Effect of Surfactant Synergism on Foam Rheology Lauryl Sultaine: AOS 14-16 blends Lauryl Betaine:...
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Transcript of Effect of Surfactant Synergism on Foam Rheology Lauryl Sultaine: AOS 14-16 blends Lauryl Betaine:...
1
Effect of Surfactant Synergism on Foam Rheology
Lauryl Sultaine: AOS 14-16 blends
Lauryl Betaine: AOS 14-16 blends
Rice University :Aarthi MuthuswamyMaura PuertoRafael VerduzcoClarence MillerGeorge Hirasaki
TU Delft, Shell RijswijkRouhi FarajzadehSebastien Bonnieu
2
Outline
• Foam experimental set up• Lauryl Sultaine & AOS14-16 blends, Lauryl Betaine &
AOS14-16 blends-N2 Foam flow in Bentheimer sandstone, 45°C.
-Regular solution theory interpretation of foam rheology.-Foam Presence of crude oil
• Interfacial rheology comparison of surfactants• Observations and conclusions
N2
GAS
MFC
Liquid Pump P1
P4
P3
P2
1.7”
2.46 ”
2.46
”
CORE
INLET
BPR
N2
GAS
OUTLET
TRAN
SDU
CERS
TO EFFLUENT
CHECK VALVE
CON
FIN
ING
PRE
SSU
RE
CON
FIN
ING
PRE
SSU
RE
OVEN 45 ⁰C
FOAM EXPERIMENTAL SET UP
4
Lauryl Sultaine –AOS 14-16 blends
5
Aqueous stability test - Sultaine AOS blends at 45⁰C
(S) 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 (AOS) 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Clear ClearUnclear
6
Foam Quality scan- 45 °C, ~ 2.5 Darcy, ~ 20 ft/day interstitial velocity
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%10
100
1000
10000
S:AOS 8:2S:AOS 1:9
AOS
Sultaine
sultaine aos sultaine aos 1:9sultaine aos 8:2
Foam Quality (%)
App
aren
t vis
cosi
ty (c
P)
Ove
rall
IN
OUT
Internal tap
N2 foamBPR ~ 25 bar=362psi
𝚪=𝒒𝒈
𝒒𝒈+𝒒𝒍
= gas flow rate = liquid flow rate
7
Regular solution theory
Assumptions:• The entropy of mixing is ideal• However the change in the Gibbs free energy (ΔGmix= ΔHmix- TΔSmix)
arising due to the interactions between the two surfactants is taken into account using an activity coefficient f in the chemical potential equation. The activity coefficient signifies the deviations from the ideal solution.
• The regular solution approximation for the activity coefficient is given as (Rubingh, 1979)
Rosen, M. J. (1991). Synergism in mixtures containing zwitterionic surfactants. Langmuir, 885-888.
Rubingh, D. N. (1979). Mixed Micelle Solutions (Vol. 1). Springer New York.
Zhou, Q., & Rosen, M. (2003). Molecular Interactions of Surfactants in Mixed Monolayers at the Air/Aqueous Solution Interface and in Mixed Micelles in Aqueous Media: The Regular Solution Approach. Langmuir, 4555-4562.
8
Calculation of β parameters- Regular solution theory
𝒙𝒎𝟏𝟐 𝐥𝐧 (
𝜶𝟏𝑪𝒎𝟏𝟐
𝒙𝒎𝟏𝑪𝒎𝟏
)
(𝟏−𝒙𝒎𝟏 )𝟐𝒍𝒏((𝟏−𝜶𝟏 )𝑪𝒎𝟏𝟐
(𝟏− 𝒙𝒎𝟏 )𝑪𝒎𝟐
)
=𝟏
𝜷𝑴=𝐥𝐧 (
𝜶𝟏𝑪𝒎𝟏𝟐
𝒙𝒎𝟏𝑪𝒎𝟏)
(𝟏− 𝒙𝒎𝟏)𝟐
α1- mole fraction of surfactant 1 in the prepared bulk solution (LB)xm1 – the mole fraction of surfactant 1 (LB) in the mixed micelleCm1, Cm2- cmc of the individual surfactants LB and AOS respectivelyCm12- cmc of the surfactant mixtureγ – surface tension X1= mole fraction of surfactant 1 (LB in this case) in the total mixed monolayer C12, C1
0, C20 are the molar concentrations of LB: AOS mixture,
LB, AOS respectively chosen to give a particular surface tension value
𝒙𝟏𝟐 𝒍𝒏(
𝜶𝟏𝑪𝟏𝟐
𝒙𝟏𝑪𝟏𝟎 )
(𝟏−𝒙𝟏 )𝟐𝒍𝒏((𝟏−𝜶𝟏 )𝑪𝟏𝟐
(𝟏− 𝒙𝟏 )𝑪𝟐𝟎 )
=𝟏
?
𝜷𝝈=𝒍𝒏(
𝜶𝟏𝑪𝟏𝟐
𝒙𝟏𝑪𝟏𝟎 )
(𝟏−𝒙𝟏𝟐)
?
?
?
9
Surface tension measurements for Sultaine-AOS blends mad in sea water Air-water interface, 20 °C
Surfactant CMC (wt%) CMC (M) Surface tension (mN/m)
LS 0.017 0.000983 33.52
8LS+2AOS 0.0073 0.00044 28.35
1LS+9AOS 0.00404 0.000313 29.74
AOS 0.00508 0.000407 28.76
0.000001 0.00001 0.0001 0.001 0.01 0.10
10
20
30
40
50
60
70
80
SultaineS:AOS 8:2S:AOS 1:9AOS
conc M
Surf
ace
tens
ion
(mN
/m)
CMC
C01
C02
C012
Du-Nuoy Padday method used
10
Interfacial tension between octane and sultaine-AOS blends, 20°C
0.000001 0.00001 0.0001 0.001 0.01 0.10
5
10
15
20
25
30
35
40
45
50
LSS:AOS 8:2S:AOS 1:9AOS
conc M
Inte
rfac
ial
tens
ion
(mN
/m)
Characterization of synergism by parameter for Sultaine AOS blends
Surfactant Bulk mole fraction LS
Interfacial mole fraction X1 LS
Sultaine8 Sultaine + 2 AOS 0.73 0.50 -1.56
1 Sultaine+ 9 AOS 0.072 0.18 +0.24AOS
Air-liquid interface
Surfactant LS X1 LS
Sultaine
8 Sultaine + 2 AOS 0.73 0.50 -1.01
1 Sultaine+ 9 AOS 0.072 Cannot solve perhaps mole fraction of LS is too low.
AOS
Octane-liquid interface
11Zhou, Q., & Rosen, M. (2003). Molecular Interactions of Surfactants in Mixed Monolayers at the Air/Aqueous Solution Interface and in Mixed Micelles in Aqueous Media: The Regular Solution Approach. Langmuir, 4555-4562
12
Foam Quality scan- 45 °C, ~ 2.5 Darcy, ~ 20 ft/day interstitial velocity
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%10
100
1000
10000
S:AOS 8:2S:AOS 1:9
AOS
Sultaine
sultaine aos sultaine aos 1:9sultaine aos 8:2
Foam Quality (%)
App
aren
t vis
cosi
ty (c
P)
Ove
rall
IN
OUT
Internal tap
N2 foamBPR ~ 25 bar=362psi
13
1 10 1001
10
100f(x) = 96.6093893646772 x^-0.237982393289041R² = 0.777445235597079
f(x) = NaN x^NaNR² = NaN Sultaine, 2.7 Darcy, 30% foam
Interstitial velocity (ft/day)
App
aren
t vis
cosi
ty (c
P)
0.1 1 10 10010
100
1000
10000
f(x) = 122.054132090756 x^-0.597475390298641R² = 0.853871131799467
f(x) = 1877.30141528283 x^-0.2828916267485R² = 0.668106872069439
S:AOS 8:2 , 2.4 Darcy, 82% foam
Interstitial velocity (ft/day)
App
aren
t vis
cosi
ty (c
P)
S:AOS Foam with crude oil, 45⁰ C, ~ 40% residual oil
Ove
rall
IN
OUT
Internal tap (foam no oil)
IN
Foam presence of crude oil
Oil ~ 60 cP
14
0.1 1 10 10010
100
1000
10000
f(x) = 2147.56279369965 x^-0.615602675867607R² = 0.977176205400423
f(x) = NaN x^NaNR² = NaN AOS, 2.6 Darcy ~ 82% foam
Interstitial velocity (ft/day)
App
aren
t vis
cosi
ty (c
P)
0.1 1 10 100100
1000
10000
f(x) = 2999.38510470392 x^-0.702109198975358R² = 0.972126937163002f(x) = 1776.54021084261 x^-0.225091738612957R² = 0.820357766680693
S:AOS 1:9, 2.4 Darcy, ~82% foam
Interstitial velocity (ft/day)
App
aren
t vis
cosi
ty (c
P)
Ove
rall
IN
OUT
Internal tap (foam)
IN
Foam presence of crude oil
S:AOS Foam with crude oil, 45⁰ C, ~ 40% residual oil
15
Lauryl Betaine –AOS 14-16 blends
16
(LB) 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0(AOS) 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Blend Scan (45 ⁰C)
Clear ClearNot Clear
17
Betaine- AOS foam quality scan- 45°CCompared at shear rate 28.3 1/s
20% 30% 40% 50% 60% 70% 80% 90% 100%100
1000
10000 LB LB:AOS 7:3 LB:AOS 1:9 AOS
Foam Quality
App
aren
t vis
cosi
ty (c
P)
2.5 Darcy
1.2 Darcy
2.6 Darcy
0.9 Darcy
Ove
rall
IN
OUT
Internal tap
N2 foamBPR ~ 5 bar=72.5psi
18
0.000001 0.00001 0.0001 0.001 0.01 0.10
10
20
30
40
50
60
70
80
LBLB:AOS 7:3LB:AOS 1:9AOS
Conc (M)
Surf
ace
Tens
ion
(mN
/m)
Surfactant CMC (wt%) CMC (M) Surface tension (mN/m)
LB 0.0136 0.00157 33.79
7LB+3AOS 0.0057 0.00034 27.9
1LB+9AOS 0.00415 0.000348 28.65
AOS 0.00508 0.000407 28.76
Surface tension measurements for Betaine-AOS blends made in sea water Air-water interface, 20 °C
19
Interfacial tension between octane and betaine-AOS blends- 20°C
0.000001 0.00001 0.0001 0.001 0.01 0.10
5
10
15
20
25
30
35
40
45
50
LBLB:AOS 7:3LB:AOS 1:9AOS
Conc (M)
Inte
rfac
ial T
ensi
on (m
N/m
)
20
Characterization of synergism by parameter- Betaine AOS blends
Surfactant Bulk mole fraction LB
Interfacial mole fraction X1 LB
Betaine
7 Betaine +3AOS 0.77 0.49 -7.08
1 Betaine+ 9 AOS 0.14 0.31 -2.72
AOS
Surfactant X1 LB
Betaine
7 Betaine +3AOS 0.37 -3.24
1 Betaine+ 9 AOS 0.30 -2.19
AOS
Octane-liquid interface
Air-liquid interface
21
1 10 10010
100
1000
LB , 2.5 Darcy, at ~60% quality, 20° C
Interstitial velocity (ft/day)
App
aren
t vis
cosi
ty (c
P)LB:AOS Foam with crude oil, ~ 30% residual oil
1 10 10010
100
1000
f(x) = 1345.7599091273 x^-0.609359540082445R² = 0.981064621291352
LB:AOS 7:3 , 1.2 Darcy at ~80%, 45° C
Interstitial velocity (ft/day)
App
aren
t vis
cosi
ty (c
P)
Ove
rall
IN
OUT
Internal tap (foam)
IN
Foam presence of crude oil
22
Ove
rall
IN
OUT
Internal tap (foam)
IN
Foam presence of crude oil
LB:AOS Foam with crude oil , ~30% residual oil (contd.)
1 10 10010
100
1000
f(x) = 750.1635990962 x^-0.627272535219658R² = 0.992071333842097
f(x) = 748.719136465846 x^-0.315929296669471R² = 0.976456200004859
LB:AOS 1:9 , 0.7 Darcy at ~90% , 45°C
Interstitial velocity(ft/day)
Appa
rent
vis
cosit
y (c
P)
0.1 1 10 10010
100
1000
10000
f(x) = 2147.56279369965 x^-0.615602675867607R² = 0.977176205400423
f(x) = NaN x^NaNR² = NaN AOS, 2.6 Darcy ~ 82% foam
Interstitial velocity (ft/day)
App
aren
t vis
cosi
ty (c
P)
Comparison of interfacial complex viscosity- Interfacial stress rheometer magnetic needle method
0.1 1 10 1001E-04
1E-03
1E-02
1E-01
LBLSAOSLS:AOS 1:9LB:AOS 1:9
Frequency (rad/s)
Com
plex
vis
cosi
ty h
*(m
Pa.s
.m)
DI water= ~0.01 mPa.s.m
All surfactant solutions made in sea water
Observations and Conclusions• Absence of crude oil: In a blend of zwitterionic Lauryl betaine and
Anionic AOS 14-16 (AOS) , betaine does not boost the foam of the blends to any better value than pure AOS itself. The same goes for blends of Lauryl sultaine and AOS where sultaine does not boost the foam of blend to any better value than AOS.
• Presence of crude oil : AOS foam performs well in the presence of crude oil that a blend is not required for the test conditions in this study.
• None of the surfactants have measurable interfacial rheology.• Regular solution theory predicts there is more synergism in Betaine
& AOS blends than in Sultaine & AOS blends. However this does not have correlation to foam strength for the test conditions. ( Rosen et.al , Journal of the American Oil Chemists’ Society, April 1988, Volume 65, Issue 4, pp 663-668)
• Pure Lauryl Betaine and Pure Lauryl Sultaine surfactants are not good foamers in interests of EOR.
Acknowledgements• Foam Experimental set up– Michiel Slob- TU Delft– Dr. Ali Akbar Eftekhari- TU Delft
• Interfacial Rheology – Dr. Gerard Fuller’s lab – Stanford University
• Surface/Interfacial tension measurements– Hakim Hamouche- Kibron
• Processes in Porous Media Consortium, Solvay, Shell Rijswijk.
Back up slides
27
Procedure to determine concentration to estimate parameter at interfaces
1E-06 1E-05 1E-04 1E-03 1E-020
10
20
30
40
50
60
70
80
f(x) = − 13.4079299801969 ln(x) − 85.0595667502185R² = 0.969775950106801f(x) = − 10.6320995010589 ln(x) − 59.1753417612303
R² = 0.950714095608722
f(x) = − 14.0942782895045 ln(x) − 80.062552908297R² = 0.962006673466344f(x) = − 10.5046045830633 ln(x) − 32.3740021495709
R² = 0.929662064381792
betaineLogarithmic (betaine)AOSLogarithmic (AOS)LB:AOS 7:3Logarithmic (LB:AOS 7:3)LB:AOS 1:9Logarithmic (LB:AOS 1:9)
concentration (M)
Surf
ace
tens
ion
(mN
/m)
Here example case of betaine AOS blends are shown
28
Du-Nuoy method- Kibron EZ-Pi Plus
Rate of pulling= 0.2 mm/s
F = 2 π r
29
Characterization of synergism by parameter for Sultaine AOS blends
Surfactant Bulk mole fraction LS
Interfacial mole fraction X1
Micellar mole fraction Xm
M
Sultaine8 Sultaine + 2 AOS 0.73 0.50 0.52 -1.56 -1.92
1 Sultaine+ 9 AOS 0.072 0.18 0.19 +0.24 +0.29AOS
Air-liquid interface(linear fit)
Surfactant LS X1 Xm M
Sultaine
8 Sultaine + 2 AOS 0.73 0.50 -1.01
1 Sultaine+ 9 AOS 0.072 Cannot solve perhaps mole fraction of LS is too low.
AOS
Octane-liquid interface (polynomial fit)
30
Characterization of synergism by parameter- Betaine AOS blends
Surfactant Bulk mole fraction LS
Interfacial mole fraction X1
Micellar mole fraction Xm
Surfactant
Betaine
7 Betaine +3AOS 0.77 0.49 0.48 -7.08 -2.84
1 Betaine+ 9 AOS 0.14 0.31 0.26 -2.72 -1.40
AOS
Surfactant X1 Xm M
Betaine
7 Betaine +3AOS 0.37 -3.24
1 Betaine+ 9 AOS 0.30 0.27 -2.19 -0.77
AOS
Octane-liquid interface
Air-liquid interface
31
Pressure History and Oil recovery LS:AOS 1:9
0 5 10 15 20 25 30 350
102030405060708090
100Oil recovery
Total injected PV
Cum
mul
ative
Oil
reco
very
(%
)
0 5 10 15 20 25 30 350
1020304050607080
0
5
10
15
20
25
30internal tap overall Interstitial velocity
Total injected PV
Pres
sure
dro
p (p
si)
Inte
rstiti
al v
eloc
ity (ft
/day
)