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EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

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Page 1: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

EOR by “Smart Water”Why ???Why ???

Page 2: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Outline

• Background– Wettability

• Capillary pressure curve• Relative permeability of oil and water

• “Smart Water” in Carbonates– Chemical mechanism– Chemical mechanism– EOR-potential

• “Smart Water” in Sandstones– Chemical mechanism – EOR-potential

Page 3: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Research direction

• Water based EOR by “Smart Water”

– How to optimize the ion composition of injection water to promote wettability alteration to improve oil recovery by water flooding.flooding.

– Detailed knowledge about the chemical mechanism in order to be able to evaluate actual field candidates for “smart” water.

– Carbonates and Sandstones

Page 4: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

What is “Smart Water”?

• “Smart water” can improve initial wetting properties of the reservoir and optimise fluid flow/oil recovery in porous medium during production.

• “Smart water” can be made by modifying the ion composition. No expensive chemicals are added.composition. No expensive chemicals are added.

• Wetting condition dictates– Capillary pressure curve; Pc=f(Sw)– Relative permeability; ko and kw = f(Sw)

Page 5: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Wetting properties in carbonates

• Carboxylic acids, R-COOH– AN (mgKOH/g)

• Bases (minor importance)– BN (mgKOH/g)

• Charge on interfaces

- - - -

+ + + + + + +

- - - -

+ + + + + + +

Ca2+ Ca2+ Ca2+

• Charge on interfaces– Oil-Water

• R-COO-

– Water-Rock• Potential determining ions

– Ca2+, Mg2+, SO42-, CO3

2-

, pH

- - - -

- - - - -SO4

2- SO42- SO4

2-

Page 6: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Spontaneous imbibition into chalk

Imbibition temperature 40 °C

50

60

70

80

Oil

prod

uctio

n, %

OO

IP

Oil A. AN=0, Test 1

0

10

20

30

40

50

1 10 100 1000 10000 100000 1000000

Time, min.

Oil

prod

uctio

n, %

OO

IP

Oil A. AN=0, Test 1

Oil D. AN=0.055, Test 7

Oil B. AN=0.06, Test 5

Oil E. AN= 0.41, Test 8

Oil C. AN=0.52, Test 6

Oil F. AN=1.73, Test 9

Page 7: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Wettability alterationStandnes and Austad, J. Pet. Sci Eng. 28 (2000) 123-143

Cationic surfactant: n-C 12N(CH3)3Br termed C12TAB• Chalk: 2 mD, T=40 oC• Oil: AN=1.0 mgKOH/g

Imbibition temperature 40 °C

0

10

20

30

40

50

60

70

0 20 40 60 80 100 120Time, days

Oil

prod

uctio

n, %

OO

IP

C12TAB, Test 1

C12TAB, Test 2

C12TAB, Test 4

Brine, Test 3

Page 8: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Can SW change wetting conditions of Chalk ??

• SO42- was important as a catalyst for

wettability alteration by C12TAB.– The efficiency increased as the temperature

increasedincreased

• Can seawater act as a wettability modifier at high temperature without using expensive surfactants ???!

Page 9: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Question:

• Why is injection of seawater such a tremendous success in the Ekofisk field??– Highly fractured– High temperature, 130 oC.– Low matrix permeability, 1 -2 mD– Low matrix permeability, 1 -2 mD– Wettability:

• Tor-formation: Preferential water-wet• Lower Ekofisk: Low water-wetness• Upper Ekofisk: Neutral to oil-wet

Page 10: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Oil recovery prognoses

400

OIL

RA

TE

, MS

TB

D (

GR

OS

S)

2001: Goal: 46%

NPD;2002: 50%

0

1972

1976

1980

1984

1988

1992

1996

2000

2004

2008

2012

2016

2020

2024

2028

OIL

RA

TE

, MS

TB

D (

GR

OS

S)

OOIP∼∼∼∼18 %

OOIP∼∼∼∼46 %

2007: Goal 55 %

Page 11: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Model brine compositionComp. Ekofisk Seawater

(mole/l) (mole/l)Na+ 0.685 0.450K+ 0 0.010Mg2+ 0.025 0.045Ca2+ 0.231 0.013Ca 0.231 0.013Cl- 1.197 0.528HCO3

- 0 0.002SO4

2- 0 0.024

Seawater: [SO42-]~2 [Ca2+] and [Mg2+]~ 2 [SO4

2-]

[Mg2+]~4 [Ca2+]

Page 12: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Effects of Sulfate and T

100 oC 130 oC

• Crude oil: AN=2.0 mgKOH/g•Initial brine: EF-water•Imbibing fluid: Modified SSW

0.0

10.0

20.0

30.0

40.0

50.0

0 5 10 15 20 25 30 35 40 45

Time (days)

Rec

over

y (%

OO

IP)

CS100-5 - SSW*4S

CS100-2 - SSW*3S

CS100-4 - SSW*2S

CS100-1 - SSW

CS100-3 - SSW/2S

CS100-6 - SSW/US

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

0 2 4 6 8 10 12 14

Time (days)

Rec

ove

ry (

%O

OIP

)

CS3-1 - SSW*4S

CS3-2 - SSW*2S

CS3-8 - SSW*2S

CS3-3 - SSW

CS3-4 - SSW/2S

CS3-5 - SSW/US

Parallel tests!

Page 13: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Sulfate adsorption-Temp. effects

0.75

1.00

C/Co SCN FL#7-1 SSW-M at 21°C A=0.174

C/Co SO4 FL#7-1 SSW-M at 21°C

�Chromatographic separation of SCN- and SO42-

0.00

0.25

0.50

0.75

0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2PV

C/C

o

C/Co SO4 FL#7-1 SSW-M at 21°C

C/Co SCN FL#7-2 SSW-M at 40°C A=0.199

C/Co SO4 FL#7-2 SSW-M at 40°C

C/Co SCN FL#7-3 at 70°C A=0.297

C/Co SO4 FL#7-3 at 70°C

C/Co SCN FL#7-4 at 100°C A=0.402

C/Co SO4 FL#7-4 at 100°C

C/Co SCN FL#7-5 at 130°C A=0.547*(Extrapolert2.6PV)C/Co SO4 FL#7-5 at 130°C

Page 14: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Is Ca2+ active in the wettability alteration??

• Crude oil: AN=0.55 mgKOH/g• Swi = 0; Imbibing fluid: Modified SSW• Temperature: 70 oC

60.0

70.0

Oil

reco

very

(%

OO

IP)

0.0

10.0

20.0

30.0

40.0

50.0

0.0 10.0 20.0 30.0 40.0 50.0 60.0

Time (day)

Oil

reco

very

(%

OO

IP)

CS100-1 - SSW*4Ca

CS100-2 - SSW*3Ca

CS100-3 - SSW

CS100-4 - SSW/2Ca

CS100-5 - SSW/UCa

Page 15: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Affinities of Ca 2+ and Mg 2+ towards the chalk surface

0.75

1.00

C/Co SCN (Brine with Mg andCa2+) at 23C [Magnesium] 1.25

1.50

1.75

2.00

T=20 oC T=130 oC

•NaCl-brine,[Ca 2+]= [Mg 2+]= 0.013 mole/l

0.00

0.25

0.50

0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6PV

C/C

o

Ca2+) at 23C [Magnesium] A=0.084C/Co Mg2+ (Brine with Mg2+and Ca2+) at 23°C

C/Co Ca2+ (Brine with Mg2+and Ca2+) at 23°C

0.00

0.25

0.50

0.75

1.00

1.25

0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0PVC

/Co

C/Co SCN (Brine with Mg and Ca2+)at 130°C

C/Co Mg2+ (Brine with Mg2+ andCa2+) at 130°C

C/Co Ca2+ (Brine with Mg2+ andCa2+) at 130°C

CaCO3(s) + Mg 2+ = MgCO3(s) + Ca2+

Page 16: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Effects of potential determining ions on spontaneous imbibition

Imbibition at 70 & 100 oC (with/without Ca & Mg)

40

60

Rec

over

y, %

OIIP

25:SWx0CaMg(+Mg@43days)

26:SWx0Sx0CaMg(+Mg@ 53 days)

27:SWx2Sx0CaMg(+Ca@43 days)

28:SWx4Sx0CaMg(+Mg@53 days)

0

20

40

0 20 40 60 80 100 120Time, days

Rec

over

y, %

OIIP

70°C

100°C 130°C

Page 17: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Suggested wettability mechanism

High T

Page 18: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Test by BP on Valhall(Webb et al. IPTC 10506, Doha, 2005)

• Complete reservoir conditions, Tres=90 oC• Oil recovery using FW and SW

– Imbibition at Pc=0: FW: 22.4 %PV and SW: 31 %PV; 40% increase– Forces imbibition at Pc=-1 psi: FW: ~45%PV and SW: ~60%PV

Page 19: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Flow conditions

• Fractured vs. non-fractured reservoir– Spontaneous imbibition– Forced imbibition

• What is the efficiency of “Smart Water” • What is the efficiency of “Smart Water” ???

Page 20: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Spontaneous vs. forced imbibition

90 oC

110 oC 120 oC

Page 21: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Environmental aspects

• Can PW water be co-injected with SW and still act as a “Smart” EOR-fluid ???– Compatibility between SW and PW

• Precipitation of CaSO4, SrSO4, and BaSO4• Precipitation of CaSO4, SrSO4, and BaSO4

Page 22: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Mixtures of PW with SW at 110 oC

40

50

60

70R

ecov

ery

(%O

OIP

)

0

10

20

30

0 10 20 30 40 50Time (Days)

Rec

over

y (%

OO

IP)

SI PW1SSW8

SI PW1SSW2

SI PW1SSW1

SI PW

"FI PW"

"FI SSW"

Crude oil: AN = 1.9 mgKOH/g. Chalk

Page 23: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

”Smart Seawater” in Chalk

110 oC 120 oC

50%

60%

70%

80%

Re

co

ve

ry F

acto

r (%

OO

IP

)

40%

50%

60%

70%

80%

Re

co

ve

ry F

acto

r (%

OO

IP

)

0%

10%

20%

30%

40%

0 10 20 30 40 50 60 70

Time (days)

Re

co

ve

ry F

acto

r (%

OO

IP

)

SSW SSW0NaCl Dil SSW 20000 Dil SSW 10000

Fig. 3. Spontaneous imbibition at 110 ºC

0%

10%

20%

30%

0 5 10 15 20 25 30 35

Time (days)

Re

co

ve

ry F

acto

r (%

OO

IP

)

SSW SSW0NaCl DilSSW 1600

DilSSW 1600 SSW4NaCl

Fig. 4. Spontaneous imbibition at 120 ºC using different imbibing fluids with different salinities and ionic composition.

EOR-potential by ”Smart Seawater” (depleted in NaCl) in Ekofisk may increase recovery by 10 % of OOIP: Money .. Money !!!!!

Page 24: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Forced Imbibition

• Smart SW in a tertiary process

50%

60%

70%

80%

Re

co

ve

ry F

acto

r %

0%

10%

20%

30%

40%

0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

PV Injected (ml)

Re

co

ve

ry F

acto

r %

F.W. SSW SSW0NaCl

Fig. 11. Forced Displacement at 120ºC at the rate of 1.0 PV/day; forced displacement by formation brine, seawater and seawater without NaCl

Page 25: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Low Salinity

0.3

0.4

0.5

0.6

0.7

Oil

Pro

duct

ion

(Tot

al P

ore

Vol

ume)

0.535 PV

0.61 PV

N. Morrow and later BP

0

0.1

0.2

0 5 10 15 20 25 30

Water Throughput (Pore Volumes)

Oil

Pro

duct

ion

(Tot

al P

ore

Vol

ume)

High Salinity Low Salinity(15,000 ppm) (1,500 ppm)

By: Webb et al. 2005.(By: Larger et al. 2007)

The average LowSal effect is ~14 %

Page 26: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Important parameters

• Initial wetting– Clay

• Different clays have different pH range for optimum adsorption

– Initial FB

• LowSal fluid– Composition

• Less important ?• Low ionic strength

important• Gradient in active ions– Initial FB

• Divalent vs. mono valent ions, important ??

• pH~5 (dissolved CO2)– Crude oil

• BN important• AN important

– Temperature• High and low T, OK

• Gradient in active ions– pH change

• Local increase in pH at the clay surface important ?

– Dynamic process• Flooding rate• Irreversible desorption

Page 27: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Suggested mechanisms

• Wettability modification towards more water-wet condition, generally accepted.

• Migration of fines (Tang and Morrow 1999).• Increase in pH lower IFT; type of alkaline flooding • Increase in pH lower IFT; type of alkaline flooding

(Mcguri et al. 2005). • Multicomponent Ion Exchange (MIE) (Lager et al.

2006).• Small changes in bulk pH can impose great

changes in Zeta-potential of the rock (StatoilHydro)• “Salting in” effects

Page 28: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Presentation linked to:

SPE 129767-PPChemical Mechanism of Low Salinity Water

Flooding in Sandstone ReservoirsFlooding in Sandstone Reservoirs

Tor Austad, Alireza RezaeiDoust and Tina Puntervold, University of Stavanger, 4036 Stavanger, Norway

This paper was prepared for presentation at the 2010 SPE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, USA, 24–28 April 2010.

Page 29: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Is Low Sal effect a “salting in” effect ?Adsorption/desorption onto kaolinite

• Quinoline

1.50

2.00

2.50

mg

PTB

BA

ads

orbe

d / g

kao

linite

Ads isotherm

Desorption HS#1

Desorption HS#2

Desorption LS#1

~25000 ppm

~25000 ppm

~11200 ppm

pH ~6.3

pH ~5.4

• Carboxylic acid

1.50

2.00

2.50

mg

Qui

nolin

e ad

sorb

ed /

g ka

olin

ite

25000 ppm

16000 ppmpH ~5

11000 ppmpH ~5.27200 ppm

pH ~5.3

pH ~5

2200 ppmpH ~5.1

3100 ppmpH ~5.1

4900 ppmpH ~5.2

2000 ppmpH ~5.6

3000 ppmpH ~5.6

4900 ppmpH ~5.3

1100 ppmpH ~5.3

1000 ppmpH ~6.0

0.00

0.50

1.00

0.0000 0.0010 0.0020 0.0030 0.0040 0.0050 0.0060

Equilibrium [PTBBA], mol/l (M)

mg

PTB

BA

ads

orbe

d / g

kao

linite

Desorption LS#1

Desorption LS#2

~4600 ppm

~2300 ppm~1300 ppm

pH ~6.1

pH ~4.5

0.00

0.50

1.00

0.0000 0.0005 0.0010 0.0015 0.0020 0.0025 0.0030 0.0035

Equilibrium [Quinoline], mol/l (M)

mg

Qui

nolin

e ad

sorb

ed /

g ka

olin

ite

Ads isotherm

Desorption HS#1 pH adj

Desorption HS#2 pH adj

Desorption HS#3

Desorption HS#4

Desorption LS#1 pH adj

Desorption LS#2 pH adj

Desorption LS#3

Desorption LS#4

Page 30: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Suggested mechanismInitial situation Low salinity flooding Final situation

Clay

NH Ca2+

O

H

H

Clay

NH Ca2+

Clay

NCa2+

H+HO

H

Fig. 1. Proposed mechanism for low salinity EOR effects. Upper: Desorption of basic material. Lower: Desorption of acidic material. The initial pH at reservoir conditions may be in the range of 5.

C HO

H

Clay

Ca2+H+

R

HO

O H

OH

Clay

Ca2+

H+H+

R

O-

CO

Clay

Ca2+H+

R

HO

O C

Page 31: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Chemical equations

• Desorption of cations by low sal water– Clay-Ca2+ + H2O = Clay-H+ + Ca2+ + OH-

• Wettability alteration– Basic material– Basic material

• Clay-NHR3+ + OH- = Clay + R3N + H2O

• Acidic material• Clay-RCOOH + OH- = Clay + RCOO- + H2O

Page 32: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Adsorption of basic materialQuinoline

Kaolinite

Nonsweeling(1:1 Clay)

Burgos et al.

Evir. Eng. Sci.,

19, (2002) 59-68.

Montmorillonite

Swelling (2:1 clay, similar in structure to illite/mica)

Page 33: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Desorption of quinoline

Kaolinite

Burgos et al. Evir. Eng. Sci.,19, (2002) 59-68.

Montmorillonite

Page 34: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Adsorption reversibility by pH

5,00

6,00 Adsorption pH 5

Desorption pH 8-9

Readsorption pH 5.5

QuinolineSamples 1-6: 1000 ppm brine.Samples 7-12: 25000 ppm brine

0,00

1,00

2,00

3,00

4,00

5,00

0 5 10 15

Ads

orpt

ion

(mg/

g)

Sample no.

Readsorption pH 5.5

Desorption pH 2.5

Page 35: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

What is the role of the acidic components ??

• Adsorption of benzoic acid onto kaolinite at 32 °C in a NaCl brine (Madsen and Lind, 1998)

pHinitial Γmax µmole/m2 µmole/m

5.3 3.7 6.0 1.2 8.1 0.1

Increase in pH increases water wetness.

No correlation between AN and LowSal effects has been detected (Larger et al.)

Page 36: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Acid – base properties similar

• BaseBH+ = H+ + BpKa=4.7

[ ][ ]B

BHpKpH a

+

+= lg [ ]B

•Acid

HA = H+ + A-

pKa = 4.9[ ]

[ ]B

BHpKpH a

+

+= lg

Fig 4. Supposed adsorption of R–COOH onto clay by H-bonding at pH 4-5. Analogue to a dimeric complex of carboxylic acid.

O C

Clay

H+

R

HO C

H

OR C

O

OR

H

O

Page 37: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Decrease in pH by CO 2 and H2S

5

6

7

8

pH

2

3

4

1.00E-10 1.00E-08 1.00E-06 1.00E-04 1.00E-02

mol added H2S or CO2

Varg H2SVarg CO2DW H2SDW CO2Seawater H2SSeawater CO2

Fig. 6. Simulated change in pH when CO 2 or H2S is dissolved into 200000 ppm Varg reservoir brine under pressure at 7 5 °C. Pressure was 100 atm to keep the gas in solution.

Page 38: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Important clay properties

Table 5 Properties of actual clay minerals (International Drilling Fluids (IDF), 1982)

Property Kaolinite Illite/Mica Montmorillonite Chlorite

Layers 1:1 2:1 2:1 2:1:1 Layers 1:1 2:1 2:1 2:1:1

Particle size (micron) 5-0.5 large sheets to 0.5 2-0.1 5-0.1

Cation exchange cap. (meq/100g)

3-15 10-40 80-150 10-40

Surface area BET-N2 (m2/g) 15-25 50-110 30-80 140

General order of affinity: Li+<Na+<K+<Mg2+<Ca2+<H+

Page 39: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Adsorption/desorption of cations

• Kaolinite and Chlorite– Non-swelling– Adsorption at edge surfaces– Great selectivity for Ca2+ over Na+– Great selectivity for Ca over Na– FW: significant amount of Ca2+ needed

• Illite/Mica and Montmorillonite/Smectite– Lattice substitutions are the main mechanism– Lower selectivity for Ca2+ over Na+

– FW: Low sal effect without Ca2+ possible ???

Page 40: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Optimal condition for low sal effect

• Balanced adsorption onto clay– Organic material– Cations

• Key process• Key process– Local increase in pH close to the clay-water

interface promoted by desorption of cations.

Page 41: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Salinity of Low Sal fluid

Desoroption

FWAds

orp

LS

Fig. 7 Probable/Typical adsorption isotherm of Ca2+ from high saline brine onto clay minerals of a reservoir rock at pH 4-8.

eq. conc. Ca2+

LS

Page 42: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Solubility of Mg(OH) 2 and Ca(OH)2 vs. pH

1E-061E-05

0.00010.001

0.010.1

1

mol

Mg2

+ or

Ca2

+

1E-111E-101E-091E-081E-071E-06

5 6 7 8 9 10 11 12 13 14

pH

mol

Mg2

+ or

Ca2

+

Mg2+ 50 °CMg2+ 100 °CCa2+ 50 °CCa2+ 100 °C

Fig. 10. Solubility of Mg(OH)2 and Ca(OH)2 versus p H at 50 and 100 oC in a 50 000 ppm NaCl brine and 6 bars.

Page 43: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Change in Mg 2+ can be related to precipitation of Mg(OH) 2

[Mg2+]mol/l

10-3

Fig. 11. Schematically change in Mg2+ concentration in the produced water during a low salinity flood. The concentration of Mg2+ is suggested to be quite similar for the initial FW and low saline brine.

pH>9pH≤ 8 pH≤ 8

Low Salinity

Page 44: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Outcrop material

• Minerals– Clay content

• Kaolinite 0 wt%• Chlorite 1.9 wt%• Chlorite 1.9 wt%• Illite 8.5 wt%

– Quartz ~57 wt%– Albite ~ 32 wt%– CaCO3 0.3 wt%

Page 45: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Brine and oil used

NaCl

(mole/l) CaCl2 .2H2O

(mole /l) KCl

(mole /l) MgCl2 .2H2O

(mole /l)

Connate Brine 1.54 0.09 0.0 0.0

Low Salinity Brine-1 0.0171 0.0 0.0 0.0

Low Salinity Brine-2 0.0034 0.0046 0.0 0.0

Low Salinity Brine-3 0.0 0.0 0.0171 0.0 Low Salinity Brine-3 0.0 0.0 0.0171 0.0

Low Salinity Brine-4 0.0034 0.0 0.0 0.0046

Total oil: AN=0.1 and BN=1.8 mgKOH/g

Res 40: AN=1.9 and BN=0.47 mgKOH/g

Page 46: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Effects if Low Sal brine composition

0

10

20

30

40

50

60

Rec

over

y (%

)

B15 - CaCl2 Brine

B14 - NaCl Brine

B16 - MgCl2 Brine

Total oil

0

0 2 4 6 8 10 12 14

PV Injected

0

20

40

60

80

100

0 2 4 6 8 10 12

Tho

usan

ds

Brine PV Injected

Sal

inity

(pp

m)

4

5

6

7

8

9

10

pH

B15-SalinityB14-SalinityB16-SalinityB15-pHB14-pHB16-pH

Page 47: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Effect of oil properties

40

50

60

Rec

over

y (%

)

0

10

20

30

0 2 4 6 8 10 12 14

PV Injection

Rec

over

y (%

)

B-15 TOATL Oil

B-11 Res-40 Oil

Page 48: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Lower initial pH by CO 2

Core No.

Swi %

TAging ° C

TFlooding ° C

Oil Low Salinity

Flood Formation Brine

B18 19.76 60 40

TOTAL Oil

Saturated With CO2

at 6 Bars

Low Salinity-1

NaCl 1000

ppm

TOTAL FW

B14 19.4 60 40 TOTAL Oil Low Salinity-1

NaCl 1000

ppm

TOTAL FW

80

Low Salinity

10

0

10

20

30

40

50

60

70

0 2 4 6 8 10 12 14 16

Oil

Rec

over

y F

acto

r (%

OO

IP)

PV Injection

B18-Cycle-1 CO2 Saturated Oil

B14-Cycle-1 Reference Curve

High Salinity

Low Salinity

High Rate

4

5

6

7

8

9

0 2 4 6 8 10 12 14

Brine PV Injected

pH

B18-Cycle-1 CO2 Saturated Oi

B14-Cycle-1 Reference Test

High Salinity

Low Salinity

HCO3- + OH- ↔ CO3

2- + H20

Page 49: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Is EOR by LowSal flooding a LowSal effect? Core No.

Swi %

TAging ° C

TFlooding ° C

Oil Low Salinity

Brine Formation Brine

B01 20.0 60 40 TOTAL Oil Low Salinity-7

NaCl 40000

ppm

Pure CaCl2 25000 ppm

B14 19.4 60 40 TOTAL Oil

Low Salinity-1

NaCl 1000

ppm

TOTAL FW

60

Low Salinity

10

0

10

20

30

40

50

0 2 4 6 8 10 12 14

Brine PV Injection

Oil

Rec

over

y F

acto

r (%

OO

IP)

B01-Cycle-1B14-Cycle-1 Reference Test

High Salinity

Low Salinity

High Rate

4

5

6

7

8

9

0 2 4 6 8 10 12 14

Brine PV Injected

pH

B01-Cycle-1

B14-Cycle-1 Reference Test

High Salinity

Low Salinity

Gradient in the concentration of the most active ions, Ca2+, most important.

Ca2+ + OH- ↔ [Ca--OH]+

Page 50: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Conclusion

• The chemical mechanism for wettability modification in sandstones and carbonates is different.

• NPD:• NPD:– 1% increase in oil recovery (OOIP) will give net

100-150 billion NOK

• Arild Nystad (former resource dir. at NPD)– IOR programs can give 3000 new billions NOK

Page 51: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Ongoing projects

• Carbonates– BP: limestone in Abu Dhabi– Maersk / UiS: limestone in Qatar– Total/NFR: Outcrop limestone– Total/NFR: Outcrop limestone– Saudi Aramco: limestone

• Sandstone:– Talisman/Total: low salinity

Page 52: EOR by “Smart Water” Why · 2010-03-01 · • Water based EOR by “Smart Water” – How to optimize the ion composition of injection w ater to promote wettability alteration

Personnel: EOR-Group