SPE 166097

High Pressure Data and Modeling Results for Phase Behavior and
Asphaltene Onsets of GoM Oil Mixed with Nitrogen
Odd Steve Hustad, Statoil ASA / NTNU, Na Jenna Jia, Schlumberger DBR Technology Center, Karen Schou
Pedersen, Calsep A/S, Afzal Memon, Schlumberger DBR Technology Center, Sukit Leekumjorn, Calsep Inc
Copyright 2013, Society of Petroleum Engineers
This paper was prepared for presentation at the SPE Annual Technical Conference and Exhibition held in New Orleans, Louisiana, USA, 30 September2 October 2013.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the S ociety of Petroleum Engineers and are subject to correction by the a uthor(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or st orage of a ny part of this paper without the written consent of the Society of Pet roleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
This paper presents high pressure PVT measurements and equation-of-state (EoS) modeling results for a GoM oil and for the oil
mixed with nitrogen in various concentrations. The data includes:
1.

2.
3.

Upper and lower asphaltene onset pressures and bubble point pressures for the reservoir fluid swelled with nitrogen. At the
reservoir conditions of 94 MPa (13,634 psia) and 94C (201.2F) asphaltene precipitation is seen after addition of 27 mole %
of nitrogen.
Viscosity data for the swelled fluids showing that addition of nitrogen significantly reduces the oil viscosity.
Slim tube runs indicating that the minimum miscibility pressure of the oil with nitrogen is significantly higher than estimated
from published correlations.

The data has been modeled using the volume corrected Soave-Redlich-Kwong (SRK) and the Perturbed-Chain Statistical
Association Fluid Theory (PC-SAFT) EoS. While both equations provide a good match of the PVT properties of the reservoir fluid,
PC-SAFT is superior to the SRK EoS for simulating the upper asphaltene onset pressures and the liquid phase compressibility of the
reservoir fluid swelled with nitrogen.
Nitrogen gas flooding is expected to have a positive impact on oil recovery due to its favorable oil viscosity reduction and phase
behavior effects.
Introduction
Oil exploration is going into regions of more extreme conditions and large oil deposits (0.3 to 4 billion BOE) are discovered in
deepwater (~2,000 m / 6,500 ft) Gulf of Mexico (GoM). Many of these deepwater reservoirs were formed during the Paleogene
geological period (lower Tertiary) and are posing a significant challenge to exploit. These reservoirs are found at approximately
8,000 m (26,000 ft) true vertical depth (TVD) and consists of Turbidite deposits under-laying thick salt deposits. The salt deposits
pose significant challenges for seismic interpretation. The oils are highly undersaturated with low bubble point pressure (~17 MPa /
~2,500 psia) and fairly reasonable temperatures (~100C / 212F). Undersaturated oils have little expansion energy. Characteristic
for these reservoirs are also their low permeability (1 30 mD). The high initial pressures (125 to 175 MPa / 18,000 to 25,000 psia)
in these reservoirs make it necessary with a primary production by pressure depletion. However, producing these reserves by
pressure depletion will only result in recovery factors in the range of 6 to 12%.
These low recoveries with large in-place oil volumes give incentives to investigate alternative drainage strategies to obtain an
Increased Oil Recovery (IOR). Water or gas injection processes are traditional IOR processes. However, making these processes
profitable presents some challenges. High cost wells (> 350 million USD per well) limits the number of wells that can be drilled for

SPE 166097

a particular reservoir. Injectivity in low permeable formations may hinder getting injection fluids into the reservoir. This is more
severe for water than for gas, especially when the displacement distances are taken into consideration. For these highly
undersaturated reservoirs gas injection may lead to asphaltene precipitation in the reservoir. Understanding these phenomena and
enabling appropriate forecasts of the impact of the gas injection is highly challenging.
The extreme conditions present other technical challenges, which need to be overcome.1 The well technologies and reservoir
technologies all have their specific technical challenges. The DeepStar technology development project, managed by Chevron and
supported by several operators, is a forum for advancing deepwater technologies.2 It is highly desirable to have the capability to
perform high pressure measurements and it is important that results from such measurements are made available to the oil
community.
Gas injection is a proven IOR process that can be economical and increase oil recovery. Gas injection will make the reservoir fluid
swell and will therefore help maintain the reservoir pressure and prolong the production rates. Gas injection may however cause
asphaltene precipitation and its impact to reservoir dynamics needs to be better understood. Asphaltene precipitation phenomena
have been studied by many authors.3-9
Presented below are results from a phase behavior study on GoM oil at high pressure. The oil has been mixed with varying amounts
of nitrogen and its properties measured. Fluid compositions, asphaltene onset and disappearance pressures are presented along with
constant mass expansion (CME) results, oil viscosities and slim tube measurements. The results show that two liquid phases are
formed prior to asphaltene precipitation and the emergence of a gas phase at 94 MPa. The oil viscosity is reduced by a factor two
during the swelling process. The minimum miscibility pressure is significantly higher than results obtained from correlations in the
literature.10-13 Phase equilibrium modeling of the measured data is presented using the Soave-Redlich-Kwong14 (SRK) EoS and the
PC-SAFT15 EoS. The established EoS models were able to reproduce the measured data. The PC-SAFT EoS is slightly superior to
the SRK EoS.
Phase Behavior Measurements
In depth studies are required to understand the possible outcome of gas injection into low permeable Turbidite formations in high
pressure GoM reservoirs. The first step in this study is to map the phase behavior properties of the selected oil when mixed with
nitrogen gas and to validate the measurements by modeling the data. In this study nitrogen (N2) is used as injection gas. The phase
behavior studies are at high pressures (94 MPa) for varying concentrations of N2. A similar study has been conducted by Gonzalez
et al.3 where variations in pressure and temperature were the main focus.
A TBP distillation was performed on the Stock Tank Oil (STO) sample to obtain data for the molar concentration, molecular weight
and density of the heavy components of the oil. The results are listed in Table 1. The STO was recombined with a synthetic gas to
obtain single phase reservoir oil, the compositions and properties of which are shown in Table 2.
Titration at 94 MPa and 94C was conducted with N2 to obtain the Asphaltene Onset Concentration (AOC). During the N2 titration
test an unknown second liquid phase appeared at 24 26 mol% nitrogen added. The second liquid phase seemed to have similar
density as the first liquid phase. Asphaltene precipitation was observed at 26 to 28 mol% nitrogen added. Figure 1 shows pictures
taken from a High Pressure Microscope (HPM) at two conditions with 26 and 28 mol% added nitrogen. A Solid Detection System
(SDS) analysis was also performed to confirm the visual results.
Table 3 presents the phase volumes from the swelling of the oil with nitrogen. The oil volume is increased by 12% prior to
asphaltene precipitation (~28 mol% N2 added) at 94 MPa and 94C.
Four additional fluid mixtures were created with varying amounts of nitrogen. The original recombined oil (labeled M0) had a
nitrogen concentration of 0.121 mol%. The first three of the additional samples contained respectively 8.853 (M1), 17.244 (M2),
and 25.925 (M3) overall mol% of N2. The last M4 mixture, with 67 mol% overall N2 concentration, split into two phases at 94 MPa
and 94C where the vapor and liquid nitrogen mol% were 79.937 and 38.231 respectively.

SPE 166097

The asphaltene onset pressure (AOP), saturation pressure and asphaltene disappearance pressure (ADP) were measured for these
fluid systems and are summarized in Figure 2 and Table 4. The AOP increases approximately linearly with increasing nitrogen
concentration. The ADP is low as compared to the saturation point and first decreases and then increases as the overall nitrogen
content increases. Once the gas concentration in the oil gets below a limiting value at ADP, due to pressure reduction, the
asphaltene will redissolve. Redissolution of asphaltene generally takes some time. In the experiments with precipitated asphaltene
(Mixtures M1, M2 and M3), enough time was probably not taken for complete equilibrium to be reached. Thus, a probable
explanation for the observed decrease in ADP may be kinetic effects.

Fig. 1 - HPM pictures of a) second liquid phase with 26 mol% added N2 and b) asphaltene precipitation with 28 mol%
added N2
140

Pressure (MPa)

120
100
80

Bubble Point Pressure

AOP (SDS+HPM)
ADP (PVT+SDS+HPM)
AOP (PVT+SDS+HPM)
Trendline (Psat)
Trendline (ADP)
Trendline (AOP)

60
40
20
0

10

20

30

40

50

60

70

N2 Concentration (mol%)

Fig. 2 - p-x phase envelope for reservoir fluid swelled with nitrogen at 94C
Constant Mass Expansion (CME) experiments were performed for four of the five mixtures. The results are illustrated in Figure 3.
The following was observed:
a. The relative volume curves become less abrupt at the saturation pressure as the concentration of nitrogen increases. This is
due to the oil becoming more volatile.
b. Above the saturation pressure the oil density increases almost linearly with pressure and the linear trend becomes more
pronounced as the concentration of nitrogen increases.
c. The slope of the Y-factor is similar for the M0, M1 and M2 mixtures, but is different for M3, which is a mixture close to
the AOC at 94 MPa. More asphaltene is precipitated for this mixture affecting the measured volumes below the saturation
pressure.
d. The compressibility pattern for the recombined reservoir fluid deviates from that seen for the fluids with added nitrogen
(M1, M2 and M3). The slopes of the compressibilities for the latter three mixtures are fairly similar.
The oil viscosity was measured with an electromagnetic viscometer (EMV), model SPL440. As can be seen from Table 5 and
Figure 4 the oil viscosity as a result of the N2 swelling dropped to half its original value. Once an equilibrium vapor phase was
formed, the equilibrium oil viscosity increased to a value slightly above its original value. This is explained by lighter and
intermediate components from the oil phase entering into the nitrogen rich equilibrium vapor phase. At 94 MPa the oil viscosity
changes linearly with nitrogen concentration during the swelling process.

SPE 166097

The various mixtures of oil were flashed to standard conditions and the STOs Refractive Indices (RI) were measured. The results
are listed in Tables 6 and 7. This data can possibly be applied with the ASIST method for asphaltene analysis.4
An attempt was made to experimentally determine the minimum miscibility pressure (MMP). The MMP was not reached at the
maximum operation pressure of 69 MPa. The runs at 94 C were conducted at 45, 55 and 68.4 MPa with oil recoveries of 70%,
75.5% and 83.2% respectively as can be seen from Table 8. Figure 5 illustrates the slim tube results and an extrapolation line is
added to the data indicating that the MMP is significantly higher. The indications are that the MMP value may be above 94 MPa.
This value is almost twice the value that may be obtained from correlations in the literature.10-13

Fig. 3 - CME result at 94C for reservoir fluid with varying nitrogen concentrations

Fig. 4 Oil viscosity at 94C for reservoir fluid with varying nitrogen concentrations

SPE 166097

Fig. 5 Slim tube oil recoveries with N2 injection at 94C

Data Evaluation
The compositions from the TBP distillation and gas chromatography (GC) were compared. Figure 6 demonstrates that the GC data
differs from the TBP distillation data. The C30+ weight % found in two TBP tests agrees well with each other. However, C30+ weight
% from GC analysis is 35.61 while the average C30+ weight % from TBP analyses is 40.42. The GC and TBP distillation are two
different processes for compositional analyses and both methods have some limitations. The TBP analysis result is influenced by
the carry-over of components from one carbon-number range to another range, temperature control and losses (especially light
ends). The GC analysis results are influenced by the sample preparation issues, GC procedure and possible loss of heavy ends in the
GC column. Moreover, the mol% results are found from the weight % composition using published default molecular weights.16
Application of correct molecular weights for individual fractions in the characterization of models is essential when establishing the
fluids molar composition. Weight % results are actual raw data from TBP and GC analyses and they should be used as such in
tandem with correct molecular weights for the fluid that is being studied.
For modeling purpose in this work, reliance was given to the TBP data. The C36+ molecular weight from TBP was 833.7. Figure 7
shows two extrapolated molecular weight curves representing C36+ molecular weights of 833.7 and 725. The later of these values
seem to coincide better with the C7-C35 trend. A C36+ molecular weight of 808 was used in establishing the models based on
adjustment for a gas/oil ratio of 102.2 Scm3/Scm3 and a STO density of 0.88 g/cm3.
The reservoir fluid composition when recombining GC analysis and TBP analysis is shown in Table 9.

Fig. 6 Boiling point data for stabilized oil

Fig. 7 Extrapolated C36+ molar distribution assuming

C36+ molecular weights of 833.7 and 725

Phase Behavior Modeling

One of the objectives of the experimental program was to establish EoS models describing the experimental data. This would be a
requirement to perform compositional reservoir simulation studies of the impact of gas injection.
Three EoS models have been established based on the measured data:

SPE 166097

22 component PC-SAFT Model15

22 component SRK-Peneloux EoS Model14,17
Nine component SRK-Peneloux EoS Model

The PC-SAFT EoS model parameters were found using the characterization procedure presented by Pedersen et al.18 The
characterization procedure of Pedersen et al.19 was used to find the SRK model parameters and the associated volume corrections.
The model parameters are listed in Tables 10, 11 and 12. The last component in each of these models represents the asphaltene
components, which are assumed to be in the C50+ aromatic fraction.20
Figure 8 illustrates how well the EoS models reproduce the p-x phase envelope data. As may be seen the saturation pressure and
AOP are represented fairly well. However, the simulated ADPs are higher than the measured values. The ADP is primarily
determined by the gas concentration in the liquid phase. Asphaltenes will redissolve when the gas concentration is below a limiting
value, which is almost constant with pressure. The data suggests that the gas concentration in the liquid phase at the ADP should be
lower when more N2 was added to the total mixture. The reason is rather that there is more asphaltene to redissolve when higher N2
amounts were added, i.e. the low ADPs seen when more N2 is added may be due to kinetic effects and simply show that the
asphaltene may require longer time to redissolve in the oil than the two hours allocated in the experimental procedure.

(a) 22 Comp PC-SAFT EoS

(b) 22 Comp SRK-P EoS
(c) 9 Comp SRK-P EoS
Fig. 8 Experimental and simulated phase envelopes for reservoir fluid swelled with N2 at 94C
Figure 9 shows experimental and simulated CME density data for the fluid mixtures M0, M1, M2 and M3 using the 22 component
PC-SAFT and SRK-Peneloux models. The oil density of the reservoir fluid is matched very well while the simulated densities are
up to 1.5% higher than the experimental values for the mixtures with nitrogen. Figure 10 shows experimental and simulated oil
compressibilities. Figure 10a is for the reservoir fluid, for which the SRK equation provides a better match at the higher pressures
while the PC-SAFT performs better at the lower pressures. As the nitrogen content is increased the PC-SAFT model becomes
superior to SRK at all pressures. The compressibilities may play an important role when evaluating gas injection. A more
compressible fluid will keep the pressure higher when the field is produced than a less compressible fluid. Since three phases are
present between the saturation pressure and the ADP, the CME simulations were carried out using a multiflash algorithm21,22 and the
simulated oil densities and compressibilities are weighted averages between the oil and the asphaltene phases. Figure 11 shows
experimental and simulated Y-factors. The Y-factor is defined as

psat p
psat
1
p
p
Y factor

Vtot Vsat Vtot

1
Vsat
Vsat

(1)

and experimentally determined from the absolute measured volumes. Near the saturation point the measured volumes of the
disappearing phase are small and this may partly explain the deviations seen between the simulated and experimental Y-factors.

SPE 166097

(a) Recombined oil (M0)

(b) Fluid mixture M1

(c) Fluid mixture M2

(d) Fluid mixture M3
Fig. 9 Experimental and simulated CME oil densities at 94C with 22 component PC-SAFT and SRK EoS

(a) Recombined oil (M0)

(b) Fluid mixture M1

(c) Fluid mixture M2

(d) Fluid mixture M3
Fig. 10 Experimental and simulated CME oil compressibilities at 94C with 22 component PC-SAFT and SRK EoS

SPE 166097

(a) Recombined oil (M0)

(b) Fluid mixture M1

(c) Fluid mixture M2

(d) Fluid mixture M3
Fig. 11 Experimental and simulated CME oil Y-factors at 94C with 22 component PC-SAFT and SRK EoS
The principle of corresponding states (CSP)20 resulted in good match of the oil viscosities as shown in Table 5. No tuning of the
model parameters to the experimental data was conducted.
Conclusions
Compositional data and PVT data are presented for a GoM reservoir fluid. A TBP analysis was performed to ensure a good
compositional description of the heavy end components. The PVT data includes measured upper and lower asphaltene onset
pressures for the reservoir fluid swelled with nitrogen and CME data for the swelled fluids.
The results indicate:
1. The asphaltene upper envelope increases almost linearly with increasing nitrogen concentration.
2. The asphaltene lower envelope is lower than what is modeled and does not behave as expected with increase in nitrogen
concentration, which may be due to kinetic effects.
3. During the oil titration with nitrogen a second liquid phase appeared between the M2 and M3 mixture compositions and
prior to asphaltene precipitation at 94 MPa and 94C.
4. The oil viscosity was reduced to half its original value before reaching the asphaltene nitrogen onset concentration at 94
MPa and 94C.
The PC-SAFT and SRK EoS performed well in representing the p-x phase envelope and the asphaltene upper onset pressure. The
lower asphaltene envelope may have some kinetic issues influencing the results.
The PC-SAFT EoS was superior to the SRK EoS in representing the oil compressibility with high concentrations of nitrogen.

Nomenclature

SPE 166097

Symbols
p
psat
T

Pressure
Saturation Pressure
Temperature

Vsat
Vtot
zi

Volume at saturation pressure

Total Volume
Overall mole % of component i

Acronyms
AOC
ADP
AOP
API
BOE
CME
CSP
EMV
EoS
GC
GoM
GOR
HPM

Asphaltene Onset Concentration

Asphaltene Disappearance Pressure
Asphaltene Onset Pressure
American Petroleum Institute
Barrel of Oil Equivalent
Constant Mass Expansion
Corresponding States Principle
Electromagnetic Viscometer
Equation of State
Gas Chromatography
Gulf of Mexico
Gas/Oil Ratio (scf/STB or Scm3/Scm3)
High Pressure Microscope

IOR
MW
PVI
PVT
RF
RI
scf
SDS
STO
STB
STP

Increased Oil Recovery

Molecular Weight
Pore Volume Injected
Pressure-Volume-Temperature
Recombined Reservoir Fluid
Refractive Index
Standard cubic feet (ft3)
Solid Detection System
Stock Tank Oil
Stock Tank Barrels
Standard Temperature and Pressure (T= 15.6
C or 60 F; p= 1.013 bar or 14.696 psia)

Acknowledgement
Statoil is acknowledged for the permission to publish these results and for the financial support. Saybolt/CoreLab, The Netherlands,
and CanMet, Edmonton Canada, are acknowledged for conducting the TBP distillation analysis. Acknowledgement is given to
Donavon Robinson and Michael Rudneski for performing a majority of the PVT, asphaltene and slim tube measurements.
References
1. Mazerov, K. 2012. HPHT Research Heats Up. Drilling Contractor (July/August).
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Technology for Deep Water. Paper presented at the 2007 Offshore Technology Conference, Houston, 30 April 3 May. Doi:
10.4043/11511-MS.
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Reservoir Oil: Experimental Investigation of Asphaltene Precipitation and Deposition. Paper SPE 159098 presented at the
SPE Annual Technical Conference and Exhibition, San Antonio, 8-10 Oct.
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Petroleomics. O.C. Mullins, E.Y. Sheu, A. Hammami and A.G. Marshall Editors, Springer, New York.
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14 (4): 235-245. SPE-59092-PA. Doi: 10.2118/59092-PA.
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Canadian Petroleum Technology 41 (7): 44-52. Doi: 10.2118/01-07-04.
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Injection. Paper SPE 74393 presented at the SPE International Petroleum Conference and Exhibition in Mexico, Villahermosa,
10-12 February. Doi: 10.2118/74393-MS.
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Houston, 5-8 May.
9. Memon, A. et al. 2012. Miscible Gas Injection and Asphaltene Flow Assurance Fluid Characterization: A Laboratory Case
Study for Black Oil Reservoir. Paper presented at the SPE EOR Conference of Oil and Gas West Asia, Muscat, Oman, 16-18
April. Doi: 10.2118/150938-MS.
10. Glas, . 1990. Miscible Displacement: Recovery Test with Nitrogen. SPE Reservoir Engineering 5 (1): 61-68. Doi:
10.2118/17378-PA.
11. Hudgins, D. A., Llave, F. M. and Chung, F. T. H. 1990. Nitrogen Miscible Displacement of Light Crude Oil: A Laboratory
Study. SPE Reservoir Engineering 5 (1): 100-106. Doi: 10.2118/17372-PA.

10

SPE 166097

12. Hanssen, J. E. 1988. Nitrogen as a Low-Cost Replacement for Natural Gas Reinjection Offshore. Paper SPE 17709 presented
at the SPE Gas Technology Symposium, Dallas, 13-15 June.
13. Sebastian, H. M. and Lawrence, D. D., 1992. Nitrogen Minimum Miscibility Pressure. Paper SPE/DOE 24134 presented at the
SPE/DOE Eighth Symposium on Enhanced Oil Recovery, Tulsa, 22-24 April.
14. Soave, G. 1972. Equilibrium Constants from a Modified Redlich-Kwong Equation of State. Chem. Eng. Sci., Vol. 27, 11981203.
15. Gross, J. and Sadowski, G. 2001. Perturbed-Chain SAFT: An Equation of State Based on a Perturbation Theory for Chain
Molecules. Ind. Eng. Chem. Res. 40 (4): 1244-1260. Doi: 10.1021/ie0003887.
16. Katz, D. L. and Firoozabadi, A. 1978. Predicting Phase Behavior of Condensate/Crude-Oil Systems Using Methane
Interaction Coefficients. JPT 30 (11): 1649-1655. Doi: 10.2118/6721-PA.
17. Peneloux, A., Rauzy, E. and Frze, R. 1982. A Consistent Correction for Redlich-Kwong-Soave Volumes. Fluid Phase
Equilibria 8 (7).
18. Pedersen, K. S., Leekumjorn, S., Krejbjerg, K. and Azeem, J. 2012. Modeling of EOR PVT Data using PC-SAFT equation.
Paper presented at the Abu Dhabi International Petroleum Exhibition & Conference, Abu Dhabi, UAE, 11-14 November. Doi:
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and Estimated Compositional Data for the Plus-Fraction. Ind. Eng. Chem. Res. 31, 1378.
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22. Michelsen, M. L. 1981. The Isothermal Flash Problem. Part II. Phase Split Calculations. Fluid Phase Equilibria 9 (21).

Table 1. Distillation Data on Stock Tank Oil

Density at

TBP Cut

15 C

(C)

(g/cm )

Loss

Weight

Cumulative

Volume

Cumulative

(%)

Weight %

(%)

% Volume

0.22

0.22

C4 Minus

0.5527

0.38

0.60

0.61

0.83

C5-36.6

0.6225

0.88

1.48

1.24

2.07

36.6-69.3

0.6677

1.62

3.10

2.14

4.21

69.3-98.9

0.7170

3.07

6.17

3.77

7.98

98.9-126.2

0.7408

3.73

9.90

4.44

12.42

126.2-151.3

0.7617

3.59

13.49

4.16

16.58

151.3-196.4

0.7852

6.78

20.27

7.61

24.19

196.4-254.0

0.8154

8.55

28.82

9.25

33.44

254.0-302.8

0.8461

8.74

37.56

9.11

42.55

302.8-344.4

0.8645

6.94

44.50

7.08

49.63

344.4+

0.9692

55.50

100.00

50.49

100.12

344.4-402.2

0.8884

7.99

52.49

7.93

57.56

402.2-450.0

0.9035

5.32

57.81

5.19

62.75

450.0-490.6

0.9240

6.87

64.67

6.55

69.30

490.6+

1.0093

35.33

100.00

30.86

100.16

0.8817

28.89

STO (ASTM D
1298)
STO API Gravity

Table 2a. Composition Analysis of Recombined Reservoir Fluid

Component
CO2

MW

Flashed Gas

Flashed Oil

Monophasic Fluid

(g/mol)

(Wt%)

(Mole %)

(Wt%)

(Mole %)

(Wt%)

(Mole %)

44.01

0.205

0.121

0.000

0.000

0.023

0.065

SPE 166097

11

H2S

34.08

0.000

0.000

0.000

0.000

0.000

0.000

N2

28.01

0.243

0.225

0.000

0.000

0.027

0.121

C1

16.04

42.661

68.963

0.000

0.000

4.818

37.091

C2

30.07

11.507

9.924

0.000

0.000

1.300

5.338

C3

44.1

16.609

9.769

0.178

0.959

2.034

5.697

i-C4

58.12

2.972

1.326

0.072

0.293

0.399

0.849

n-C4

58.12

10.461

4.668

0.414

1.687

1.548

3.290

i-C5

72.15

3.700

1.330

0.396

1.300

0.769

1.316

n-C5

72.15

4.436

1.595

0.667

2.191

1.093

1.870

C6

84

3.488

1.077

1.633

4.608

1.842

2.709

Mcyclo-C5

84.16

0.505

0.156

0.369

1.041

0.385

0.565

Benzene

78.11

0.060

0.020

0.052

0.157

0.053

0.083

Cyclo-C6

84.16

0.400

0.123

0.330

0.929

0.338

0.496

96

1.350

0.365

2.248

5.550

2.146

2.761

Mcyclo-C6

98.19

0.412

0.109

0.825

1.992

0.778

0.979

Toluene

92.14

0.094

0.026

0.237

0.610

0.221

0.296

107

0.479

0.116

2.963

6.564

2.682

3.096

C7

C8
C2-Benzene

106.17

0.027

0.007

0.187

0.417

0.169

0.196

m&p-Xylene

106.17

0.018

0.004

0.392

0.876

0.350

0.407

o-Xylene

106.17

0.012

0.003

0.177

0.395

0.158

0.184

C9

121

0.248

0.053

2.860

5.604

2.565

2.618

C10

134

0.091

0.018

3.814

6.748

3.394

3.128

C11

147

0.017

0.003

3.355

5.410

2.978

2.502

C12

161

0.004

0.001

3.109

4.577

2.758

2.116

C13

175

0.001

0.000

3.335

4.517

2.958

2.088

C14

190

0.001

0.000

3.074

3.835

2.727

1.773

C15

206

0.000

0.000

3.234

3.721

2.868

1.720

C16

222

0.000

0.000

2.814

3.005

2.496

1.389

C17

237

0.000

0.000

2.764

2.764

2.451

1.278

C18

251

0.000

0.000

2.743

2.591

2.434

1.198

C19

263

0.000

0.000

2.641

2.380

2.342

1.100

C20

275

0.000

0.000

2.336

2.014

2.072

0.931

C21

291

0.000

0.000

2.245

1.829

1.991

0.845

C22

305

0.000

0.000

2.122

1.649

1.882

0.762

C23

318

0.000

0.000

2.015

1.502

1.788

0.694

C24

331

0.000

0.000

1.921

1.376

1.704

0.636

C25

345

0.000

0.000

1.823

1.253

1.617

0.579

C26

359

0.000

0.000

1.790

1.182

1.588

0.546

C27

374

0.000

0.000

1.758

1.115

1.560

0.515

C28

388

0.000

0.000

1.743

1.065

1.546

0.492

C29

402

0.000

0.000

1.758

1.037

1.560

0.479

C30+

750

0.000

0.000

35.610

11.256

31.588

5.202

Calculated
MW (g/mol)
Mole Percent

25.9

237.1

53.78

46.22

Table 2b. Property of Recombined Reservoir Fluid

STO Properties at
Standard Condition

Measured

MW
Density (g/cc)

0.880

Calculated

C30+
Properties

237

750

0.880

1.034

123.5

12

SPE 166097

Single Stage Flash Data

3

GOR (Scm /Scm )

102.3
3

STO Density (g/cm )

0.880

STO API Gravity

29.1

Mass Balance Error (wt%)

0.56

Properties

Flashed Gas

Flashed Oil

Monophasic

C 7+

0.70

86.84

40.51

C10+

0.02

64.83

29.97

C12+

0.00

52.67

24.34

C20+

0.00

25.28

11.68

C30+

0.00

11.26

5.20

C 7+

2.75

95.89

85.37

C10+

0.11

86.00

76.30

C12+

0.01

78.83

69.93

C20+

0.00

55.12

48.90

C30+

0.00

35.61

31.59

Mole %

Weight %

Molar Mass
C 7+

101.34

261.79

260.29

C10+

137.05

314.51

314.44

C12+

167.42

354.84

354.83

C20+

516.97

516.97

C30+

750.00

750.00

Density (g/cc)
C 7+

0.745

0.893

0.893

C10+

0.781

0.912

0.912

C12+

0.805

0.926

0.926

C20+

0.974

0.974

C30+

1.034

1.034

Fluid Density at STP

0.880

Condition (g/cm )
Gas Gravity (Air=1)
Dry Gross Heating Content
(Btu/scf)
Wet Gross Heating Content
(Btu/scf)

0.896
1538
1512

SPE 166097

13

Table 3. Volume vs. N2 Injection Concentration at 94 MPa and 94C

Step

N2 Overall

Total Volume

No.

Conc. (mol%)

(cm )

(cm )

(cm )

40.357

40.357

10

41.515

41.515

20

43.084

43.084

30

45.715

45.715

35

47.125

47.125

40

49.067

45.417

3.650

45

50.993

44.098

6.895

Liquid Volume

Vapor Volume

Table 4. AOP, Saturation Pressure and ADP at 94C

Fluid
Mixture

Psat

Added N2
(mol%)

AOP
b

(MPa)

ADP
c

(MPa)

(MPa)

M0

17.59

M1

29.99

41.37

13.79

M2

18

46.20

75.77

6.89

M3

27

68.02

94.00

4.14

M4

67

13.79

Added mol% per (100% - added mol% N2) reservoir fluid

Measured by PVT cell

AOP measured by SDS and HPM systems

AOP/ADP measured by PVT c ell equipped w ith SDS and

HPM systems

Table 5. Experimental and Simulated Viscosity Measurement (cP) at 94C

Experimental Pressure (MPa)

Fluid Mixture

SRK-P (CSP Model) Pressure (MPa)

PC-SAFT (CSP Model) Pressure (MPa)

103.4

94

84

103.4

94

84

103.4

94

84

M0

2.026

1.865

1.706

2.179

2.053

1.916

2.031

1.912

1.912

M1

1.712

1.573

1.451

1.844

1.734

1.614

1.652

1.548

1.436

M2

1.407

1.295

1.194

1.461

1.369

1.270

1.242

1.171

1.096

M3

1.101

1.025

0.960

1.130

1.069

1.004

1.016

0.939

0.855

Pressure (MPa)

Fluid Mixture
Eq. oil of M4 at
94 MPa

103.4

96.5

94

2.075

1.952

1.908

Table 6. Refractive Index of STO at 40C

Solvent

M0

M1

M2

M3

M4

1.4795

1.4798

1.4800

1.4799

1.4796

C7

1.4383

1.4367

1.4361

1.4472

1.4405

C11

1.4523

1.4480

1.4484

1.4553

1.4499

C15

1.4625

1.4571

1.4539

1.4618

1.4571

No
solvent

Table 7. Asphaltene Onset Concentration (Oil Vol% / Solvent

14

SPE 166097

Vol%) of Stock Tank Oils for Different Solvents at 40C

Solvent

M0

M1

M2

M3

M4

C7

69 / 31

69 / 31

69 / 31

69 / 31

59 /41

C11

68 / 32

69 / 31

68 / 32

70 / 30

62 / 38

C15

79 / 21

78 / 22

79 / 21

72 / 28

65 / 35

Table 8. Oil Recovery (%) from Slim Tube Displacements at

Displacement Pressure and 94C
Pressure

Material

Gas Breakthrough

1.0 PVI

1.2 PVI

68.43

82.9

83.2

84.9

0.845

55

75.1

75.1

77.4

0.799

45

70.1

70.1

71.1

0.729

(MPa)

Balance

(PVI)

Toulene rinsed ROS in slim tube with back calculation

Table 9. Reservoir fluid composition generated by recombining GC

analysis flashed gas composition with TBP analysis in Table 1.
Component

Weight %

Mole %

Molecular
Weight

Density
(g/cm3)

N2

0.027

0.123

CO2

0.023

0.066

C1

4.823

37.769

C2

1.301

5.435

C3

2.064

5.88

iC4

0.336

0.726

nC4

1.520

3.285

iC5

0.418

0.728

nC5

1.282

2.232

C6

1.831

2.669

C7

2.985

C8

3.420

4.025

92.9

0.7188

4.029

106.6

0.7416

C9
C10-C11

3.219

3.355

120.5

0.7619

6.026

5.438

139.2

0.7852

C12-C14

7.584

5.444

175.0

0.8154

C15-C17

7.752

4.589

212.2

0.8461

C18-C20

6.155

3.038

254.5

0.8645

C21-C25

7.087

2.838

313.7

0.8884

C26-C30

4.718

1.694

350.0

0.9035

C31-C35

6.093

1.763

434.2

0.9240

C36+

31.335

4.872

808

1.0093

Table 10. PC-SAFT EoS Parameters

Component

zi (mol%)

(ngstrm)

(K)

SPE 166097

N2

15

0.12

1.205

3.313

90.960

CO2

0.07

2.073

2.785

169.210

C1

37.77

1.000

3.704

150.030

C2

5.44

1.607

3.521

191.420

C3

5.88

2.002

3.618

208.110

iC4

0.73

2.262

3.757

216.530

nC4

3.28

2.332

3.709

222.880

iC5

0.73

2.562

3.830

230.750

nC5

2.23

2.690

3.773

231.200

C6

2.67

3.058

3.798

236.770

C7

4.02

3.114

3.790

249.483

C8

4.03

3.516

3.786

251.013

C9

3.36

3.929

3.783

252.492

C10-C11

5.44

4.480

3.778

254.375

C12-C14

5.44

5.544

3.772

256.256

C15-C17

4.59

6.593

3.769

260.434

C18-C20

3.04

7.821

3.768

262.374

C21-C25

2.84

9.484

3.770

266.129

C26-C30

1.69

10.457

3.771

269.291

C31-C49

3.31

14.767

3.775

275.595

C50-C80

2.56

28.648

3.597

247.386

C50-C80-A

0.76

11.000

4.530

500.000

Non-zero Binary Interaction Coefficients

kij

N2

CO2

CO2

-0.0315

C1

0.0278

0.12

C2

0.0407

0.12

C3

0.0763

0.12

iC4

0.0944

0.12

nC4

0.07

0.12

iC5

0.0867

0.12

nC5

0.0878

0.12

C6

0.08

0.12

C7

0.13

0.1

C8

0.13

0.1

C9

0.13

0.1

C10-C11

0.13

0.1

C12-C14

0.13

0.1

C15-C17

0.13

0.1

C18-C20

0.13

0.1

C21-C25

0.13

0.1

C26-C30

0.13

0.1

C31-C49

0.13

0.1

C50-C80

0.13

0.1

C50-C80-A

0.17

0.1

C1- C9

0.017

Table 11. 22 Component SRK-Peneloux EoS Parameters

Component

zi

Tc

Pc

Acentric

Volume

(mol%)

(C)

(MPa)

Factor

Correction

16

SPE 166097

(cm /mol)
N2

0.12

146.950

3.394

0.0400

0.92

CO2

0.07

31.050

7.376

0.2250

3.03

C1

37.77

-82.550

4.600

0.0080

0.63

C2

5.44

32.250

4.884

0.0980

2.63

C3

5.88

96.650

4.246

0.1520

5.06

iC4

0.73

134.950

3.648

0.1760

7.29

nC4

3.28

152.050

3.800

0.1930

7.86

iC5

0.73

187.250

3.384

0.2270

10.93

nC5

2.23

196.450

3.374

0.2510

12.18

C6

2.67

234.250

2.969

0.2960

17.98

C7

4.02

254.641

3.168

0.4595

10.05

C8

4.03

278.352

2.819

0.4986

17.62

C9

3.36

300.277

2.555

0.5384

24.58

C10-C11

5.44

326.702

2.300

0.5908

32.17

C12-C14

5.44

369.652

1.969

0.6877

42.61

C15-C17

4.59

409.299

1.799

0.7834

43.96

C18-C20

3.04

447.802

1.644

0.8851

42.59

C21-C25

2.84

496.827

1.527

1.0142

29.98

C26-C30

1.69

525.114

1.492

1.0850

16.98

C31-C49

3.31

640.904

1.383

1.2935

-47.31

C50-C80

2.56

815.372

1.416

1.0274

-289.03

C50-C80-A

0.76

1069.410

1.435

1.2740

-289.03

Non-Zero Binary Interaction Coefficients

kij

N2

CO2

CO2

-0.0315

C1

0.0278

0.12

C2

0.0407

0.12

C3

0.0763

0.12

iC4

0.0944

0.12

nC4

0.07

0.12

iC5

0.0867

0.12

nC5

0.0878

0.12

C6

0.08

0.12

C7

0.13

0.1

C8

0.13

0.1

C9

0.13

0.1

C10-C11

0.13

0.1

C12-C14

0.13

0.1

C15-C17

0.13

0.1

C18-C20

0.13

0.1

C21-C25

0.13

0.1

C26-C30

0.13

0.1

C31-C49

0.13

0.1

C50-C80

0.13

0.1

C50-C80-A

0.17

0.1

C1 - C9

0.017

Table 12. Nine Component SRK-Peneloux EoS Parameters

SPE 166097

Component

17

zi (mol%)

Tc
(C)

Pc
(MPa)

N2
0.123
-146.950
3.394
C1
37.769
-82.550
4.600
CO2+C2+C3
11.382
71.473
4.512
C4-C6
9.641
192.223
3.374
C7-C11
16.847
296.957
2.631
C12-C20
13.071
406.335
1.814
C21-C49
7.843
578.658
1.444
C50-C80
2.558
815.372
1.410
C50-C80-A
0.765
1069.410
1.470
Non-Zero Binary Interaction Coefficients
kij
N2
C1
CO2+C2+C3
C1
0.0278
CO2+C2+C3
C4-C6
C7-C11
C12-C20
C21-C49
C50-C80
C50-C80-A

0.0587
0.0800
0.1300
0.1300
0.1300
0.1300
0.1700

0.0007

0.0170

0.0007
0.0006
0.0006
0.0006
0.0006
0.0006

Acentric
Factor

0.0400
0.0080
0.1318
0.2434
0.5348
0.7788
1.1758
1.0274
1.2740

Volume
Correction
3

(cm /mol)

0.92
0.63
3.89
11.85
22.63
45.34
3.27
-289.03
-289.03