Download - Crude oil emulsion 2
Formation and characteristics of crude oil emulsion formed in chemical flooding
Haris Ramzan
Mechanical Engineer
Nazeer Hussain University
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.
Effect of Alkaline
Crude oil: Shengli crude oil
Production: ASP flooding Alkaline : Na2CO3
Surfactant:Petroleum sulphonate
Polymer: HPAM
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
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
Table1. Composition of crude oil fractions
Fractionw / %
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
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
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
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
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/Na2CO3 solution
Aqueous phase
Interfacial tension
Crude oils Model oil
Saturate Aromatic ResinⅠ Asphaltene Crude oil
Gu Dong1#
w % 4.60 2.53 1.46 1.44 10.00
o/w / mNּm-1 35.70 24.52 22.76 19.38 11.89
o/s / mNּm-1 13.36 5.61 4.63 0.056 0.93
w % 3.00 3.00 3.00 3.00 3.00
o/w / mNּm-1 33.03 17.90 15.78 12.75 19.27
o/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)
Crude oils Model oil
Saturate Aromatic ResinⅠ Asphaltene Crude oil
Gu Dong4#
w % 4.02 2.19 1.38 1.14 10.00
o/w / mNּm-1 33.55 18.85 18.36 16.90 17.21
o/s / mNּm-1 9.12 7.11 4.30 0.86 1.71
w % 3.00 3.00 3.00 3.00 3.00
o/w / mNּm-130.07 14.42 13.33 7.03 21.48
o/s / mNּm-110.45 5.32 2.62 0.43 1.35
Table6-2. Interfacial tension between model oils and aqueous phase (45 C)
Crude oils Model oil
Saturate Aromatic ResinⅠ Asphaltene Crude oil
Da Qing
w % 6.66 1.58 1.45 0.10 10.00
o/w / mNּm-139.96 33.57 27.63 33.68 30.46
o/s / mNּm-118.31 11.97 8.24 12.81 4.04
w % 3.00 3.00 3.00 3.00 3.00
o/w / mNּm-136.51 30.24 26.34 28.22 29.40
o/s / mNּm-114.68 10.30 2.64 4.07 2.86
Table6-3. Interfacial tension between model oils and aqueous phase (45 C)
0.0 0.1 0.2 0.3 0.4 0.50.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
Inte
rfa
cia
l sh
ea
r vi
sco
sity /
mN
s m
-1
Shear rate/ rad s-1
1.2% Na2CO
3
Di st i l l ed wat er
Figure2. Interfacial shear viscosity between 2% asphaltene model oil(Gu Dong 1#) and distilled water /1.2% Na2CO3 solution, 25 C.
Interfacial shear viscosity
Biconical disc water
oilSteel-wire
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% Na
2CO
3
Di st i l l ed wat er
Inte
rfa
cia
l sh
ea
r vis
co
sity
/ m
N s
m-1
Shear rate/ rad s-1
Figure3. Interfacial shear viscosity between 2% asphaltene model oil(Gu Dong 4#) and distilled water /1.2% Na2CO3 solution, 25 C.
0.0 0.1 0.2 0.3 0.4 0.5
0.00
0.01
0.02
0.03
0.04
0.05
In
terf
acia
l sh
ear
vis
co
sit
y/m
N s
m-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.
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
Inte
rfa
cia
l sh
ea
r vis
co
sity
/ m
N s
m-1
Shear rate/ rad s-1
Saturate Aromatic Resin Asphaltene
Figure5. Interfacial shear viscosity between model
oils(Gu Dong 1#) and 1.2% Na2CO3 solution, 25 C.
0.0 0.1 0.2 0.3 0.4 0.5
0.00
0.02
0.04
0.06
0.08
0.10
Interfacial shear viscosity
/ m
N s
m-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% Na2CO3 solution, 25 C.
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
Inte
rfa
cia
l sh
ea
r vis
co
sity
/ m
N s
m-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.
0 10 20 30 40 500
10
20
30
40
50
60
70
80
90
100
S
epar
atio
n of
wat
er/
%
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
Se
pa
ratio
n o
f w
ate
r/%
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%Na2CO3 water solution(B), 60 C
(A) (B)
Stability of emulsions
0 10 20 30 40 50 600
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
Sep
arat
ion
of w
ater
/%
-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
Sep
arat
ion
of
wat
er/%
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%Na2CO3 water solution(B), 60 C
(A) (B)
0 10 20 30 40 50 60 70
0
10
20
30
40
50
60
70
80
90
100
110
S
ep
ara
tio
n o
f w
ate
r/%
Separation time/min
Reaction time 1 d 3 d 9 d 14d 21d 34d 77d 84d
0 10 20 30 40 50 60 700
10
20
30
40
50
60
70
80
90
100
Se
pa
ratio
n o
f w
ate
r/%
Separation time/ min
Reaction time 1 d 3 d 9 d 14d 21d 27d 34d 77d 84d
0 10 20 30 40 50 60 700
10
20
30
40
50
60
70
80
90
100
S
ep
ara
tio
n o
f w
ate
r/%
Separation time/min
Reaction time 1 d 3 d 9 d 14d 21d 27d 34d 77d 84d
0 10 20 30 40 50 60 700
10
20
30
40
50
60
70
80
90
100
S
ep
ara
tio
n o
f w
ate
r/%
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
0 1 2 3 4 5 6 7 8 9 106
7
8
9
10
11
12
13
14
15
16
Inte
rfac
ial t
ensi
on
/mN
m-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
Inte
rfac
ial s
hea
r vi
sco
sity
/mN
s m
-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
418.
84
719.
47
1376
.8614
62.7
7
1593
.23
1732
.77
2849
.13
2918
.06
2953
.90
-0.02
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
Abs
orba
nce
2000 4000 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
Abs
orba
nce
2000 4000 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 groups Reaction of saturate and NaOH
IR parameters of fractions and crude oils
1380
1460
A
ADegree 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
1380
1460
A
AFractions
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
1380
1460
A
AFractions
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
1380
1460
A
AFractions
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
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.
•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.
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
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
0 10 20 30 40 50-0.002
0.000
0.002
0.004
0.006
0.008
0.010
0.012In
terf
acia
l vis
co
sit
y/m
Nm
s-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)
0.0 0.1 0.2 0.3 0.4 0.50.000
0.005
0.010
0.015
0.020
0.025
0.030In
terf
acia
l vis
co
sit
y/m
Nm
s-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 )℃
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
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
Conclusion:
The emulsion(o/w) formed in polymer
flooding is stabilized by the steric and
electrostatic stabilization of the polymers
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
Aqueous
Model oil
0.0% TRS 0.1% TRS 0.3% TRS 0.5% TRS
IFTmN.m-1
Timemin
IFTmN.m-1
Timemin
IFTmN.m-1
Timemin
IFTmN.m-1
Timemin
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
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
s /
mN
s m
-1
/ 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
s /
mN
s m
-1
/ 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 model 3% asphaltene model
Interfacial shear viscosity
0 20 40 60 80 100 120
0.0
0.2
0.4
0.6
0.8
1.0
vol.-
% o
il s
eper
atio
n
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
sepa
ratio
n of
oil
phas
e / %
t / min
petroleum sulfonate 0.0 wt%
petroleum sulfonate 0.1 wt%
petroleum sulfonate 0.3 wt%
petroleum sulfonate 0.5 wt%
3% crude model 3% asphaltene model
Stability of Emulsions
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.
Thanks