SPE 64465
Modelling Phase Behaviour Including the Effect of Pressure and Temperature on
Asphaltene Precipitation
Bruce F. Kohse, Computer Modelling Group Ltd.; Long X. Nghiem, Computer Modelling Group Ltd.; Haruo Maeda,
Teikoku Oil Co. Ltd.; and Kenji Ohno, Japan National Oil Corporation
Copyright 2000, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE Asia Pacific Oil and Gas Conference and
Exhibition held in Brisbane, Australia, 16–18 October 2000.
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Abstract
This paper describes a procedure for matching PVT data of a
typical oil that includes asphaltene precipitation data. The
fluid PVT data are from constant composition expansion,
differential liberation and separator test experiments. The
experimental precipitation data consist of measurements of
precipitation onset pressures at different temperatures.
The PVT data are validated for consistency using Hoffman
plots, and matched with the Peng-Robinson equation of state1.
A pure solid model is used to model the asphaltene
precipitate2,3,4. The equations describing effect of pressure and
temperature on the solid model are given. The parameters of
the solid model are adjusted to match the asphaltene
precipitation data.
Experimental data
The experimental PVT includes compositional analysis,
constant composition expansion, differential liberation and
separator data. Asphaltene precipitation data consist of
measurements of onset pressures at four different temperatures
as shown in Table 1. It was also reported that there was no
asphaltene precipitation observed at the reservoir temperature
of 218.3 °F. In addition, the result of a bulk filtration
experiment on the fluid at 100 °F and 2100 psia showed 1.6
weight % precipitate.
Model Development
The procedure used to develop the model is given below:
1. Initial fluid characterization
2. Data consistency checks
3. Development of initial working model of fluid
4. Specification of asphaltene component parameters
5. Regression to match fluid PVT data
6. Validation of asphaltene component parameters for
isothermal predictions
7. Determination of solid model parameters for non-
isothermal predictions
8. Prediction of Asphaltene Precipitation Envelope (APE)
Steps 4 through 6 were repeated with different values of
the asphaltene component parameters until an optimal
combination of parameters was obtained. The remainder of
this paper describes each of the above steps.
Initial Fluid Characterization
The compositional data for the bottomhole sample as given
in the PVT report was determined by flashing the fluid at
ambient conditions and analyzing the resulting liquid and gas
phases. Compositional information for pure components and
single carbon number fractions to C30+ was provided. The data
includes the mole fraction of components in the gas phase,
weight fraction of components in the liquid phase, molecular
weights of the components, molecular weights of the phases,
and API gravity of the liquid phase. The live fluid composition
and molecular weight were also reported, based on a measured
GOR for the flash.
To generate critical properties for the single carbon
number fractions (SCN’s) to use in the equation of state
model, specific gravities are required. For SCNs up to C29,
generalized specific gravities and normal boiling points are
taken from Whitson5. The specific gravity of the C30+ fraction
is calculated from the reported liquid phase API gravity. The
calculated physical properties of the oil are shown in Table 2.
Once the physical properties of the SCNs are known, the
critical properties are calculated using the Lee-Kesler
correlations6.
Using the Peng-Robinson equation of state1, the initial
characterization process results in a 42 component model
which predicts the bubble point pressure at the reservoir
temperature to within 10 psi of the measured value.
Data Consistency Checks
The experimental differential liberation and separator data
were checked for material balance errors and internal
2 B.F. KOHSE, L.X. NGHIEM, H. MAEDA, K. OHNO
consistency. The internal consistency of the data is evaluated
by checking the linearity of the trends on Hoffmann plots.
To facilitate easier interpretation of the Hoffmann plots,
the C7+ SCN’s of the 42-component model are first lumped to
create the pseudo components C7, C8, C9, C10 and C11+. The
properties of the pseudo components are calculated using the
Lee-Kesler mixing rules7.
The calculated material balance errors are very low: 0.51%
for the differential liberation experiment, and -0.60% for the
separator experiment. The results of the Hoffmann plots,
shown in Figures 1 through 3, are also good; deviations from
linearity are apparent for only the lightest and heaviest
components, particularly at low pressures, which is the
expected result.
The results of the data consistency checks indicate that the
experimental data may be used reliably for tuning the equation
of state model.
Development of Initial Working Model of Fluid
The initial working model of the fluid is generated by
lumping the full 42 component model into a smaller number
of pseudo components. The number of components in the
working model should be adequate to fully describe the phase
behavior, yet small enough to allow easy manipulation of the
component parameters for tuning purposes.
The full 42-component model is first tuned to match the
experimental reservoir bubble point pressure by adjusting the
hydrocarbon interaction coefficient exponent. Once this is
done, the lumping scheme is determined by grouping together
components that have similar K-values at the bubble point.
This lumping technique resulted in the following set of 12
components and pseudo components for the initial working
model: CO2, C1-N2, C2, C3, C4, C5, C6, C7-C8, C9-C13, C14-C20,
C21-C29 and C30+. Lumped component properties are again
generated using the Lee-Kesler mixing rules.
The adequacy of the lumping scheme is checked by
generating phase envelopes for both the many-component and
the lumped models. As shown in Figure 4, the phase
envelopes are nearly identical for the two cases.
Specification of Asphaltene Component Parameters
The asphaltene precipitate is modelled as a pure solid as
described in Nghiem et al.2,3,4. The heaviest pseudo component
in the fluid model is split into a non-precipitating component
(C30+) and a precipitating component (C30+ASP). These two
components have the same critical properties and acentric
factors, but may have different binary interaction parameters
and different volume shift parameters.
The binary interaction parameters between hydrocarbon
components are calculated according to the following
formula8:
θ
 2v1 / 6 v1 / 6 
 ci cj 
δ ij = 1 −  (1)
 v1ci/ 3 + v 1cj/ 3 
 
where vci and vcj are the critical volumes of the components
and θ is an adjustable parameter. Different values of the
parameter θ can be applied to different groups of components.
SPE 64465
In order to adjust the interaction parameters for the asphaltene
component independently, three groups were defined. θ2
applies to interactions between C30+ASP and the components
C1-N2 through C5, θ3 applies to interactions between C30+ASP
and the components C6 through C30+, while θ1 applies to all
other pairs of hydrocarbon components.
An average value of the θ parameter applicable for
reservoir fluids is 1.2. From previous work with the asphaltene
model, it was known that interaction parameters between the
asphaltene component and the light components should be
approximately 0.20 to 0.24. The corresponding values of θ2
are in the range 1.8 to 2.5. Several values within this range
were investigated. The criteria used to select the best
parameters will be discussed later.
Initial volume shift parameters were determined using a
temperature dependent volume shift calculation, which
ensures that the saturated liquid density for a component
predicted by the equation of state with volume shift matches
the saturated liquid density given by Rackett’s correlation9. It
was found that setting the volume shift for the asphaltene
component to a value slightly higher than that for the non-
precipitating C30+ component gave good results.
The mole fraction of the C30+ASP component is determined
using the following formula:
z C30+ ASP = w ASP M oil / M C30+ ASP (2)
Using the experimental value of the weight % asphaltene
in the dead oil of wASP = 6.1%, the mole fraction of the C30+ASP
component is 0.012873.
Regression to Match Fluid PVT Data
The fluid model with asphaltene component present can
now be tuned to match the experimental PVT data. The
following data were used:
• Bubble point pressure at reservoir temperature (218.3 °F)
• Bubble point pressure at 100 °F
• Constant composition experiment data at 218.3 °F
(relative fluid volumes and liquid saturations)
• Constant composition experiment data at 100 °F (relative
fluid volumes and liquid saturations)
• Differential liberation data (liquid density, oil formation
volume factor, gas oil ratio, gas compressibility factor,
gas formation volume factor, gas density and residual oil
gravity)
• Separator test data (separator gas oil ratio, oil formation
volume factor and stock tank oil gravity)
The critical temperatures, critical pressures, acentric
factors and volume shifts of the C7+ pseudo components were
adjusted during regression to match the experimental data. A
regression grouping method was applied to each of these
variables to ensure that initial trends in the values were
maintained. CO2 binary interaction parameters and volume
shifts for the light components were also adjusted. The θ
parameters for the hydrocarbon interaction parameters were
not varied during regression, as these were manually adjusted
to give the desired precipitation trends.
SPE 64465 MODELLING PHASE BEHAVIOUR INCLUDING THE EFFECT OF P AND T ON ASPHALTENE PRECIPITATION 3

The results of the final regression are shown in Table 3 for The molar volume of the solid affects the amount of
the bubble point results, the separator data and the differential asphaltene precipitation within the asphaltene deposition
liberation residual density. The results of the constant envelope. Increasing the solid molar volume results in greater
composition expansion and differential liberation simulations amounts of solid precipitated. As the amount of solid
are shown in Figures 5 through 12. These results illustrate that precipitate at 100 °F and 2100 psia is known to be 1.6 weight
the full model, including the asphaltene component, can %, the solid molar volume can be adjusted for isothermal runs
provide a good match to the fluid PVT data. until the model predictions match the experimental data. The
Asphaltene Model Equations final value of solid molar volume was found to be 0.5752
The general solubility equation that relates the solid l/mol.
fugacity to liquid fugacity of a pure component is (see for The θ3 parameter for the interactions between the
example Ref. 10): asphaltene and the light components controls the slope of the
precipitation curve below the bubble point. As there is no
∆H tp  1 
ln f s (p, T ) = ln f l (p, T) −  − 1  experimental data on the amount of solid precipitated below
R  T Ttp  the saturation pressure curve, the θ3 parameter was adjusted to
produce trends which have been observed in other asphaltene
∆C p   Ttp   T 
ln   + 1 − tp 
− (3) precipitation studies. That is, a maximum in asphaltene
R   T  
  T  precipitation is observed at the bubble point of the fluid, and
the asphaltene is dissolved back into the oil as pressure
p
decreases below the bubble point due to change in
∫ (v s − v l ) dP
1
+ composition of the oil. It is assumed that all of the asphaltene
RT
p tp will dissolve back into the oil at sufficiently small pressures
below the bubble point. Behavior of this kind has been
It is shown in the Appendix that this equation can be used to reported by Hammami et al.11.
derive an expression relating the fugacity of the solid at any With a fixed value of solid molar volume, different values
pressure and temperature to the solid fugacity at a reference
of the θ2 parameter were investigated to determine their effects
condition, as follows:
on the shape of the isothermal precipitation curves. For
example, Figure 13 shows precipitation curves for θ2 = 1.8.
v s  p − p tp p − p tp 
*
ln f s = ln f s* +  −  This value was considered too small, as it resulted in
R  T T *  precipitation decreasing then increasing with decreasing
  (4) pressure for the higher temperatures. The precipitation curves
∆H tp  1 1  ∆C p   T*  
− ln  − Ttp  1 − 1  with the final selected value of θ2 = 2.1 are shown in Figure
 − −  
R  T T*  R   T   T T *  14.
Each time the asphaltene component parameters were
This is the form of the asphaltene fugacity equation used for changed, the model was re-tuned to the experimental data and
predicting the effect of pressure and temperature on asphaltene the isothermal cases were run again until the correct trends in
precipitation. the precipitation curves were predicted.
For isothermal predictions, Equation (4) can be simplified Determination of Solid Model Parameters for Non-
to give: Isothermal Predictions
To use the fugacity relation given in equation (4), the triple
ln f s = ln f s* + v s (p − p * ) / RT (5) point temperature and pressure, enthalpy of fusion at the triple
point and the liquid-solid heat capacity difference must be
Validation of Asphaltene Component Parameters for known in addition to the parameters used in the isothermal
Isothermal Predictions model.
Given the tuned equation of state model with specified
The triple point is the point where solid, vapor and liquid
asphaltene component parameters obtained above, the solid
coexist at equilibrium. Figure 15 shows a typical pressure-
model given in equation (5) can be used to predict the amount
temperature diagram with the location of the triple point12. For
of solid precipitate for isothermal cases.
asphaltene, the triple-point pressure is very low and can be set
In order to use this equation, the reference fugacity ln f s* at to zero. The triple-point temperature is close the melting point
the reference pressure p* and the molar volume of the solid vs temperature of asphaltene at atmospheric pressure as the solid-
must be known. The reference fugacity is set equal to the liquid coexistence curve has a very steep slope (see Figure
fugacity of the asphaltene component in the liquid phase 15). The melting point temperature in K can be estimated from
predicted by the equation of state at a known asphaltene the following correlation13:
deposition onset pressure. The solid molar volume is normally Tf = 374.5 + 0.02617 M s − 20172 / M s (6)
set slightly higher than the molar volume of the asphaltene
component predicted by the equation of state. where Ms is the molecular weight of the asphaltene
component.
4 B.F. KOHSE, L.X. NGHIEM, H. MAEDA, K. OHNO SPE 64465

As for the isothermal runs, the reference fugacity is set The final asphaltene precipitation envelope is shown in
equal to the fugacity of the asphaltene component in the liquid Figure 19. This figure shows the results of the model
phase at a known asphaltene deposition onset pressure. The incorporating the known amount of solid precipitate at 100 °F
molar volume of the solid is also set as for the isothermal runs. and 2100 psia, and uses three onset points to define the
This leaves the heat of fusion and the heat capacity difference parameters in the solid model. As well as the precipitation
as adjustable parameters to fit any experimental data. envelope, quality lines from 0.25 to 1.5 weight % are also
The experimental onset pressures at either two or three shown. The calculated points on all curves are determined to
temperatures may be used to tune the parameters in the solid within +/- 1 psia.
model. Since there are three unknown parameters in the model
(reference fugacity, heat of fusion and heat capacity Conclusions
difference) if only two data points are used, one of the An equation of state model has been developed and tuned to
unknown parameters must be set to an assumed value. The match experimental fluid PVT behavior. An asphaltene
approach used in this work is to set the heat capacity component has been included in the fluid model to allow
difference to zero, as is commonly done for solids modelling. modelling of asphaltene precipitation as a function of pressure
If three onset points are used, heat of fusion and heat capacity and temperature. The solid model is capable of predicting the
difference may both be calculated to fit the experimental data. APE and the amount of precipitation within the envelope. The
Fugacities of the asphaltene component in the liquid phase solid model can be tuned using only two experimental
are determined from the equation of state at the experimental asphaltene deposition onset pressures, but can also be adjusted
onset pressures. One of these fugacities is used as the to fit additional experimental data.
reference fugacity in the model, while the others are used to
calculate the value of the heat of fusion, and optionally, the Nomenclature
heat capacity difference. This completes the definition of the fs = solid fugacity
model, which can now be used to predict asphaltene fs* = reference solid fugacity
precipitation at any pressure and temperature. fl = liquid fugacity
Prediction of Asphaltene Precipitation Envelope M = molecular weight
The asphaltene precipitation envelope (APE) is determined by Ms = molecular weight of asphaltene
performing flashes at varying pressures for a number of p = pressure
temperatures. Plots of the precipitation curves for p* = reference pressure
temperatures from 100 to 190 °F are shown in Figures 16 and ptp = triple-point pressure
17. Flash calculations using a small pressure step are used to R = gas constant
locate the precipitation onset pressures to within 1 psia. These T = temperature
calculated onset pressures taken together define the asphaltene Tf = temperature of fusion
precipitation envelope. T* = reference temperature
Two calculated APE are shown on Figure 18. These curves Ttp = triple-point temperature
were generated before final adjustment of the solid molar vc = critical volume
volume, and are shown to illustrate the ability of the model to vl = liquid molar volume
predict the correct shape of the envelope with only 2
experimental onset points. One curve is calculated using the vs = solid molar volume
experimental onset pressures at 100 and 190 °F. This curve is ∆Cp = heat capacity difference (C p l − C ps ) [cal/mol K]
labeled “APE (2-pt fit).” The second calculated curve is ∆Htp = enthalpy of fusion at triple-point [cal/mol]
generated by using a third experimental data point at 120 °F, δij = binary interaction coefficient
allowing both heat of fusion and heat capacity difference to be θ = parameter in binary interaction coefficient equation
adjusted to match the experimental data. This curve is labeled
“APE (3-pt fit).” It can be seen that the model developed using Acknowledgements
only 2 experimental onset points matches the trend in the The authors wish to thank Japan National Oil Corporation and
experimental asphaltene deposition envelope very well. Use of Teikoku Oil Co. Ltd. for the permission to publish this work.
the third point allows fine tuning of the model.
The parameters of the solid model for these two cases are References
shown in Table 4. The values for the enthalpy of fusion at the 1. Peng, D.-Y. and Robinson, D.B.: “A New Two-Constant
triple point resulting from this solution procedure are in the Equation of State,” Ind. Eng. Chem. Fundam., Vol. 15 (1976)
range of 40,000 to 50,000 cal/mol. This is approximately 5 59-64
times higher than the enthalpy of fusion obtained by Chung14 2. Nghiem, L.X. and Coombe, D.A.: “Modeling Asphaltene
for asphaltene. It is possible that these large values are a result Precipitation During Primary Depletion,” Soc. Petrol. Eng. J.
(June 1997) 170-176.
of the fitting procedure used in this work. However, enthalpies
3. Nghiem, L.X., Coombe, D.A., and Farouq Ali, S.M.:
of fusion obtained from work on other fluids are very similar “Compositional Simulation of Asphaltene Deposition and
to those reported here. Plugging,” paper SPE 54378, Proceedings 1999 SPE Asia
SPE 64465 MODELLING PHASE BEHAVIOUR INCLUDING THE EFFECT OF P AND T ON ASPHALTENE PRECIPITATION 5

Pacific Oil and Gas Conference and Exhibition, Jakarta, ln f s (p, T ) − ln f s (p * , T * ) =

Indonesia, 20–22 April 1999.
4. Nghiem, L.X., Kohse, B.F., Farouq Ali, S.M. and Doan, Q.: ln f l (p, T ) − ln f l (p * , T * )
“Asphaltene Precipitation: Phase Behaviour Modelling and
Compositional Simulation,” paper SPE 59432, Proceedings ∆H tp  1 1 
−  − 
2000 SPE Asia Pacific Conference on Integrated Modelling for R  T T * 
Asset Management, Yokohama, Japan, 25–26 April 2000.
5. Whitson, C.H.: “Characterizing Hydrocarbon Plus Fractions,” ∆C p   T *  1 1 
Soc. Petrol. Eng. J. (August, 1983) 683-694. − ln   − Ttp  − 
R   T   T T * 
(A.2)
6. Kesler, M.G., and Lee, B.I.: “Improve Prediction of Enthalpy of 
Fractions,” Hydrocarbon Processing (March 1976) 153-158.
p p*
7. Lee, B.I., and Kesler, M.G.: “A Generalized Thermodynamic 1 1
Correlation Based on Three-Parameter Corresponding States,” −
RT ∫ v l,T dp +
RT * p
∫ v l,T* dp
AIChE J., Vol. 21 (May 1975) 510-527. p tp tp
8. Chueh, P.L. and Prausnitz, J.M.: “Vapor-Liquid Equilibria at
High Pressures: Calculation of Partial Molar Volumes in v s (p − p tp ) v s (p * − p tp )
Nonpolar Liquid Mixtures,” AIChE J., Vol. 13 (November + −
1967) 1099-1107.
RT RT *
9. Kokal, S.L. and Sayegh, S.G.: “Gas-Saturated Bitumen Density In addition the following expression for liquid phase fugacities
Predictions Using the Volume-Translated Peng-Robinson
can be derived:
Equation of State, J Can. Petrol. Technol., Vol 29 (September-
October 1990) 77-82.
ln f l (p, T) − ln f l (p * , T * ) =
[ ln f l (p, T) − ln f l (p tp , T)]
10. Firoozabadi, A: Thermodynamics of Hydrocarbon Reservoirs,
McGraw-Hill, New York (1999) 298-299.
11. Hammami, A., Phelps, C.H., Monger-McClure, T. and Little,
T.M.: “Asphaltene Precipitation from Live Oils: An [
− ln f l (p * , T * ) − ln f l (p tp , T * ) ]
+ [ ln f , T )] =
Experimental Investigation of the Onset Conditions and
Reversibility,” Proceedings AIChE 1999 Spring National l (p tp , T) − ln f l (p tp *
(A.3)
Meeting, Houston, TX, March 14-18, 1999.
p p*
12. Sandler, S.I.: Chemical and Engineering Thermodynamics, John 1 1
Wiley & Sons, New York (1977) 243.
RT ∫ v l,T dp −
RT * p
∫ v l,T* dp
13. Won, K.W.: “Thermodynamics for Solid-Liquid Equilibria: Wax p tp

[ ]
tp
Formation from Heavy Hydrocarbon Mixtures,” Fluid Phase
Equilibria, Vol. 30 (1986) 265-279. + ln f l (p tp , T) − ln f l (p tp , T * )
14. Chung, T.-H.: “Thermodynamic Modeling for Organic Solid
Precipitation,” paper SPE 24851, Proceedings 67th Annual The triple point pressure for asphaltene is very small. At very
Technical Conference and Exhibition of the SPE, Washington, low pressures, ideal gas behavior is approached and the
DC, October 4-7, 1992. asphaltene liquid fugacity is approximately equal to the
pressure, and is independent of temperature. Thus the last term
Appendix- Effect of Pressure and Temperature on in the bracket in Equation (A.3) is zero. Substituting Equation
Solid Fugacity (A.3) into Equation (A.2) gives:
Writing equation (3) for the solid fugacity at (p,T) and the
solid fugacity at a reference condition (p*,T*), then subtracting ln f s (p, T ) − ln f s ( p * , T * ) =
yields the following equation: ∆H tp  1 1 
−  − 
ln f s (p, T ) − ln f s (p * , T * ) = ln f l (p, T ) − ln f l (p * , T * ) R  T T * 
∆C p   T *  1 1 
∆H tp  1 1  ∆C p   T *  1 1  − ln   − Ttp  − 
(A.4)
−  − − ln − Ttp  −  (A.1) R   T 
R  T T *  R   T   T T *    T T * 

p p* v  ( p − p tp ) (p * − p tp ) 
+ s  − 
∫ (v s − v l )T dp − RT * ∫ (v s − v l )T
1 1
+ * dp R  T T * 
RT
p tp p tp
 
which is Equation (4).
Assuming that the solid molar volume, vs, is constant,
Equation (A.1) becomes:
6 B.F. KOHSE, L.X. NGHIEM, H. MAEDA, K. OHNO SPE 64465

Table 1: Experimental Asphaltene Precipitation Onset Pressures

Temperature (°F) Onset Pressure (psia)

100 7690
120 7230
170 4360
190 3500

Table 2: Oil Fraction Physical Properties

Molecular Weight Specific Gravity

Live Oil 122.4 0.77472
C6+ fraction 231.5 0.86767
C7+ fraction 239.6 0.87220
C30+ fraction 580.0 0.96434

Table 3: Regression Results

Experimental Calculated
Saturation Pressure at 218.3 °F (psia) 2560 2558
Saturation Pressure at 100 °F (psia) 2000 2003
Separator GOR (scf/bbl) 516 509
Separator Formation Volume Factor 1.306 1.309
Separator Stock Tank API Gravity 32.0 32.2
Differential Liberation Residual Density (g/cm3) 0.876 0.874

Table 4: Solid Model Parameters

vs (l/mol) ∆Cp (cal/mol K) ∆Htp (cal/mol)

Using 2 onset points 0.59 0.0 43166
Using 3 onset points 0.59 13.4 42895
SPE 64465 MODELLING PHASE BEHAVIOUR INCLUDING THE EFFECT OF P AND T ON ASPHALTENE PRECIPITATION 7

10000

1000

Pressure * K value (psia)

100

10

0.1

0.01
-4.00 -3.00 -2.00 -1.00 0.00 1.00 2.00 3.00 4.00
F factor

p = 1600 psia p = 800 psia p = 250 psia p = 65 psia p = 14.7 psia

Figure 1: Hoffmann Plot for Differential Liberation

1000

100
Pressure * K value (psia)

10

0.1

0.01
-3.00 -2.00 -1.00 0.00 1.00 2.00 3.00
F factor

sep. #1, p= 59 psia

Figure 2: Hoffmann Plot for Separator Stage 1

1000

100
Pressure * K value (psia)

10

0.1

0.01
-3.00 -2.00 -1.00 0.00 1.00 2.00 3.00
F factor

sep. #2, p= 13.7 psia

Figure 3: Hoffmann Plot for Separator Stage 2

8 B.F. KOHSE, L.X. NGHIEM, H. MAEDA, K. OHNO SPE 64465

3000

2500

2000

Pressure (psia)
1500

1000

500

0
0 200 400 600 800 1000 1200
Temperature (deg F)

42 comp 12 comp Critical

Figure 4: Phase Envelopes for 42-Component and 12-Component Models

1.30

1.25

1.20
Relative Volume

1.15

1.10

1.05

1.00

0.95
1000 2000 3000 4000 5000 6000 7000 8000
Pressure (psia)

ROV Psat Exp. ROV

Figure 5: CCE at 218.3°°F – Relative Volumes

105

100
Liquid Volume, % cell vol.

95

90

85

80

75

70
1000 2000 3000 4000 5000 6000 7000 8000
Pressure (psia)

Liq. Vol. Exp. Liq. Vol.

Figure 6: CCE at 218.3°°F – Liquid Volumes

SPE 64465 MODELLING PHASE BEHAVIOUR INCLUDING THE EFFECT OF P AND T ON ASPHALTENE PRECIPITATION 9

2.40

2.20

2.00

Relative Volume
1.80

1.60

1.40

1.20

1.00

0.80
0 1000 2000 3000 4000 5000 6000 7000 8000
Pressure (psia)

ROV Psat Exp. ROV

Figure 7: CCE at 100°°F – Relative Volumes

110

100
Liquid Volume, % cell vol.

90

80

70

60

50

40

30
0 1000 2000 3000 4000 5000 6000 7000 8000
Pressure (psia)

Liq. Vol. Exp. Liq. Vol.

Figure 8: CCE at at 100°°F – Liquid Volumes

600 1.40

1.35
500
Gas-Oil Ratio (scf/bbl)

1.30
Relative Oil Volume

400
1.25

300 1.20

1.15
200
1.10
100
1.05

0 1.00
0 500 1000 1500 2000 2500 3000 3500
Pressure (psia)

GOR Exp. GOR ROV Exp. ROV

Figure 9: Differential Liberation – Gas-Oil Ratios and Oil Formation Volume Factors
10 B.F. KOHSE, L.X. NGHIEM, H. MAEDA, K. OHNO SPE 64465

1.00 1.40

0.98 1.20

Gas Compressibility Factor

1.00
0.96

Gas FVF
0.80
0.94
0.60
0.92
0.40
0.90 0.20

0.88 0.00
0 500 1000 1500 2000 2500 3000 3500
Pressure (psia)

Gas Z Exp. Gas Z Gas FVF Exp. Gas FVF

Figure 10: Differential Liberation – Gas Compressibility Factors and Formation Volume Factors

0.84 2.40
2.20
0.82
2.00
Oil SG (Water = 1)

Gas SG (Air = 1)
0.80 1.80
1.60
0.78
1.40
0.76 1.20
1.00
0.74
0.80
0.72 0.60
0 500 1000 1500 2000 2500 3000 3500
Pressure (psia)

Oil SG Exp. Oil SG Gas SG Exp. Gas SG

Figure 11: Differential Liberation – Oil and Gas Specific Gravities

3.00 0.025

2.50
0.020
Gas Viscosity (cp)
Oil Viscosity (cp)

2.00
0.015
1.50

0.010
1.00

0.50 0.005
0 500 1000 1500 2000 2500 3000 3500
Pressure (psia)

Oil Visc. Exp. Oil Visc. Gas Visc. Exp. Gas Visc.

Figure 12: Differential Libearation – Oil and Gas Viscosities

SPE 64465 MODELLING PHASE BEHAVIOUR INCLUDING THE EFFECT OF P AND T ON ASPHALTENE PRECIPITATION 11

2.00

1.50

Solid Precipitate (wt %)

1.00

0.50

0.00
0 2000 4000 6000 8000
Pressure (psia)

100.00 deg F 120.00 deg F 170.00 deg F 190.00 deg F

Figure 13: Isothermal Solid Precipitation Curves with θ 2 = 1.8

2.00

1.50
Solid Precipitate (wt %)

1.00

0.50

0.00
0 2000 4000 6000 8000
Pressure (psia)

100.00 deg F 120.00 deg F 170.00 deg F 190.00 deg F

Figure 14: Isothermal Solid Precipitation Curves with θ 2 = 2.1

Figure 15: Pure component Pressure-Tempature Phase Diagram

12 B.F. KOHSE, L.X. NGHIEM, H. MAEDA, K. OHNO SPE 64465

2.00

Solid Precipitate (wt %)

1.50

1.00

0.50

0.00
0 2000 4000 6000 8000
Pressure (psia)

100.00 deg F 120.00 deg F

Figure 16: Aspahltene Precipitation at 100 abd 120 ° F

1.00

0.80
Solid Precipitate (wt %)

0.60

0.40

0.20

0.00
0 2000 4000 6000 8000
Pressure (psia)

150.00 deg F 170.00 deg F 190.00 deg F

Figure 17: Aspahltene Precipitation at 150, 170 and 190 ° F

SPE 64465 MODELLING PHASE BEHAVIOUR INCLUDING THE EFFECT OF P AND T ON ASPHALTENE PRECIPITATION 13

10000

8000

Exp. Psat
Pressure (psia)
6000
Exp. APE
Psat
APE (2-pt fit)
4000
APE (3-pt fit)

2000

0
50 100 150 200 250
Temperature (F)

Figure 18: Comparison of APE Curves Using 2 or 3 Experimental Data Points

10000

8000
Psat (exp)
APE (exp)
Psat
6000 APE
Pressure (psia)

0.25 wt%
0.5 wt%
0.75 wt%
4000 1.0 wt%
1.25 wt%
1.5 wt%
1.6 wt% (exp)
2000

0
50 100 150 200 250
Temperature (F)

Figure 19: Final APE with Precipitation Quality Lines