PAPER 2009-037

Effect of Pressure and CO2 Composition

Changes on Distribution of Asphaltene
Molecular Weight in Heavy Crude Oil
M. SADEQI MOQADAM, H. FIROOZINIA, R. KHARRAT, M.H. GHAZANFARI
Tehran Petroleum Research Center, Petroleum University of Technology

A.R. ALAMATSAZ
University of Calgary

This  paper  is  accepted  for  the  Proceedings  of  the  Canadian  International  Petroleum  Conference  (CIPC)  2009,  Calgary, 
Alberta,  Canada,  16‐18  June  2009.    This  paper  will  be  considered  for  publication  in  Petroleum  Society  journals. 
Publication rights are reserved. This is a pre‐print and subject to correction. 

Abstract
Thermodynamic modeling can be used for predicting of
asphaltene deposition and precipitation by using polydisperse
data of heavy organic fractions. Accurate measurement of
asphaltene molecular weight distribution at reservoir
conditions could enhance the performance of model predictions.
However, in the best of our knowledge there is no reported
experience in the literature that extracts the molecular weight
distribution of asphaltene in both solid and liquid phases at
different reservoir conditions. In this work the high pressure,
high temperature asphaltene measurement setup has been used,
and the asphaltene precipitation amount due to pressure
reduction and CO2 injection processes were measured for one
of the Iranian heavy crudes. The molecular weight distributions
of asphaltene in liquid phase at different gas compositions as
well as total asphaltene content were measured by GPC
apparatus. Colloidal thermodynamic model applied and the
asphaltene molecular weight distributions in both solid and
liquid phases were predicted at different conditions. New
experimental method has been proposed for investigation of
asphaltene MW distribution behavior with thermodynamic
changes (pressure depletion and CO2 injection) at reservoir
condition. In addition, asphaltene average MW (number or
weight average or both) for each sample has been measured. It
has been observed that asphaltene MW distribution shifted to
the right (toward higher MW values) with addition of CO2 and
pressure depletion above bubble point. Reversely, its
distribution shifted to the left by reducing pressure below
bubble point. Measured average distributions confirmed that
asphaltene aggregates grow with pressure depletion and CO2
injection and their sizes decrease with pressure depletion below
bubble point. Our obtained results clearly illustrate that the
molecular weight distribution of asphaltene in solid and liquid
phases is sensitive to composition changes at reservoir
condition. Predictive capabilities of colloidal model are
critically evaluated on the measured data of asphaltene
molecular weight distribution in liquid phase.

1
1. Introduction
Asphaltenes are the heaviest component in crude oil. They
are defined as the portion of oil that is soluble in aromatics like
benzene and toluene and insoluble in straight chain n-alkanes
(light aliphatic) such as n-pentane or n-heptane [1, 2]. Asphaltene
precipitation and deposition have long been recognized as
problems in the production facilities. It can threaten the
economic recovery of oil, or increase considerably the cost of
production. The changes in reservoir pressure, temperature, and
composition can cause asphaltene to precipitate from the crude
oil [1].
Several models have been developed to predict asphaltene
precipitation behaviour of crude oil. Solid and colloidal
thermodynamic models are two powerful models which are
highly accepted by researchers in prediction of asphaltene
behaviour. Solid model was developed by Nghiem at 1993 [3].
In this model, the precipitated asphaltene is represented as pure
solid with the oil and gas modelled with an equation of state.
CMG software currently uses this model to predict asphaltene
precipitation behaviour. Hirschberg applied Flory-Huggins
model for asphaltene precipitation [4]. Asphaltene was assumed
to be homogeneous in this model. Later on Mansoori and Jiang
[5]
applied Scott and Magat [6] heterogeneous model on
asphaltene precipitation. Mansoori supposed that asphaltene
suspended as a colloid in crude oil by resins which act as
peptizing agents.
This paper presents experimental investigations of the
effect of pressure and CO2 composition changes on asphaltene
precipitation in one of the Iranian oil reservoirs. Colloidal was
applied to our experimental data in atmospheric conditions.
First, They were used to get an acceptable match by the model.
Afterward, it was used to predict the MW distribution of
asphaltene particles in both solid and liquid phase. Some
improvements have been performed on this model to make it
more precise and less dependent on matching parameters. This
was done by eliminating one of the essential matching
parameters which is used to predict its MW distribution [7].
Knowing exact molecular weight value of a component is
an essential factor for prediction of its behavior. Any error in
calculation of MW causes enormous effect on the results of
predicting models. For some components such as asphaltene,
because of wide variety of its molecular sizes, instead of a
constant value, a distribution used for its molecular weight
description. In the last two decade, many scientists have worked
on MW of asphaltene extensively [8,9]. In the best of our
knowledge, most of these researches focused on asphaltene
distribution with addition of solvents at atmospheric conditions.
In the next part of this paper, it has been tried to measure
asphaltene MW distribution due to different thermodynamic
changes (pressure reduction and CO2 injection) at reservoir
pressure. Better understanding of asphaltene MW distribution
behavior at reservoir condition can help us to make
thermodynamic models more realistic.
2
2. Experimental
2.1 High Pressure High Temperature Setup
The procedure of our experiment is briefly as follows. The
crude oil under investigation was taken at reservoir condition.
Its composition and properties are presented in table 1 and 2.
The oil is transferred to PVT cell in isobar process. It was tried
to avoid any pressure depletion during whole transfer processes.
The temperature of sample was raised to reservoir temperature
(96°C). It was shaken for 5 days inside PVT cell to
thermodynamic equilibrium condition regain. Afterward,
Different thermodynamic changes imposed to the oil. They can
be pressure depletion or CO2 injection in our experiments. It
may cause the asphaltene precipitation. After each
thermodynamic change, oil was mixed for two more days. 0.5-
micron high pressure metal filter is used to separate the
precipitated asphaltene in the oil. Deasphalted oil at reservoir
condition was transferred to sampler. After temperature of the
oil reduce to ambient temperature, it was transferred to a
beaker. Thereafter, samples were analyzed for n-heptane
insoluble asphaltenes using the ASTM D-6560 [10] procedure
(IP-143). The amount of asphaltene precipitated at each step
was calculated through the change of asphaltene content in the
oil phase. This can lead better understanding of asphaltene
precipitation behavior with every thermodynamic change.
2.2 Asphaltene MW distribution
measurement
In the second part of experiments, Obtained asphaltene was
used for determination of MW distribution with gel permeation
chromatography (g.p.c) or size exclusive chromatography.
Average molecular weights were determined for asphaltene
particles extracted from IP143 method. ASTM D6579-06 is
standard method used for average molecular weight and MW
distributions. The solvent used in this method is
Tetrahydrofuran (THF).
3. Modeling of Asphaltene Precipitation
(Colloidal model)
3.1. Primary concepts
Colloidal model is a heterogeneous model for prediction of
asphaltene behavior. Its heterogeneity is included by dividing
asphaltene into different segments and applying model to each
of them individually. Consequently, this model can improve the
prediction behavior of asphaltene.
Brief history and equations used in this model is as
follows. Mansoori [5] obtained the following formula by using
equation of chemical potential of liquid and solid phase which
was derived by Scott and Magat [6]:
L
VfAi S
/ VfAi  exp(NsAi ) ................................................................... (1)
Where
  (1 / N sAL  1 / N sAS )  (1  1 / N sAL )V fBL  f L (V fBL ) 2 ....(2) Kawanaka et al. proposed equations 11 and 12 for
calculation of asphaltene MWD in both liquid and solid phases:

F L ( M Ai )  {V L /[V L  V S exp( N sAi )]}

 2

f  1/ Nc VMB A B   2kABAB / RT .....................................(3)
(n CA / n AL ) F C ( M Ai )
........................(11)

k AB =interaction parameter between asphaltene and solvent

which is defined by: F S ( M Ai )  {V S /[V S  V L exp( N sAi )]}
........................(12)
k AB  a  bM B ............................................................................. (4) (n CA / n AS ) F C ( M Ai )

Kawanaka et al. [11] used continuous model of asphaltene

precipitation to apply the model to all asphaltene segments.
They defined specific continues model for this purpose. This
model needed molecular weight distribution (MWD) of total
asphaltene content in crude oil. They used gamma function for
their MWD determination. Some parameters of this function
have been found by experimental approximation obtained by
some researchers and the others used as matching parameters.
Equation 5 shows the general form of distribution proposed by
Kawanaka et al.
F ( M Ai )  [( M Ai  M A0 )  1 / ( )   ] ....................................(5)
exp[( M Ai  M A0 ) /  ]
Where
3.2. Modification of Model
Some modifications have been performed on model to
make it more precise. It was tried to measure as much input
parameters as it possible through experimental tests. This can
help us to decrease both uncertainty of the model and matching
parameters needed for getting better match. After matching
data, this model has been used for prediction of asphaltene
molecular weight in both liquid and solid phases.
3.3. Input Parameters of Model
Molar volume and solubility parameters of asphaltene and
asphaltene-free oil are the main input data needed in this model.
Different equation of state can be used to calculate each of these
parameters.

3.3.1. Asphaltene molar volume

  ( M A  M A0 ) 2 /  ................................................................(6)
Molar volume of asphaltene is calculated by following
formula:

   /( M A  M A0 ) .....................................................................(7) MW (asph)
Vm(asph)  ............................................................. (13)
 (asph)


( )   t  1  exp(t )dt ...........................................................(8) As it was discussed, asphaltene is divided into different
0 fractions and both molecular weight and density of each fraction
are needed for modeling. Variations in density of asphaltene
fractions are assumed to be negligible. Asphaltene density was
measured in our experiments. It had the value of 1.148 gr / cm 3
They proposed two estimated values for M A0 , M A based
instead of 1.2 gr / cm 3 used in Kawanaka‘s paper [11].
on other researcher’s experiments and used  as their matching
parameters. It was decided to use experimental graph obtained by GPC
(Figure 1) instead of gamma curve. This can help us in solving
By some simple calculation Equation 9 finally can be derived. the problem with less matching parameters. Although this
strategy makes our results more reliable, it may make severe

V fAL   dV fAi   {(M Ai / M A )V AC /
L problems in matching process.
0 ...............................(9)
[V  V exp( N sAi )]}  F ( M Ai )dM Ai
L S
By use of exact values of molecular weight and density,
correct value of molar volume is expected.
With the total volume fraction of asphaltene in the liquid
L
phase, V fA , the mount of asphaltene in liquid phase in 3.3.2. Asphaltene solubility parameter

Hirschberg [4] found the following formula for calculation

equilibrium with solid phase will be  AV fAV L . Therefore, the
L
of asphaltene solubility parameter. The same formula was used
amount of asphaltene deposited will be calculated by: in our model.

W Ad  W At   AV fAL V L .........................................................(10)  a = 20.04(1  1.07  10 3 T ) .....................................................(14)

3
 In this formula,  a was assumed to be independent of
pressure.
3.3.3. Solvent molar volume
Molar volume of solvent is calculated by the following
formula.
VmB  ( Z L  R  T ) / P .............................................................. (15)
3.3.4. Solvent solubility parameter
Solubility parameter of solvent is calculated by use of
Equation 16. Derivative of pressure-temperature relation of
Peng-Robinson EOS has been substituted in this equation and
consequently Equation 17 was derived.
 U   P 
2    T    P ..................................................... (16)
 V T  T 
0.5
 2  da  V  b( 2 1)  1 
 PR   a  T ln sat  
 4b  dT   Vsat  b( 2 1) V 
 depletion
3.4. Matching Parameters in Model
After all of these parameters obtained, the model can be
developed. a, b and WAt are three parameters that should be
matched by experimental data. In model developed by
Kawanaka [11],  is another matching parameter in calculation
of molecular weight distribution. In our modification, MWD
applied to the model experimentally.
4. Results and Discussions
4.1. Experimental asphaltene precipitation
results at reservoir condition
The experimental results for asphaltene precipitation due to
changes in pressure and CO2 composition are shown in figure 2
and 3. As can be seen, above the bubble point by decreasing the
pressure the amount of asphaltene precipitation increases. This
can be explained by density and solubility difference of oil and
asphaltene particles. When pressure of the oil above bubble
point decreases, its density and solubility also decrease. As a
result, solubility difference between asphaltene and oil increases
and it induce asphaltene precipitation. When the pressure
decreases below the bubble point, the light components separate
from oil and go into the gas phase and consequently the
solubility of asphaltene in oil increases. This causes some
asphaltene precipitates are re-dissolved back into the oil. Figure
2 also shows that the maximum amount of asphaltene
precipitation occurs at a point close to the bubble point pressure.
Figure 3 shows that increase in CO2 gas causes the amount
of asphaltene precipitation to increase. As can be seen, rising
trend of asphaltene precipitation has approximately linear trend.
Asphaltenes extracted from these two experiments are used for
determination of MW distribution in the next step.
4.2. Modeling results
Figure 4 is the result of matching between the model and
experimental results for data of precipitated asphaltene due to
addition of n-heptane. The values obtained for each matching
parameter are given in table 3.
After precipitation data was matched, the results of model
can be used. One of these results, which are very interesting, is
calculating MWD of liquid phase and solid phase of asphaltene.
These distributions can be calculated at different condition of
solvent addition by use of Equations 11 and 12. Some of the
distributions obtained by this model are depicted in figure 5 and
6. As it is shown in these figures, asphaltene molecular weight
increases with addition of n-heptane. The number of molecules
in solid phase also increases and reversely decreases in liquid
phase.
4.3. Behavior of asphaltene MW distribution
at reservoir condition
..... (17) 4.3.1. Asphaltene MW distribution change due to pressure
In order to understand Asphaltene MW distribution
behavior with pressure depletion below and above bubble point,
its distribution has been measured for asphaltene particles
obtained at pressure far above the bubble point (4000 psia), a
pressure close to bubble point(1000 psia) and below the bubble
point pressure (670 psia). Table 4 shows the average asphaltene
for mentioned pressures. As it can be seen, average MW
increases when the pressure decreases to near bubble point
pressure and afterward it shows a decrease by reducing
pressure. Figure 7 also illustrates the distribution curve of the
pressures. Reducing pressure above bubble point causes graph
to shift to the right (toward higher molecular weights) but below
bubble point, it shifts to the left.
4.3.2. Asphaltene MW distribution change with CO2
injection
In this part, asphaltene MW distribution changes with
injection of solvent were investigated. The asphaltene obtained
by three various CO2 injections were used to determine the
distributions.
Table 5 shows the variation of number, weight and Z
average of asphaltene molecular weights. As can be seen in this
table, all average values show an increase in MW distributions
with addition of CO2 to the oil. This method for determination
of asphaltene MW distribution in liquid phase can be used for
better thermodynamic modeling of asphaltene particles. The
variation of average molecular weights is clearly illustrated in
figure 8.
Figure 9 also shows MW distributions of asphaltene with
addition of 34.4, 51.48 and 57.11 CO2 mole percent to the oil.
As it depicts, with addition of more CO2 to the oil, MWD graph
shifts to the right.
4
 Distribution behavior of asphaltene particles for both 7. NOMENCLATURE
injection and depletion processes can be explained by its
molecular aggregation. Both reduction of pressure and CO2 L S = volume
V fAi and V fAi fractions of asphaltene
injection make asphaltene particles instable in solution. So, segment i to mixture volume in
aggregation process enhanced and they formed larger liquid and solid phase respectively
aggregates. Reversely, pressure depletion below bubble point solvent volume fraction in liquid
causes its partial dissolution. In the other word, some asphaltene V fBL =
phase
clusters separate from the aggregates and dissolve into the
solution. It makes the asphaltene aggregates smaller and its A and B = solubility parameter of asphaltene
and asphaltene free oil (solvent)
molecular weights lower. [Mpa0.5]
= ratio of asphaltene molar volume to
Some scientist report two maxima distributions in their N sA solvent molar volume
experiments with addition of alkanes at atmospheric condition R universal gas constant
[8,9]
, But this was not observed in none of our experimental
=
[(Mpa.m3)/(Kmol. °k)]
results at reservoir condition. This shows that asphaltene T temperature [°k]
particles dissolved in the THF has the same structures in
=
solution. To confirm our MWD experimental results, for two of a,b = Two independent constant
our injection, experiments repeated once more. MB = average molecular weight of solvent
(deasphalted oil)
M A0 = initial MW value of asphaltene
5. Conclusions = Mean MW value of asphaltene
MA
The main conclusions are as follows:
 = variance of gamma distribution
WAt = total amount of asphaltene in the
1. This work illustrates the successfully measurement of crude oil [gr]
asphaltene precipitation due to pressure depletion and CO2
injection by using blind cell. A = asphaltene density[gr/cm3]
total liquid and solid volume [cm3]
2. The results of experiments confirmed that as pressure V L ,V S =
decreases, above the bubble point, the asphaltene content VmB = Solvent Molar Volume [cm3]
of the crude oil will decrease, and the minimum content of
asphaltene will occur at saturation pressure. Decreasing the ZL = liquid molar volume
pressure below the bubble point pressure causes the
asphaltene redissolve back into the solution.
3. Since asphaltenes have vast variety of molecular sizes, the
use of MWD instead of average MW in predictive models 7. REFERENCES
can better represent the asphaltenes behavior. So this
makes the colloidal model really powerful in prediction of 1. Civan, F., Reservoir Formation Damage; Elsevier Inc.,
asphaltene precipitation. Second Edition, (2007)
4. Modifications implementation which have been performed
on colloidal model make it less dependent on matching 2. Wang, X., Creek, J.L., Buckley, J.S., Screening for
parameters. Potential Asphaltene Problems; SPE 103137, Sep. 24-27,
(2006)
5. The asphaltene molecular weight distributions in both solid
and liquid phases were extracted from colloidal 3. Nghiem, L.X., Hassam, M.S., Nutakki, R., George, A.E.D.,
thermodynamic modeling. Efficient Modelling of Asphaltene Precipitaion; SPE
26642, (1993)
6. An experimental method has been proposed for
determination of asphaltene molecular weight distribution 4. Hirschberg, A, Dejong, L.N.J., Schipper, B.A., Meijer,
behavior with pressure depletion and CO2 injection at J.G., Influence of Temperature and Pressure on Asphaltene
reservoir condition. Flocculation; KoninWijke/Shell E&P Laboratoriurn,
7. The distributions shift the right (higher molecular weights) (1984)
with pressure depletion above bubble point and CO2
5. Mansoori, G.A., Jiang, T.S., Asphaltene Deposition and its
injection. Reversely, it shifted toward left (lower molecular
Role in Enhanced Oil Recovery Miscible Gas Flooding;
weights) by reducing the pressure below bubble point.
Proc., third European Conference on Enhanced Oil
Number and weight average molecular weights showed
Recovery, Rome, April (1985)
similar trends with thermodynamic changes.
6. Scott, R.L., Magat, M., The Thermodynamics of High-
Polymer Solutions: I. The Free Energy of Mixing of
6. Acknowledgements Solvents and Polymers of Heterogeneous Distribution; J
Chem Phys 13, pp. 172–177, (1945)
The authors would like to thank from financial supports of
ICOFC and Petroleum University of Technology (PUT) on this 7. Firoozinia, H., Sadeqi Moqadam, M., Kharrat, R.,
research. Ghazanfari, M.H., Experimental and Modeling Study of
Asphaltene Precipitation at Reservoir Conditions: The

5
8. Mansoori, G.A., Vazquez, D., Shariaty-Niassar, M.,
Polydispersity of heavy organics in crude oils and their
role in oil well fouling; Journal of Petroleum Science and
Engineering (2007)

9. Dabir, B., Nematy, M., Mehrabi, A.R., Rassamdana, H.,

Sahimi, M., Asphalt flocculation and deposition (III. The
weight distribution); Fuel Vol. 75, No. 14, pp. 1633-1645,
1996

10. Standard Test Method for Determination of Asphaltenes

(Heptane Insolubles) in Crude Petroleum and Petroleum
Products; ASTM D 6560, (2000)

11. Kawanaka, S., Park, S.J., Mansoori, G. A., Organic

Deposition from Reservoir Fluids: A Thermodynamic
Predictive Technique; SPE Reservoir Engineering, May
(1991)

12. Yarranton, W., Masliyah, J.H., Molar Mass Distribution

and Solubility Modelling of Asphaltenes; AIChE Journal,
Vol. 42, No. 12, (1996)

13. Standard Test Methods for Separation of Petroleum into

Four Fractions; ASTM D 4124, (1997)

6
 Table 1: Oil composition
Recombined Oil
Components
(Mole %)
H2S 0.02
N2 0.13
CO2 2.07
C1 17.06
C2 8.05
C3 6.88
iC4 1.33
nC4 4.43
iC5 2.38
nC5 2.79
C6 3.35
C7 3.03
C8 1.60
C9 0.81
C10 1.67
C11 2.62
C12+ 41.79
Total 100

Table 2: Oil physical properties

Characteristic of Oil
Reservoir pressure (Psia) 4000
Reservoir Temperature (°F) 205
Saturation pressure (Psia) 1067
3
Density (lb / ft ) 52.8
GOR (scf / bbl) 240.43
°API 20
Formation volume factor 1.18
3
*Asphaltene Density (gr/cm ) 1.148
**SARA Content of STO (Wt. %)
Saturate 44.845
Aromatic 34.835
Resin 12.212
Asphaltene 8.108
[7, 12]
* The procedure for measurement of asphaltene density is given elsewhere .
**The detail work for SARA fractionation is given in ASTM D-4124 [13].

7
 Mw distribution(sarvak)

1.80E-04

1.60E-04

1.40E-04

1.20E-04

1.00E-04
fw

8.00E-05

6.00E-05
4.00E-05

2.00E-05
0.00E+00
0 5000 10000 15000 20000 25000 30000
Mw

Figure 1: Asphaltene molecular weight distribution of the oil (For total asphaltene content)

1.4
1.3
Asphaltene Precipitation

1.2
1.1
1
0.9
0.8
0.7
0.6
0.5
0.4
0 500 1000 1500 2000 2500 3000 3500 4000 4500
pressure

Figure 2: Effect of pressure depletion on the amount asphaltene deposition

8
 1.4

1.2
Asphaltene Precipitation
1

0.8
Experimental Values
0.6 Average values

0.4

0.2

0
20 30 40 50 60
CO2 Mole Percent

Figure 3: Effect of CO2 injection on the amount of asphaltene deposition

Matching of model with experimental result

0.09
Precipitated Asphaltene(% )

0.08
0.07
0.06
0.05 Model Results
0.04 Experimental Results
0.03
0.02
0.01
0
0 5 10 15 20 25 30 35
Solvent Ratio

Figure 4. Matching of colloidal model with experimental results

9
 Table 3: Matching parameters used for colloidal model
Matching Parameters
WAt 9.5
A -0.0117
B -0.00003

Figure 5: Comparison of solid and liquid phases MWD when 4 cm3 of n-heptane added to 1 gr of stock tank oil

Figure 6: Comparison of solid and liquid phases MWD when 6 cm3 of n-heptane added to 1 gr of stock tank oil

10
 Table 4: Variation of asphaltene average MW in liquid phase due to pressure depletion

Pressure (psia) 4000 1000 670

MW 5024.2 6232.4 5765.3

MW of asphaltene in depletion process

1.2

0.8
Frequency

P=4000 psia
0.6 P=1000 psia
P=670 psia
0.4

0.2

0
2.4 2.9 3.4 3.9 4.4 4.9
Log(MW)

Figure 7) Asphaltene MW distribution at different pressures

Table 5) Variation of number, weight and Z average asphaltene molecules due to CO2 injection

CO2 mole Percent 34.4 (1) 34.4 (2) 51.48 (1) 51.48 (2) 57.11

Mn : 2722.7 2758.5 3158.1 3227.4 3322.3

Mw : 6056.8 6118.1 7232.9 7079.3 7986.8

Mz : 10109 10105 11808 11371 13617

11
 8500

8000

7500

Asphaltene MW in Liquid Phase

7000

6500

6000

5500

5000

4500

4000
34.4 (1) 34.4 (2) 51.48 (1) 51.48 (2) 57.11
CO2 m ole percent

Figure 8) Comparison of asphaltene average molecular weights extracted from oil with injection of different CO2 amounts

MWD of asphaltene in injection process

1.2

0.8 34.4 - 1
Frequancy

34.4 - 2
0.6 57.11
51.48 - 1
0.4
51.48 - 2
0.2

0
2.5 3 3.5 4 4.5 5
Log(MW)

Figure 9) Variation of asphaltene MW distribution in the oil with CO2 injection

12