Stabilization and Destabilization of Crude Oil Emulsion

1. Formation and characteristics of crude oil
emulsion formed in chemical flooding
Haris Ramzan
Mechanical Engineer
Nazeer Hussain University

2. Back ground
Stable emulsions formed
in polymer or ASP
flooding of oil recovery.
Purpose
Study the influence of indigenious interfacial
active fractions from crude and alkali, surfactant,
polymer on interfacial property between crude
and water, and stability of crude emulsion.

3. Effect of Alkaline
Crude oil: Shengli crude oil
Production: ASP flooding
Alkaline : Na2CO3
Surfactant:Petroleum sulphonate
Polymer: HPAM

4. Crude oil: Daqing crude oil
Paraffin crude oil
Acid-number: 0.183
Paraffin: 18.6%
Resin:12.1%
Asphaltene: 0.1%
Production: ASP flooding
Alkaline : NaOH
Surfactant:Petroleum sulphonate
Polymer: HPAM

5. Crude oil
Pentane
treat
Asphaltene
Insoluble Soluble
AI2O3
adsorption
Benzene
Saturate Resin1 Resin2
Benzine/ethanol
Aromatic
EthanolPetroleum
ether
Separation of crude oil fractions
Gu Dong 1#
Gu Dong 4#
Da Qing crude oils

6. Table1. Composition of crude oil fractions
Fraction
w/ %
Gu Dong 1#
Gu Dong 4#
Da Qing
Saturate 47.08 46.54 68.09
Aromatic 23.65 28.18 17.25
Resin1 14.73 13.81 14.47
Resin2 0.11 0.12 0.10
Asphaltene 14.43 11.35 0.09
Parameters of crude fractions

7. Fraction
Oxygen in 100g crude oil/g
Gu Dong 1#
Gu Dong 4#
Da Qing
Saturate 0.118 0.140 0.375
Aromatic 0.170 0.211 0.086
Resin1 0.194 0.264 0.214
Asphaltene 0.316 0.317 0.001
Table2. Oxygen in crude oil fractions

8. Fractions Gu Dong 1#
Gu Dong 4#
Da Qing
Saturate 2.397 3.014 0.4760
Aromatic 5.386 5.242 1.039
Resin 6.001 8.002 5.101
Asphaltene 16.45 8.378 4.213
Crude oil 3.640 3.217 0.517
Table3. Acid number of crude oils and their fractions

9. Crude oils Saturate Aromatic ResinⅠ Asphaltene Crude oil
Gu Dong 1#
434 601 1025 1499 433
Gu Dong 4#
503 728 1117 1308 427
Da Qing 485 773 1396 2433 480
Table4. MW of crude oils and their fractions

10. Table5. Composition of model oil(w%)
Crude oil Saturate Aromatic ResinⅠ Asphaltene
Gu
Dong1#
10.00 4.59 2.25 1.49 1.44
Gu
Dong4#
10.00 4.02 2.19 1.49 1.14
Da Qing 10.00 6.43 1.52 1.41 0.01
Model oils
Distilled water or NaOH/Na2
CO3
solution
Aqueous phase
Interfacial tension

11. Crude oils
Model oil
Saturate Aromatic ResinⅠ Asphaltene Crude oil
Gu Dong1
＃
w % 4.60 2.53 1.46 1.44 10.00
γo/w
／ mNּm-1
35.70 24.52 22.76 19.38 11.89
γo/s
／ mNּm-1
13.36 5.61 4.63 0.056 0.93
w % 3.00 3.00 3.00 3.00 3.00
γo/w
／ mNּm-1
33.03 17.90 15.78 12.75 19.27
γo/s
／ mNּm-1
11.22 4.37 3.12 0.0053 0.762
Table6-1. Interfacial tension between model oils
and aqueous phase (45 °C)

12. Crude oils
Model oil
Saturate Aromatic ResinⅠ Asphaltene Crude oil
Gu Dong4
＃
w % 4.02 2.19 1.38 1.14 10.00
γo/w
／ mNּm-1
33.55 18.85 18.36 16.90 17.21
γo/s
／ mNּm-1
9.12 7.11 4.30 0.86 1.71
w % 3.00 3.00 3.00 3.00 3.00
γo/w
／ mNּm-1
30.07 14.42 13.33 7.03 21.48
γo/s
／ mNּm-1
10.45 5.32 2.62 0.43 1.35
Table6-2. Interfacial tension between model oils
and aqueous phase (45 °C)

13. Crude oils
Model oil
Saturate Aromatic ResinⅠ Asphaltene Crude oil
Da Qing
w % 6.66 1.58 1.45 0.10 10.00
γo/w
／ mNּm-1
39.96 33.57 27.63 33.68 30.46
γo/s
／ mNּm-1
18.31 11.97 8.24 12.81 4.04
w % 3.00 3.00 3.00 3.00 3.00
γo/w
／ mNּm-1
36.51 30.24 26.34 28.22 29.40
γo/s
／ mNּm-1
14.68 10.30 2.64 4.07 2.86
Table6-3. Interfacial tension between model oils
and aqueous phase (45 °C)

14. 0.0 0.1 0.2 0.3 0.4 0.5
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
Interfacialshearviscosity/mNsm
-1
Shear rate/ rad s
-1
1.2% Na2
CO3
Di s t i l l ed wat er
Figure2. Interfacial shear viscosity between 2% asphaltene
model oil(Gu Dong 1#
) and distilled water /1.2% Na2
CO3
solution, 25 °C.
Interfacial shear viscosity
Biconical disc
water
oil
Steel-wire

15. 0.0 0.1 0.2 0.3 0.4 0.5
0.00
0.02
0.04
0.06
0.08
0.10
1.2% Na2
CO3
Di s t i l l ed wat er
Interfacialshearviscosity/mNsm
-1
Shear rate/ rad s
-1
Figure3. Interfacial shear viscosity between 2% asphaltene
model oil(Gu Dong 4#
) and distilled water /1.2% Na2
CO3
solution, 25 °C.

16. 0.0 0.1 0.2 0.3 0.4 0.5
0.00
0.01
0.02
0.03
0.04
0.05
Interfacialshearviscosity/mNsm
-1
Shear rate/rad s
-1
1.2% NaOH
distilled water
Figure4. Interfacial shear viscosity between 2% resin model
oil(Da Qing) and distilled water /1.2% NaOH solution, 25 °C.

17. 0.0 0.1 0.2 0.3 0.4 0.5
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
Interfacialshearviscosity/mNsm
-1
Shear rate/ rad s
-1
Saturate
Aromatic
Resin
Asphaltene
Figure5. Interfacial shear viscosity between model
oils(Gu Dong 1#
) and 1.2% Na2
CO3
solution, 25 °C.

18. 0.0 0.1 0.2 0.3 0.4 0.5
0.00
0.02
0.04
0.06
0.08
0.10
Interfacialshearviscosity/mNsm
-1
Shear r at e/ rad s
-1
Saturate
Aromatic
Resin
Asphaltene
Figure6. Interfacial shear viscosity between model
oils(Gu Dong 4#
) and 1.2% Na2
CO3
solution, 25 °C.

19. 0.0 0.1 0.2 0.3 0.4 0.5
-0.02
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
Interfacialshearviscosity/mNsm
-1
Shear rate/ rad s
-1
Saturate
Aromatic
Resin
Asphaltene
Figure7. Interfacial shear viscosity between model
oils(Da Qing) and 1.2% NaOH solution, 25 °C.

20. 0 10 20 30 40 50
0
10
20
30
40
50
60
70
80
90
100
Separationofwater/%
Separation time / min
Reaction time
1 d
3 d
6 d
8 d
47d
54d
0 10 20 30 40 50 60 70
0
20
40
60
80
100
Separationofwater/%
Separation time/min
Reaction time
1 d
3 d
4 d
7 d
15d
21d
Figure11 Stability of the emulsion formed of asphaltene model oil
(Gu Dong 1#
) and distilled water(A) or1.2%Na2
CO3
water solution(B), 60 °C
(A) (B)
Stability of emulsions

21. 0 10 20 30 40 50 60
0
10
20
30
40
50
60
70
80
90
100
Separation time/min
Reaction time
1 d
3 d
6 d
8 d
47d
54d
Separationofwater/%
-2 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32
-10
0
10
20
30
40
50
60
70
80
90
100
Separationofwater/%
Separation time/min
Reaction time
1 d
3 d
9 d
14d
21d
27d
34d
77d
84d
Figure13 Stability of the emulsion formed of asphaltene model oil
(Gu Dong 4#
) and distilled water(A) or1.2%Na2
CO3
water solution(B), 60 °C
(A) (B)

22. 0 10 20 30 40 50 60 70
0
10
20
30
40
50
60
70
80
90
100
110
Separationofwater/%
Separation time/min
Reaction time
1 d
3 d
9 d
14d
21d
34d
77d
84d
0 10 20 30 40 50 60 70
0
10
20
30
40
50
60
70
80
90
100
Separationofwater/%
Separation time/ min
Reaction time
1 d
3 d
9 d
14d
21d
27d
34d
77d
84d
0 10 20 30 40 50 60 70
0
10
20
30
40
50
60
70
80
90
100
Separationofwater/%
Separation time/min
Reaction time
1 d
3 d
9 d
14d
21d
27d
34d
77d
84d
0 10 20 30 40 50 60 70
0
10
20
30
40
50
60
70
80
90
100
Separationofwater/%
Separation time/ min
Reaction of time
1 d
3 d
14d
21d
27d
34d
77d
84d
Figure16 Stability of the emulsion formed with Da Qing crude
model oil and 1.2%NaOH water solution, 60 °C.
Saturate Asphaltene
Resin Crude oil

23. 0 1 2 3 4 5 6 7 8 9 10
6
7
8
9
10
11
12
13
14
15
16
Interfacialtension/mNm
-1
Reaction time/week
1 2 3 4 5 6 7
0.0250
0.0275
0.0300
0.0325
0.0350
0.0375
0.3 rad s
-1
0.1 rad s
-1
Interfacialshearviscosity/mNsm
-1
Reaction time/day
Da Qing crude oil
(3.0% saturate model oil, 0.6% NaOH solution, 25℃)
Interfacial tension Interfacial shear viscosity
Interfacial active fractions

24. 418.84
719.47
1376.86
1462.77
1593.23
1732.77
2849.132918.06
2953.90
-0.02
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
Absorbance
20004000
Wavenumbers (cm-1)
719.66
971.46
1377.13
1462.43
1563.90
1710.58
2850.55
2922.10
2954.72
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
0.22
0.24
0.26
0.28
0.30
Absorbance
20004000
Wavenumbers (cm-1)
Figure19 IR spectroscopy of saturate fraction(A) and
the interfacially active components(B) formed
in the reaction of saturate and NaOH.
C-O stretching vibration
carboxylic groupsReaction of saturate and NaOH

25. IR parameters of fractions and crude oils
1380
1460
A
A
Degree of branch
1600
(1600 1460)
A
A +
Degree of aromaticity
(1750 1650)
(1600 1460)
A
A +
:
Content of carbonyl in the hydrocarbon
1100
(1600 1460)
A
A +
Content of ether in the hydrocarbon
3200
(1600 1460)
A
A +
Content of acid, alcohol and phenol
in the hydrocarbon

26. 1380
1460
A
A
Fractions
Saturate 0.463 － 0.037 0.031 －
Aromatic 0.479 0.166 0.090 0.088 0.021
Resin1 0.696 0.355 0.385 0.201 0.204
Asphaltene 0.769 0.356 0.435 0.171 0.254
Crude oil 0.626 0.148 0.0928 0.0299 0.0327
1600
(1600 1460)
A
A +
(1750 1650)
(1600 1460)
A
A +
: 1100
(1600 1460)
A
A +
3200
(1600 1460)
A
A +
Table7-1 IR parameters of fractions and crude oils
Gu Dong1# crude oil

27. 1380
1460
A
A
Fractions
Saturate 0.390 － 0.003 0.002 －
Aromatic 0.394 0.127 0.062 0.049 0.015
Resin1 0.546 0.265 0.264 0.095 0.150
Asphaltene 0.676 0.303 0.421 0.213 0.232
Crude oil 0.595 0.154 0.084 0.074 0.028
1600
(1600 1460)
A
A +
(1750 1650)
(1600 1460)
A
A +
: 1100
(1600 1460)
A
A +
3200
(1600 1460)
A
A +
Table7-2 IR parameters of fractions and crude oils
Gu Dong4# crude oil

28. 1380
1460
A
A
Fractions
Saturate 0.369 － 0.052 0.045 －
Aromatic 0.386 0.162 0.199 0.067 0.024
Resin1 0.440 0.237 0.336 0.123 0.069
Asphaltene 0.584 0.262 0.312 0.107 0.052
Crude oil 0.510 0.108 0.071 0.020 0.019
1600
(1600 1460)
A
A +
(1750 1650)
(1600 1460)
A
A +
: 1100
(1600 1460)
A
A +
3200
(1600 1460)
A
A +
Table7-3 IR parameters of fractions and crude oils
Da Qing crude oil

29. Conclusion
•Carboxylic acids in the fractions of asphaltene
from Gu Dong crude, the resin from Da Qing crude
and the fatty acid in the fractions of saturate from
Da Qing crude are responsible for decreasing
the interfacial tension;
•These acids have smaller relatively molecule mass,
more branch chain, more oxygen but they are not
able to stabilize emulsion. It is the acids with lager
relatively molecule mass are responsible for stabilizing
the emulsions.

30. •For model oil and alkali solution system the salt or
soap formed by fast reaction of the acid, ester with
smaller relatively molecule mass and alkali is responsible
for decreasing the interfacial tension. The salt or soap
formed by slow reaction of the acid, ester with lager
relatively molecule mass and alkali is responsible
for stabilizing crude oil emulsions.

31. Effect of Polymer
Polymer:
Hydrolyzed polyacrylamide(HPAM)
MW: 12-18 ×106
Hydrolysis degree:25%.
Concentration: 1000-2500 mg/L
Emulsion:
O/W emulsion
Daqing crude oil

32. Table 1 Interfacial tension between model oil
and HPAM solution (mNm-1
)
Model
oilHPAM/mg/L
Jet fuel Resin Asphaltene Crude
0 52.2 17.2 15.2 23.0
25 52.8 24.2 20.4 30.1
50 55.4 27.7 19.1 29.9
100 54.7 26.2 20.6 29.8
200 46.2 22.8 18.7 27.9
300 48.6 24.4 17.8 27.1
400 49.1 17.1 18.2 31.1
Interfacial tension

33. 0 10 20 30 40 50
-0.002
0.000
0.002
0.004
0.006
0.008
0.010
0.012
Interfacialviscosity/mNms
-1
HPAM concentration/mgL
-1
Interfacial shear viscosity
Figure1 Interfacial shear viscosity between resin model oil and HPAM solution
(oil: 1 ％ resin model oil ， water: HPAM solution ， T: 25℃ ， shear rate: 0.3
rads-1
)

34. 0.0 0.1 0.2 0.3 0.4 0.5
0.000
0.005
0.010
0.015
0.020
0.025
0.030
Interfacialviscosity/mNms
-1
shear rate/rads
-1
HPAM con.
(mg/L)
0
5
10
20
50
Figure2 Interfacial shear viscosity between asphaltene model oil and HPAM solution
(oil: 1 ％ asphaltene model oil ， water: HPAM solution ， T: 25 )℃

35. System Interfacial shear viscosity/mNms-1
Crude model oil/synthetic
formation water
0.1103
Crude model oil/HPAM solution
（ 50mg/L ）
0.1416
T: 25 , shear rate: 0.3rads℃ -1
.
Table2 Interfacial shear viscosity between crude model oil
and HPAM solution

36.
Resin model
oil/5 ％
Asphaltene
model
oil/5 ％
Crude
oil
0 -11.6 -9.1 -21.1
50 - -11.3
100 -15.10 -44.5 -13.5
200 -42.8 -25.1
HPAM/mgL-1
Table3 Zeta potential on the surface of oil drops/mV
Zeta potential

37. Conclusion:
The emulsion(o/w) formed in polymer
flooding is stabilized by the steric and
electrostatic stabilization of the polymers

38. Effect of Surfactant
Surfactant:
Petroleum sulphonate
Active content in the surfactant is 48.69 wt%.
Concentration: 0.3%
Emulsion:
O/W emulsion
Shengli crude oil

39.
Aqueous
Model oil
0.0% TRS 0.1% TRS 0.3% TRS 0.5% TRS
IFT
mN.m-1
Time
min
IFT
mN.m-1
Time
min
IFT
mN.m-1
Time
min
IFT
mN.m-1
Time
min
3%
asphaltene
4.388 850 0.118 750 0.0066 110 0.0012 60
3% resin 6.854 200 0.0212 80 0.0082 30 0.0013 25
3% crude
oil
8.583 350 0.989 220 0.0168 130 0.0099 110
Table 2 Effects of petroleum solfonate on IFT
Interfacial tension

40. 0.0 0.1 0.2 0.3 0.4 0.5
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
ηs
/ mN s m
-1
ω / rad s
-1
petroleum sulfonat 0.0 wt%
petroleum sulfonat 0.1 wt%
petroleum sulfonat 0.2 wt%
petroleum sulfonat 0.3 wt%
petroleum sulfonat 0.5 wt%
0.0 0.1 0.2 0.3 0.4 0.5
0.0
0.1
0.2
0.3
0.4
0.5
ηs
/ mN s m-1
ω / rad s
-1
petroleum sulfonate 0.0 wt
%
petroleum sulfonate 0.1 wt
%
petroleum sulfonate 0.3 wt
%
petroleum sulfonate 0.5 wt
%
petroleum sulfonate 0.2 wt
%
3% crude model3% asphaltene model
Interfacial shear viscosity

41. 0 20 40 60 80 100 120
0.0
0.2
0.4
0.6
0.8
1.0
vol.-% oil seperation
time / min
petroleum sulfonate 0.0%
petroleum sulfonate 0.1%
petroleum sulfonate 0.3％
petroleum sulfonate 0.5％
0 20 40 60 80 100 120
0
20
40
60
80
100
separation of oil phase / %
t / min
petroleum sulfonate 0.0 wt
%
petroleum sulfonate 0.1 wt
%
petroleum sulfonate 0.3 wt
%
petroleum sulfonate 0.5 wt
%
3% crude model3% asphaltene model
Stability of Emulsions

42. Conclusion:
The emulsion(o/w) formed in ASP flooding is
stabilized by the interfacial film, steric and
electrostatic stabilization of asphaltene,
polymers and the interfacial active substances
formed by reaction of alkali and crude oils.

43. Thanks