Petroleum Science and Technology, 25:949965, 2007

Copyright Taylor & Francis Group, LLC

ISSN: 1091-6466 print/1532-2459 online
DOI: 10.1080/10916460500526981

Empirical Equations for Estimating ADE

of Crude Oils
M. A. Fahim
Chemical Engineering Department, Kuwait University, Safat, Kuwait

Abstract: There has been an increasing interest in the construction of asphaltene

deposition envelope (ADE) to determine a safe zone of operation during oil production. Equations of state are usually used for calculations of ADE; however, the
method requires tuning some experimental Pressure Volume Temperature (PVT) data
of the reservoir fluid. The objective of this study is to develop a simple, accurate,
and reliable empirical equation for estimating the ADE by determining the upper
and lower onset pressures as well as the saturation pressures. Three simple empirical equations are developed to calculate these onset pressures of several crude oils.
Experimentally measured compositions, saturation, and onset pressures of 33 crude
oil samples, primarily from the Middle East, at different temperatures were used to
develop the equations. Another set of compositions and upper saturation and lower
onset pressures of different crude oil samples from the literature were used to test the
accuracy of the empirical equations. The results were also compared with equations of
state predictions. The results indicate that the method is accurate, valid, reliable, and
eliminates the splitting and characterizing of the heavy fraction, which is necessary
for the equations of state predictions. The method is useful for estimating the ADE
of crude oils where experimental data is not available.
Keywords: asphaltene, deposition, emperical, envelope

INTRODUCTION
The formation of asphaltene is a flow assurance problem experienced by a
large number of operators. It can be caused be thermodynamic considerations
such as pressure and temperature changes. It can also be caused by compositional changes during production. For example, it can be caused during
CO2 or gas injection operations. Gas breakthrough can cause it as well. The
stability of oils under reservoir conditions can be studied by construction of
Address correspondence to M. A. Fahim, Kuwait University, Department of
Chemical Engineering, P.O. Box 5969, Safat, Kuwait. E-mail: fahimoose@yahoo.com
949

950

M. A. Fahim

what is called the asphaltene deposition envelope (ADE). A key evaluation in

asphaltene formation and stabilization in the determination of the pressure/
temperature phase envelope of asphaltene flocculation onset (ADE) will be
studied in this work.
Several previous attempts have been made to model asphaltene deposition with varying degrees of success. The colloidal method of Leontaritis was
used to calculate asphaltene flocculation conditions for CO2 C oil mixtures
but only at one temperature. Both Hirschberg et al. (1984), Chung (1992),
and Burke et al. (1990) have treated asphaltene as a pure liquid phase in
equilibrium with a solvent using the Flory-Huggins polymer solution theory. The modeling of the temperature and pressure dependence of asphaltene
deposition, using an equation of state for vapor-liquid equilibrium, was reasonably successful. Chung (1992) also used a simple regular solution theory
approach for solid asphaltene liquid equilibrium and was able to fit solubility
data for asphaltene in various solvents at ambient conditions, but this method
seems unlikely in giving good results under typical reservoir conditions. His
regressed asphaltene molar volume is an order of magnitude smaller than
Hirschbergs and seems suspect as the specific gravity of asphaltene is unacceptably high. Finally, Kawanaka et al. (1991) used a similar approach
to Hirschberg but with a continuous mixture for the asphaltene phase, and
obtained good agreement with solvent titration experiments and correct qualitative behavior at reservoir pressures.
Hirschbergs model appeared to be a good starting point but was not easily incorporated into multi-flash as it treats asphaltene-liquid equilibrium separately from vapor-liquid equilibrium, which is physically unrealistic. Therefore, the approach chosen was to treat asphaltene as a solid phase in equilibrium with the reservoir fluid, which was used with an equation of state.
Multi-flash can handle either a pure solid phase or a solid mixture. Although
in reality an asphaltene deposit is a complex mixture, given the lack of experimental data on asphaltene compositions, it was decided to treat it as a
pure solid pseudo component phase in the examples investigated to date.

DATA COLLECTION
The input data required to build the method are:





a compositional analysis of the reservoir fluid

C7C molecular weight and gravity
the amount of asphaltene and resin in the oil
reservoir temperature.

A total of 33 samples of different crudes were collected from literature

and used. The following parameters should be available: compositional analyses, C7C density and molecular weight, reservoir temperature, asphaltene,

Empirical Equation for ADE

951

and resin weight percentage. These parameters were used to calculate upper
and lower onset pressure and saturation pressure and constructing ADE. The
compositional data collected and onset experimental pressures and satutation
are shown in Table 1 (Fahim and Andersen, 2005).
EQUATION DEVELOPMENT
The molecular weight and specific gravity of the heptane plus-fraction are
used as an input variable distinguishing the plus-fraction. The density and
molecular weight of the total plus-fraction is important in the proposed
method because it reflects the paraflinic-naphthenic-aromatic (PNA) content
of the plus-fraction. A large density indicates a high content of aromatic compounds and a low density indicates a high content of paraffinic and naphthenic
content. Extending the plus-fraction into C10 might increase the accuracy of
the proposed method. However, it would reduce its simplicity. No distinction
is made between iso-paraffins and normal paraffins for two reasons: first,
concentrations of these hydrocarbons are usually very small when compared
with methane and heptane plus-fraction, and second, the simulation results
have indicated minor change in the estimated pressure when iso and normal
are lumped as a single component. A similar treatment has been used by
Elsharkawy (2003) in predicting the saturation pressure by EOS.
The objective function in this case is:
P D f.H2 S; N2 ; CO2 ; C1 ; C2; : : : ; C7C; C7C; MWC7C; aspht%; Resin%; T/
(1)
where P is the calculated pressures (upper, saturation, and lower) of the
crude oil sample. The objective is to minimize the average relative error
(ARE) between measured (P) and estimated pressure for all the experimentally measured samples in this study. The average relative error is defined
as:
X

ARE D
.P Pcalc /=Pcalc =n
(2)
Multiple regression and error minimization resulted in the following empirical equations.
For the upper onset pressure the following equation is obtained:




Pons
u D 4:3243 H2 S C 2:6047 N2 C 0:6890 CO2 C 0:6503 C1

C 0:9273 C2 C 0:0086 C3
0:0811 CC
7
0:2003 Resin
with r 2 D 0:992.

3:981C4

0:5878 C5 C 0:1817 C6

C


0:1305MWCC
7 C 210:89 C7 C 0:908 Asph

0:8988 T C 0:001 T2 C 12:4148 LN.T/

(3)

Table 1. Crudes that were used in generation of ADE methods

952

Sample
no.

Mole%
H2 S

Mole%
N2

Mole%
CO2

Mole%
C1

Mole%
C2

Mole%
C3

Mole%
C4

Mole%
C5

Mole%
C6

Mole%
C7

C7C

MW
C7C

Asph.
Wt%

Resin
Wt%

T,
K

Upper
press.,
MPa

Sat.
press.,
MPa

Lower
press.,
MPa

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
39
30
31
32
33

0.000
0.000
0.000
0.050
0.370
0.000
0.013
0.000
0.000
0.000
0.000
0.000
3.220
3.220
3.220
3.220
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
1.510
0.370
0.050
0.050
0.050
0.050
0.050
0.050

0.000
0.570
0.970
0.090
0.090
0.800
0.070
0.480
0.480
0.480
0.480
0.510
0.490
0.490
0.490
0.490
0.480
0.480
0.480
0.480
0.800
0.210
0.210
0.310
0.310
0.690
0.090
0.090
0.090
0.090
0.090
0.090
0.090

0.830
2.460
0.200
1.020
1.220
0.050
0.910
0.920
0.920
0.920
0.920
1.420
11.370
11.370
11.370
11.370
0.920
0.920
0.920
0.920
0.050
2.560
2.560
3.020
3.020
2.000
1.220
1.020
1.020
1.020
1.020
1.020
1.020

40.690
36.370
27.550
42.410
23.990
51.020
43.080
43.430
43.430
43.430
43.430
6.040
27.360
27.360
27.360
27.360
43.430
43.430
43.430
43.430
51.020
25.200
25.200
44.290
44.290
29.770
23.990
42.410
42.410
42.410
42.410
42.410
42.410

11.630
3.470
7.430
10.780
10.140
8.090
10.690
11.020
11.020
11.020
11.020
7.000
9.410
9.410
9.410
9.410
11.020
11.020
11.020
11.020
8.090
7.080
7.080
6.360
6.360
14.400
10.140
10.780
10.780
10.780
10.780
10.780
10.780

7.150
4.050
9.020
6.920
8.390
6.020
6.860
6.550
6.550
6.550
6.550
6.860
6.700
6.700
6.700
6.700
6.550
6.550
6.550
6.550
6.020
5.560
5.560
4.880
4.880
9.460
8.390
6.920
6.920
6.920
6.920
6.920
6.920

3.540
1.930
6.140
4.460
5.330
3.970
4.400
4.490
4.490
4.490
4.490
4.180
3.980
3.980
3.980
3.980
3.490
3.490
3.490
3.490
3.970
6.200
6.200
4.620
4.620
5.300
5.330
4.470
4.470
4.470
4.470
4.470
4.470

2.860
1.570
4.160
3.290
4.390
3.210
3.230
3.530
3.530
3.530
3.530
4.160
3.200
3.200
3.200
3.200
3.530
3.530
3.530
3.530
3.210
4.920
4.920
3.710
3.710
3.950
4.390
3.290
3.290
3.290
3.290
3.290
3.290

2.410
1.620
3.160
2.860
4.690
2.670
2.810
2.700
2.700
2.700
2.700
3.160
1.980
1.980
1.980
1.980
2.700
2.700
2.700
2.700
2.670
3.940
3.940
2.890
2.890
4.020
4.690
2.860
2.860
2.860
2.860
2.860
2.860

30.870
47.960
41.390
28.110
42.190
24.170
27.940
26.880
26.880
26.880
26.880
66.680
32.290
32.290
32.290
32.290
26.880
26.880
26.880
26.880
24.170
43.330
43.330
29.920
29.920
29.450
41.390
28.110
28.110
28.110
28.110
28.110
28.110

0.930
0.959
0.856
0.853
0.874
0.875
0.846
0.865
0.865
0.865
0.865
0.902
0.877
0.877
0.877
0.877
0.865
0.865
0.865
0.865
0.875
0.832
0.832
0.833
0.833
0.860
0.874
0.852
0.852
0.852
0.852
0.852
0.852

217.0
329.0
217.9
209.0
245.5
368.9
205.2
228.1
228.1
228.1
228.1
281.0
248.8
248.8
248.8
248.8
228.1
228.1
228.1
228.1
368.9
208.7
208.7
213.1
213.1
230.3
245.5
209.5
209.5
209.5
209.5
209.5
209.5

1.240
15.800
1.200
0.550
0.900
4.600
0.260
1.300
1.300
1.300
1.300
7.800
1.400
1.400
1.400
1.400
1.300
1.300
1.300
1.300
4.600
0.940
0.940
0.490
0.490
1.500
3.300
0.500
0.500
0.500
0.500
0.500
0.500

4.6
8.3
7.3
7.3
7.0
7.6
7.4
7.0
7.0
7.0
7.0
7.5
10.4
10.4
10.4
10.4
18.8
18.8
18.8
18.8
13.5
4.6
4.6
6.4
6.4
2.1
2.3
11.3
11.3
11.3
11.3
11.3
11.3

386
373
365
322
386
361
384
389
313
354
414
377
361
383
400
422
372
377
383
389
361
328
394
328
394
383
386
322
339
355
372
389
425

65.0
35.6
20.1
65.5
27.4
36.4
42.7
42.9
52.0
44.0
42.0
20.8
37.2
27.9
25.2
26.2
46.6
44.8
43.7
42.2
36.1
26.2

33.0

26.2
27.2
59.9
53.5
49.6
46.8
49.1
40.5

27.4
20.1
12.9
17.6
12.6
29.4
21.8
23.1
22.2
22.6
22.7

17.0
18.4
19.7
20.8
21.9
22.3
22.3
22.4
29.0
10.8
8.4
23.4
20.3
17.2
11.8
17.6
19.7
20.4
21.3
22.4
23.4

14.0
12.0
9.7
8.2
6.9
26.4
12.7
13.5
12.3
13.0
13.5

10.7
18.8
16.1
20.3

13.3
26.1

13.0

9.5
8.8
9.5
10.6
10.5
11.9

Experimental values not available.

Empirical Equation for ADE

953

For the saturation pressure the following equation is obtained:

Psat D 1:1107 H2 S C 1:5585N2 C 0:5764 CO2 C 0:469 C1 C 0:0751 C2
C 0:7932 C3

0:314 C4

0:0284 MWCC
7

0:303 C5 C 0:763 C6

0:0217 CC
7


20:41 CC
7 C 0:011 Asph

0:025 Resin C 0:0296 T

(4)

with r 2 D 0:996:
For the lower onset pressure the following equation is obtained:

Pons
L D 7:115 H2 S

11:931 C3

17:603 N2
0:600 C4

C 0:569 MWCC
7

6:706 CO2
2:477C5

571:4:3 CC
7

4:842C1 C 8:098 C2

37:166 C6 C 0:201 CC
7

2:422 Asph

0:052 Resin

0:333 T C 139:32LN.T/

(5)

with r 2 D 0:992:
In all equations, P is the pressure in MPa, T is the reservoir temperature
in K, composition analysis of (N2 ; CO2 ; H2 S; C1 , :C6 ; CC
7 ) is in the mole
percent, MWC7C is the molecular weight of the heptane plus, and  C7C is
the specific gravity of the heptane plus fraction and Asph% and Resin% is the
weight percent of asphaltene and resin in the crude. It is important that the
summation of mole percentages of all components forming the hydrocarbon
must be equal to 100%. The degree of fitness of these equations are shown
in Figure 1. The range of variables used to develop Eqs. (3)(5) are given in
Table 2.
Estimation of Resin Content
Resin is a very important factor in asphaltene precipitation since it precipitates
simultaneously with asphaltene and its quantity should be known, but in
many cases resin content is not available for crude oil. A correlation has
been developed to estimate resin content of any crude by knowing asphaltene
Table 2. Summary of error analysis for the proposed empirical method
Upper pressure
ARE
AAE
R2

0.20
3.3
0.992

Saturation pressure
0.20
2.94
0.996

Lower pressure
0.98
5.83
0.991

954

M. A. Fahim

Figure 1. Comparison of experimental pressure and calculated pressure from empirical equations: (a) upper pressure, (b) saturation pressure, (c) lower pressure.

content, sulphure content, and American Petroleum Institute (API) gravity of

crude oil. A total of 37 different crudes (with known resin contents) were
used (Speight, 1993) to generate the proposed correlation. The objective is
to minimize the ARE between measured resin wt% and estimated resin wt%
for all the experimentally measured samples in this study. Multiple regression
and error minimization resulted in the following empirical equations:
Resin wt% D 0:326375 asph wt%

0:12388Oil wt%

C 6:089721S wt% C 0:493571API

(6)

with r 2 D 0:92:
It can be observed that properties used in this equation are measured at
ambient conditions, and we first assume that the resin and asphaltene % in
Eq. (6) will have the same values at high pressures. Resin and asphaltene that
precipitated on depressurizing redissolve at pressures lower than the saturation
pressures and that assumption might be justified.

Empirical Equation for ADE

955

COMPARISON WITH EQUATION OF STATE MODEL

The proposed model is compared with an equation of state model (EOS) and
with experimental data to show the accuracy of the proposed model.
The Soave-Redlich Kwong equation of state (SRK-EOS) is under consideration in this work because it is commonly used by the petroleum industry
for predicting phase behavior and volumetric properties of hydrocarbon reservoir fluid mixtures. The equation is given by:
P D

RT
V b

a
V .V C b/

(7)

where P is the pressure, V is the molar volume, T is the absolute temperature,

and R is the universal gas constant.
This equation can predict the upper, saturation, and lower pressures and
vapor/liquid equilibrium calculations. For saturation pressure, it has reasonable accuracy if the heptane plus-fraction of the hydrocarbon fluids is properly
characterized (Jhaveri and Youngren, 1988), but it has significant deviation
in predicting the upper and lower pressures.
The ADE is determined by performing flashes at varying pressures for
a number of temperatures. Flash calculations using a small pressure step
are used to locate the precipitation onset pressures. These calculated onset
pressures taken together define the asphaltene precipitation envelope.

TUNING OF EOS
It is important to know that when EOS is used to predict ADE (upper, saturation, and lower pressures), it shows good results for saturation pressure
while the upper and lower pressure have a large deviation from experimental
values (maximum deviation for upper pressure was 165% and for lower pressure 126%, while saturation pressure was 20%). The ranges of variables used
in this work are given in Table 3. To tune EOS, experimental onset pressures
at given temperatures were used. Then the critical properties (mainly critical
temperature and pressure) of the crude oils were changed. This will help in
adjusting the calculated values of upper and lower pressure by EOS. Table 4
and Figures 2 and 3 show the importance of tuning the EOS in the calculation
of upper and lower pressure.

Table 3. Ranges of variables used in the developing proposed empirical method

Min
Max

%,
H2 S

%,
N2

%,
CO2

%,
C1

%,
C2

%,
C3

%,
C4

%,
C5

%,
C6

%,
C7

,
C7C

MW,
C7C

W%,
Asph

W%,
resin

Res,
T(K)

0
3.22

0
0.97

0.05
11.37

6.04
51.02

3.47
14.4

4.05
9.46

1.93
6.2

1.57
4.92

1.62
4.69

24.17
73.56

0.832
0.959

205.2
368.9

0.26
15.8

2.08
18.8

322
433

Table 4. Comparison of untuned and tuned EOS in predicting ADE with empirical method versus corresponding experimental values
Upper ADE

Saturation

Lower ADE

956

No.

Exp

Empirical
method

EOS
not tuned

EOS
tuned data

EOS
tuned model

Exp

Empirical
method

EOS
not tuned

EOS
tuned data

EOS
tuned model

Exp

Empirical
method

EOS
not tuned

EOS
tuned data

EOS
tuned model

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
39
30
31
32
33

65.0
35.7
20.1
47.6
27.4
36.4
42.7
42.9
47.3
45.4
44.3
20.8
37.2
27.9
25.2
26.2
46.6
44.8
43.7
42.2
36.1
26.2

35.5

26.2
27.2
59.9
53.5
49.6
46.8
49.1
40.5

64.8
35.3
20.2
45.6
27.5
36.8
46.8
44.3
46.1
45.5
44.8
21.3
32.1
29.2
27.9
27.0
45.3
44.7
44.0
43.5
35.4
25.1
12.3
37.2
27.2
26.2
28.8
60.6
54.3
50.2
47.5
45.7
44.0

*
73.9
*
30.0
30.0
43.0
24.5
41.6
42.5
42.2
42.0
17.8
30.3
30.4
30.7
31.3
42.3
42.0
41.6
41.7
95.8
21.2
10.4
32.1
23.6
26.0
31.7
27.9
26.2
26.0
26.2
25.1
27.8

65.1
35.6
20.7
46.2
27.5
36.6
42.8
43.0
47.3
45.5
44.6
21.1
34.9
29.5
26.9
24.9
46.6
45.3
43.9
42.4
36.2
26.6

35.7

26.0
31.7
58.0
53.7
49.7
46.8
49.1
43.5

64.9
35.2
20.8
44.2
27.6
37
46.9
44.4
46.1
45.6
45.1
21.6
29.8
30.8
29.6
25.7
45.3
45.2
44.2
43.7
35.5
25.5
12.4
37.4
27
26
27.7
58.8
53.9
49.8
47.2
46.1
40.5

27.4
27.3
12.9
17.6
12.6
29.4
21.8
23.1
22.2
22.6
22.7

17.0
18.4
19.7
20.8
21.9
22.3
22.3
22.4
29.0
10.8
8.4
23.4
20.3
17.2
11.8
17.6
19.7
20.4
21.3
22.4
23.4

26.9
27.4
12.9
25.3
11.4
31.1
22.8
22.5
22.0
22.2
22.3
9.5
18.2
18.9
19.4
20.2
22.1
22.3
22.5
22.7
27.2
10.9
8.7
22.6
20.4
17.1
12.3
19.6
20.2
20.7
21.2
21.8
23.0

27.3
24.4
12.6
24.9
12.1
32.0
22.6
24.2
23.2
23.7
24.0
9.8
17.1
18.7
20.0
21.1
23.5
23.8
24.1
24.5
31.2
12.1
8.8
22.0
18.4
17.0
12.0
17.5
18.8
19.9
21.2
22.0
23.4

27.1
26.1
12.3
24.5
12.1
32.6
21.4
24.5
23.5
23.9
24.2

17.1
18.8
19.9
21.2
23.6
23.9
24.2
24.5
32.6
11.4
8.7
22.0
18.0
17.0
12.0
17.5
18.8
20.0
21.1
21.9
23.2

26.6
26.2
12.3
32.2
10.9
34.3
22.4
23.9
23.3
23.5
23.8
9.7
18.3
19.3
19.6
20.6
23.8
23.9
24.4
24.8
30.8
11.5
9
21.2
18.1
16.9
12.1
19.5
19.5
20.4
21.4
21.6
23.5

4.0
23.1
9.7
8.3
6.9
26.4
12.7
13.5
12.3
13.0
13.5

10.7
18.8
16.1
20.3

13.3
26.1

13.0

9.5
8.8
9.5
10.6
10.5
11.9

4.0
23.2
9.7
9.8
6.8
26.3
11.7
13.2
12.8
13.0
13.1
5.3
15.8
16.8
16.5
16.8
12.9
13.1
13.2
13.4
26.3
7.7
4.1
16.2
12.5
13.0
6.8
7.2
9.1
10.3
11.1
11.5
11.6

*
9.3
*
12.7
5.3
9.6
19.5
16.0
15.2
15.3
15.7
8.2
11.7
14.3
13.2
15.3
15.8
15.9
16.1
16.2
9.7
8.9
6.1
18.9
14.6
12.2
7.8
6.5
15.9
17.2
18.6
20.5
20.3

3.7
21.7
8.9
11.1
6.1
30.3
12.3
15.8
13.5
14.2
14.9

10.1
16.0
13.5
18.8

15.8
30.6

12.2

6.9
8.5
9.8
11.0
10.7
14.2

3.7
21.8
8.9
12.6
6
30.2
11.3
15.5
14
14.2
14.5
8
15.2
14
13.9
15.3
13.1
13.4
13.5
15.9
30.8
8
4.3
16
12.8
12.7
6.6
6.9
8.9
11.0
10.9
11.1
11.9

Experimental values not available.

 No convergence.

Empirical Equation for ADE

957

Figure 2. ADE comparison of proposed method with experimental, tuned, and untuned EOS (Crude 28).

Figure 3. ADE comparison of proposed method with experimental, tuned, and untuned EOS (Crude 9).

958

M. A. Fahim

The heaviest component can be divided into two componentsone is

nonprecipitating and the other is precipitating based on the weight of asphaltene in the crude. The mole fraction of asphaltene can be calculated according
to the following:
Zasph D Wt%asph  Moil =MWasph :

(8)

The asphaltene properties TC and PC are then tuned to satisfy the precipitation condition. Values of P  and fa can be found from extrapolation to 0
mole % precipitation.
RESULTS AND DISCUSSION
The accuracy of the empirical method is compared with the experimental
values reported from literature and with EOS (SRK). The statistical results
of various crude oils for the empirical method are shown in Table 2. This
table reports the average relative error (ARE) and the average absolute error
(AAE) for the 33 crude oil samples that were used to derive the equations. The
proposed method has the smallest errors for the measured saturation pressures
of the Middle East crudes that were used to develop the method. The current
method has the advantage of being simple and accurate, eliminating the need
for splitting the heptane plus-fraction.
It is important to know that as the number of points used to tune the
EOS increase, the accuracy of estimating ADE pressure increases. A sample
crude was taken and a different number of tuning points were used and shows
that with three points of tuning it gave ARE D 2.36 and the AAE D 6.52,
while using four points of tuning gave ARE D 2.75 and AAR D 4.69, and
using five points of tuning gave ARE D 0.031 and the AAE D 3.24. The
error analysis for EOS prediction is given in Tables 5 and 6.
A total of five samples of different crudes at different temperatures were
used for testing the proposed empirical equations (Table 7). Also three different crude samples were used to test the effect of gas injection and were compared with experimental values as shown in Table 8. The error analysis results
for crudes tested in Table 7 are shown in Table 9. Also an ADE for two different crudes was generated by the proposed equations and compared with experimental and tuned and untuned EOS as shown in Figures 2 and 3. As shown
Table 5. Summary of error analysis for ADE pressures calculated by
untuned EOS compared with experimental
Upper pressure
untuned EOS
ARE
AAE

9.40
30.40

Saturation pressure
untuned EOS
1.66
5.00

Lower pressure
untuned EOS
17.44
45.88

Empirical Equation for ADE

959

Table 6. Summary of error analysis for ADE pressures calculated by

tuned EOS compared with experimental
Upper pressure
tuned EOS
ARE
AAE

0.60
1.70

Saturation pressure
tuned EOS
1.44
4.66

Lower pressure
tuned EOS
0.49
11.90

in the figures, the proposed and tuned EOS are very close to experimental
data while the untuned EOS has a large deviation from experimental points.
Effect of Crude Properties and Composition on ADE
With many parameters such as gas injection, the changing of asphaltene
content has been studied and the effects of each one on ADE have been
studied. The crude oil stability increases as the asphaltene content increases.
Experience has shown that heavy precipitation of asphaltene occurs with
crude of low asphaltene content as in Hasi Masoud wells. The effect of initial
asphaltene content on ADE is predicted and compared with experimental data
as shown in Figure 4.

Figure 4. Effect of asphaltene mole% on ADE (Crude 28).

Table 7. Crudes used for testing the empirical method

No.

%,
H2 S

%,
N2

%,
CO2

%,
C1

%,
C2

%,
C3

%,
C4

%,
C5

%,
C6

%,
C7

,
C7C

MW,
C7C

W%,
Asph

W%,
resin

Res,
T(K)

34
35
36
37
38
39

1.900
0.099
0.014
0.013
0.013
0.050

0.090
0.317
0.065
0.173
0.070
0.090

2.110
0.830
0.920
0.841
0.914
1.020

29.500
27.800
44.221
40.054
43.079
42.410

13.710
9.560
10.902
10.346
10.689
10.780

9.310
8.000
7.217
7.046
6.861
6.920

5.320
5.170
4.427
4.608
4.396
4.470

4.030
4.070
3.072
5.237
3.233
3.290

4.150
4.410
2.554
3.025
2.814
2.860

29.880
39.740
26.608
30.413
27.931
28.110

0.832
0.846
0.853
0.846
0.845
0.852

209.8
223.2
215.9
204.8
204.1
209.5

0.500
0.900
0.500
0.500
0.400
0.500

1.050
1.530
0.860
6.000
7.900
11.300

397.1
391.6
390.4
392.1
388.8
432.7

960
Table 8. Crudes used for testing the empirical method for gas injection

No.

%,
H2 S

%,
N2

%,
CO2

%,
C1

%,
C2

%,
C3

%,
C4

%,
C5

%,
C6

%,
C7

,
C7C

MW,
C7C

W%,
Asph

Res,
T(K)

16
40
41

3.220
0.01
0.00

0.490
0.32
0.16

11.370
2.29
0.14

27.360
17.6
77.44

9.410
5.25
3.95

6.700
6.14
2.56

3.980
6.63
1.78

3.200
5.84
1.32

1.980
5.00
0.94

32.290
50.92
11.71

0.877
0.852
0.86

248.8
210
233.6

1.400
1.00
8.3

400
389
342

Empirical Equation for ADE

961

Table 9. Error analysis for crude used to test the empirical method
Pupper, Bar

Psat , Bar

Plower , Bar

No.

Exp

Calc

Exp

Calc

Exp

Calc

34
35
36
37
38
39

25.9
23.1
55.1
51.7
52.4
44.1
ARE
AAE

26.0
21.3
55.1
51.3
46.8
44.0
3.18
3.40

16.2
13.5

20.8
23.8
23.6
ARE
AAE

16.3
14.2

20.9
22.6
23.0
0.42
2.64

10.8
9.0

8.0
12.2
12.0
ARE
AAE

10.8
9.1

8.0
12.5
11.5
0.43
2.43

Table 10. Properties of injected gases

No.

%,
H2 S

%,
N2

%,
CO2

%,
C1

%,
C2

%,
C3

%,
iC4

%,
nC4

%,
iC5

%,
nC5

%,
C6

%,
C7

MW

1
2
3
4

0.03
0.00
0.00
0.00

0.59
1.00
0.00
0.00

5.03
0.00
1.00
0.00

65.76
0.00
0.00
0.00

11.32
0.00
0.00
0.00

8.58
0.00
0.00
1.00

2.16
0.00
0.00
0.00

3.62
0.00
0.00
0.00

1.24
0.00
0.00
0.00

1.14
0.00
0.00
0.00

0.51
0.00
0.00
0.00

0.03
0.00
0.00
0.00

25.6
28.0
44.0
44.0

The upper onset pressure equation was used to investigate the effect of
injection of different gases such as scrubber gas (CO2 ) and H2 S; N2 ; C3 , and
natural gas. A list of gases used is given in Table 10. The results of the
injection of nitrogen, gas 1, and C3 on the upper part of ADE and saturation
pressure are shown in Figures 5, 6, and 7. In these figures the prediction by
the corresponding equation and EOS is also shown.
It is important to note that EOS can be tuned using the onset point
generated in this work, and consequently, it can be used to determine the
percentage of asphaltene precipitated. Figure 8 shows the effect of CO2 injection on asphaltene precipitation obtained by EOS tuned by a proposed
model compared to experiential values.

CONCLUSIONS
The empirical methods that have been proposed to estimate upper, saturation,
and lower pressure of ADE for any crude oil have several advantages over the
equation of state. It is simple and gives an approximate estimation for ADE and
eliminates the need for splitting and characterizing the heptane plus-fraction.

962

M. A. Fahim

Figure 5. Effect of N2 injection on upper onset pressure and saturation pressures

calculated from a proposed model versus experimental (Crude 16).

Figure 6. Effect of gas (gas 1) injection on upper onset pressure and saturation
pressures calculated from a proposed model versus experimental (Crude 40).

Empirical Equation for ADE

963

Figure 7. Effect of C3 injection on saturation pressures calculated from a proposed

model versus experimental.

Figure 8. Effect of CO2 injection on asphaltene precipitation. Comparison of experimental with EOS tuned with model (Crude 2).

964

M. A. Fahim

The proposed methods were tested with different crude oils and were also
tested against EOS and the result was satisfactory. The EOS has a large
deviation compared to the proposed method and experimental values and
tuning of the EOS is very important and will improve it. Injection of different
gasses also showed that the model gave a satisfactory result compared to the
EOS that requires splitting of C7C into different subtractions.

ACKNOWLEDGMENT
M. A. Fahim would like to thank Kuwait University for granting him a sabbatical year (2002/2003), where he spent a portion of it at Denmark Technical
University.

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Burke, N. E., Hobbs, R. D., and Kashon, S. F. (1990). J. Petrol. Technol.
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Hirschberg A., DeJong, L., and Meijer, J. (1984). Soc. Petrol. Eng. 24:283.
Huggins, M. (1941). Chem. Phys. 9:440.
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Jamaluddin, A. K. M., Creek, J., McFadden, C. S., DCruz, D. Thomas, J.,
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Kabir, C. S., and Jamaluddin, A. K. M. (1990). SPE J. 53155.
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Vafaie-Sefti, M., et al. (2003). Fluid Phase Equil. 260:111.

Empirical Equation for ADE

NOMENCLATURE

L
V

!
a
b
fL
fV
K
MW
n
P
Pc
R
r2
T
Tc
V
w
x
y
z

Dimensionless factor
Dimensionless factor
Fugacity coefficient liquid phase
Fugacity coefficient in vapor phase
Density
Acentric factor
First parameter in EOS
Second parameter in EOS
Fugacity in liquid phase
Fugacity in vapor phase
Equilibrium coefficient
Molecular weight
Number of components
Pressure
Critical pressure
Gas constant
Correlation coefficient
Temperature
Critical temperature
Molar volume
Weight fraction
Mole fraction in liquid phase
Mole fraction in gas phase
Mole fraction in feed

965