant to each tube. Typically, the following dosages are
chosen: 0 (blank), 10, 50, 100 and 200 ppm. For some crudes, such as California, up to
1,000 ppm of dispersant may be required.
Note: Prepare 1.25% (v/v) solutions of dispersant in toluene. This makes dosing the tubes
easy:
10 l = 10 ppm
2. Fill to 100% mark (total volume 12.5 ml) with hexane and mix.
3. Add sufficient crude oil or asphaltene solution to the hexane so that the blank gives between
4 and 10% sediment (volume determined above). This typically requires about 100 l. Use
the Eppendorf pipette to dose the tubes.
4. Shake vigorously for 60 seconds.
5. Allow the tubes to stand. Observe and record present sedimentation due to gravity after 15
minutes and 60 minutes. Calculate the % dispersion from the volume of sedimentation in the
treated sample ( S treat ) and blank ( S blank ).
% Dispersed = 100 x [(S blank S treat ) / S blank

Notice that as the amount of dispersancy increases, the amount of precipitate decreases and
the supernatent solution gets darker.

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Nalco/Exxon Energy Chemicals, L.P.

APPENDIX

CH3
CH3

CH2

CH2 - (CH2)4 - S - (CH2)4 - CH2

H3C

H3C
N

CH2 - CH2 - CH3

CH3 C2H5
CH3

CH3

H3C
CH2
S

Ni+2

CH3
CH3

CH2

CH2 - (CH2)4 - S - (CH2)4 - CH2

H3C

H3C
N

CH2 - CH2 - CH3

CH3 C2H5
CH3

CH3

H3C
CH2
S

Figure 7A-1

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APPENDIX

Resins

Figure 7A-2

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Figure 7A-3

alphatics

mixed naphthenics alphatics

mixed aromatics naphthenics

LMW aromatics

HMW aromatics

asphaltenes

APPENDIX

Nalco/Exxon Energy Chemicals, L.P.

February 6, 1998

Figure 7A-4

alphatics

mixed naphthenics alphatics

mixed aromatics naphthenics

LMW aromatics

HMW aromatics

asphaltenes

APPENDIX

Nalco/Exxon Energy Chemicals, L.P.