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Transcript of Visosifying Surfactant for Chemical EOR EOR Workshop “Mario Leschevich”, 3-5 Nov. 2010 Mikel...
Visosifying Surfactant for Chemical EOR
EOR Workshop “Mario Leschevich”, 3-5 Nov. 2010
Mikel Morvan, Guillaume Degré, Rhodia Alain Zaitoun, Jérôme Bouillot, Poweltec.
Rhodia/Poweltec
2
Contents
• Introduction to viscosifying surfactants for EOR
• Rhodia and Poweltec methodology: application to synthetic field cases
• Viscosity measurements
• Fluid propagation tests
• Core flood tests
• Viscosifying surfactant: application to field case
• Conclusion
3
Introduction to viscosifying surfactants for EOR
• Introduction to surfactant mesophases in aqueous solutions
Packing Parameter (P) = VH/(lc.a0)
Spherical micelles P ~ 1/3
Cylindrical micelles P~ 1/3 to ½(Wormlike micelles or Hexagonal phases)
Lamellar phase P ~ 1
Molecular dimension, concentration and environment determine (T, S)
mesophases sequences
4
• Rheological properties of surfactant micelles in aqueous solutions
Spherical Micelles Cylindrical Micelles
Low viscosityNewtonian fluid
Entanglements
Analogy with polymer
Typical surfactant flooding(S, SP, ASP)
L 1 m
Viscosifying surfactant as an alternative approach to
SP & ASP flooding
Breakage/recombination dynamic
..)5.21()( s
= volume fraction
00 G G0: Elastic modulus: Relaxation time
Introduction to viscosifying surfactants for EOR
5
Presence of giant micelles of ≈ 5nm in diameter. A structure is visible, since they appear mostly in parallel configuration, with an inter particle distance 15 to 20nm.
Cryo-TEM image of wormlike micelles in aqueous solution
Introduction to viscosifying surfactants for EOR
6
Contents
• Introduction to viscosifying surfactants for EOR
• Rhodia and Poweltec methodology: application to synthetic field cases
• Viscosity measurements
• Fluid propagation tests
• Core flood tests
• Viscosifying surfactant: application to field case
• Conclusion
7
Rhodia & Poweltec methodology: application to synthetic field cases
Solubility Rheology Injectivity
Viscosifying surfactant
formulation
Coreflood
RHODIA
POWELTEC
Injectivity Adsorption Oil Recovery
Chemistry selection
Millifluidic screening tests
Petrophysic experiments
8
• Principle of high-throughput screening for viscosity measurements developed at Rhodia LOF
• Formulation composition (surfactant & salt concentrations) are imposed thanks to syringe pumps
QL
RP
8
4 Viscosity
3
. 4
R
Q
Shear rate
• Formulation viscosity is determined by pressure drop measurement
Capillary (length L, radius R)
ΔP
Pressure sensor
heating
ΔP
Pressure sensor
heating
Formulation
Mixing
MeasureQ1
Q2
Q3
Surfactantsolution
Saturated salt sol
Water
[Ca2+
] (g/L)
[sur
fact
ant]
(% w
/w)
0 5 100.1
0.15
0.2
0.25
0.3
0.35
5
10
15
20
visc
osit
y (c
P)
Map viscosity performance versus reservoir brine variations prior to full characterization using traditional rheometer
Rhodia & Poweltec methodology: application to synthetic field cases
9
Viscosity measurements
0 0.1 0.2 0.3 0.4 0.50
20
40
60
80
concentration (%w/w
)
Abs
. vis
cosi
ty (
cP)
0 0.1 0.2 0.3 0.4 0.50
20
40
60
80
concentration (%w/w
)
Abs
. vis
cosi
ty (
cP)
0.1 0.3 0.5 0.7 0.90
50
100
150
200
concentration (% w/w)
Abs
. vis
cosi
ty (
cP)
0.1 0.3 0.5 0.7 0.90
100
200
300
400
500
concentration (% w/w)
Abs
. vis
cosi
ty (
cP)
Our viscosifying surfactants are salt tolerant (including divalent ions) with favorable impact of high brine concentration
Salinity (g/L TDS)
T (°C)
0
32°C
51°C
200
80°C
96
90°C
6
Field 3
Field 2
Field 1
Field 3
Shear rate: 4 s-1
Viscosity measurements applied to various reservoir cases
9
10
Flow curve measurements in one reservoir condition
10-2
10-1
100
101
102
103
100
101
102
103
104
shear rate (s-1
)
visc
osit
y (c
P)
0.9%
0.7%
0.5%
0.3%
0.1%
Shear thinning behavior indicates that a decrease of shear rates lead to an increase of viscosity. Required surfactant concentration is thus reduced
Viscosity measurements
11
• Principle of miniaturized core flood test developed at Rhodia LOF
Syringe pump
Porous mediaInjectivity, porous media
PcorePcapillary
Imposed flow rate
CapillaryAdsorption
Syringe pump
Porous mediaInjectivity, porous media
PcorePcapillary
Imposed flow rate
CapillaryAdsorption
5 cm
Syringe pumpCapillaryviscometer
Pressure sensor
Pressure sensorcore
• A miniaturized core flood test has been developed to measure fluid propagation in single-phase condition
• This miniaturized test can be used prior to full coreflood study to pre-screen performances of new surfactant formulations.
Rhodia & Poweltec methodology: application to synthetic field cases
12
• An illustration of permeability measurement from (Q, P) curve
Syringe pump
Porous mediaInjectivity in porous media
PcorePcapillary
Imposed flow rateCapillaryAdsorption
0 2 4 60
50
100
150
200
250
300
Q (mL/min)
P
(mba
r)
0 100 200 3000
50
100
150
200
250
300
time (s)
pre
ssu
re (
mb
ar)
Q = 5 mL/min
Q = 4 mL/min
Q = 3 mL/min
Q = 2 mL/min
Q = 1 mL/min
k
Patmosph..
Millifluidic set-up used to measure mobility & permeability reduction
Rhodia & Poweltec methodology: application to synthetic field cases
13
Mobility Reduction is also called “Resistance Factor RF”
pressure drop during viscosifying surfactant slug injection at q cm3/h
pressure drop during initial brine injection at q cm3/h
Mobility Reduction
Background on mobility & permeability reduction
Permeability Reduction “Residual Resistance Factor RRF”
Visco. Surf
P
PRm
=
pressure drop during brine injection after viscosifying surfactant slug at q cm3/h
pressure drop during initial brine injection at q cm3/h
Permeability Reduction
Initial brine
Brine - After visco surf.
P
PRk
=
Initial brine
Rhodia & Poweltec methodology: application to synthetic field cases
14
• Example of flow behavior in representative porous media (Clashach sandstone) using miniaturized core flood test
Rheometer Bulk viscosity
Viscosity in porous media injection in coresimpose Q and measure P
100
102
104
100
101
cisaillement (s-1
)
visc
osit
e, R
m C2
C1
Miniaturized core dataBulk rheology
Flow in porous media match bulk rheologyGood propagation of viscosifying surfactant in porous media
Fluid propagation tests
kr
8
Mean pore radius
Sr
Q
Darcy’s Law
Flow rate
Q
Shear rate
Pressure drop viscosity
PWater
Surf
Water
Surfm
P
PR
..
Capillary bundle model
15
• Representative porous media: synthetic core
• Surfactants solution is injected in water saturated cores to evaluate propagation properties in porous media
• Surfactants solution is injected in oil saturated cores to measure oil recovery efficiency (additional oil after water flooding)
Core flood tests
pH
BYPASS
CALIBRATED
Porous medium
INJ ECTION WATER
CHEMICALSOLUTION
PUMP
spectro
PUPSTREAM DOWNSTREAM
CAPILLARY
P
PTOTAL LENGTHP
pH
BYPASS
CALIBRATED
Porous medium
INJ ECTION WATER
CHEMICALSOLUTION
PUMP
spectro
PUPSTREAM DOWNSTREAM
CAPILLARY
P
PTOTAL LENGTHP
kS
QLP
Darcy’s law
1cm
16
• Porous media: clashach sandstone core• Kw = 1133 mD at 50°C – Injection brine: sea water
Mobility and permeability reduction measurements in monophasic conditions
Water
Surfm
P
PR
.
.
.
BeforeSurfbrine
AfterSurfbrinek P
PR
Mobility Reduction values match bulk rheology: product has a good injectivityPermeability Reduction is close to Rkw=1, showing no core damage
Core flood tests
17
Core flood sequence Core - Clashach sandstone:• Porosity: = 0.18
• Pore radius (est.): Rp = 3.4 µm
• Water permeability: Kw = 1133 mD at 50°C
• Residual oil saturation: Sor = 0.49
(oil = 4.2 cp @50°C) (before injecting surfactant)
Fluid formulation:• Injection brine: sea water (39 g/L
TDS)
• Surfactant concentration: 3 g/L
• Temperature: 50°C
Protocol1. Saturation with oil until Swi
2. Water injection until Sor
3. Surfactant injection
4. Oil recovery measurement
Results
Sor reduction: 12%Sor reduction: 12%
No Sor reduction with HPAM
No Sor reduction with HPAM
Core flood tests: oil recovery efficiency
18
Contents
• Introduction to viscosifying surfactants for EOR
• Rhodia and Poweltec methodology: application to synthetic field cases
• Viscosity measurements
• Fluid propagation tests
• Core flood tests
• Viscosifying surfactant: application to field case
• Conclusion
19
Viscosifying surfactant: application to field case
• Temperature: T = 51°C
• Permeability: k ~ 1 – 2 D
• Oil viscosity @ 51°C : = 100 - 200 cP
• Brine concentration: 6.2 g/L TDS
Reservoir conditions
• Select best viscosifying surfactant that matches reservoir characteristics
• Compare recovery performance with polymer flooding
Methodology
20
Absolute viscosity measurements in reservoir conditions show that same viscosity (20 cP - 10 s-1) as selected for HPAM solution (0.09%w/w)
is obtained at a concentration of 0.3%w/w.
10-1
100
101
102
100
101
102
103
shear rate (s-1
)
visc
osit
y (c
P)
0.5%
0.4%
0.3%
0.2%
0.1%
HPAM 0.09%
Viscosifying surfactant: application to field case
21
• Thermal stability of surfactant solution
Viscosity measured at 50°C at low shear rate (10s-1)
0 20 400
0.2
0.4
0.6
0.8
1
time (days)
/0
Surfactant concentration 0.3% w/wTemperature T = 51°CBrine concentration: 6.2 g/L TDSOxygen content < 50 ppb
Fluid formulation
Anaerobic ageing of surfactant solution shows that no viscosity loss is observed over one month - On going ageing
Viscosifying surfactant: application to field case
22
Regular polymer flooding (HPAM) experiment
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Water Saturation Sw
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1After polymer injection
Initial kr (oil)
Initial kr (water)
Oil
Rel
ativ
e P
erm
eab
ilit
y k
ro
Wat
er R
elat
ive
Per
mea
bil
ity
krw
Drop of water mobility
Krw = 0,131
Krw = 0,02
No Sor reduction is observed after HPAM injection
Reservoir core plug
Viscosifying surfactant: application to field case
23
Oil recovery experiments after polymer injection (HPAM)
Injection of a 0.3%w/w surfactant solution after HPAM has mobilized a significant fraction of the residual oil saturation (+16% OOIP)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Water Saturation Sw
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1Initial kr (oil)After TAV flush (water)After TAV flush (oil)Initial kr (water)
Oil
Rel
ativ
e P
erm
eab
ilit
y k
roW
ater Relative P
ermeab
ility krw
Drop of water mobility
Mobilization of extra oilKrw = 0.131
Krw = 0.02
Reservoir core plug
Viscosifying surfactant: application to field case
24
Simulation
• Five Spot Pattern (1 Injector 4 Producers)
• Multilayer Reservoir, Strong vertical heterogeneity
• Reservoir thickness = 10 m
• Comparison between
• Waterflood
• Polymer Flood
• Viscosifying Surfactant Flood
Evaluation of viscosifying surfactant in synthetic field case
25
Simulation
Evaluation of viscosifying surfactant in synthetic field case
26
Recovery Factor RF @ 6 years RF @ 11 years
Water flood 33 % 39 %
Polymer flood 40 % 46 %
Viscosifying surfactant 50 % 56 %
Simulation
Evaluation of viscosifying surfactant in synthetic field case
27
Contents
• Introduction to viscosifying surfactants for EOR
• Rhodia and Poweltec methodology: application to synthetic field cases
• Viscosity measurements
• Fluid propagation tests
• Core flood tests
• Simulation
• Viscosifying surfactant: application to field case
• Conclusion
28
Conclusion
• Specific millifluidic tools have been developed to screen viscosifying surfactants from Rhodia
• Following performances have been measured for viscosifying surfactants in different conditions
• Viscosity at low concentration: 0.1 to 0.5% w/w
• Sor reduction in coreflood Sw = 10 to 20% (oil at least 100 cps)
• High temperature / high salinity tolerance
• Shear thinning / recombination dynamics (Unlike Polymer)
• Limited surface facility Capex required
• Perspectives
• Pursue experiment on field case reservoir: adsorption measurements, additional oil recovery tests, simulation and extrapolation at pilot scale to evaluate economics