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Smart Water Flooding in Carbonates and Sandstones:

A New Chemical Understanding of the EOR-potential

Tor Austad
(tor.austad@uis.no)

University of Stavanger, Norway

Example: Smart Water in Chalk

Spontaneous imbibition: Tres=90 oC; Crude oil AN=0.5; Swi=10%
Chalk: 1-2 mD

Formation water: VB
Seawater: SW
Seawater depleted in NaCl
Seawater depleted in NaCl and spiked with 4x sulfate

Example: Smart Water in Limestone

Spontaneous imbibition at 130C of FW and SW into

Res# 4-12 using crude oil with AN=0.50 mgKOH/g. Low
perm. 0.1-1 mD.
4

Example: Smart Water in Sandstone

Low Salinity EOR-effect under forced displacement
60

50

Recovery (%)

40

30

Low Salinity

High Salinity

B15-Cycle-2
20

10

0
0

10

PV Injection

HS: 100 000 ppm;

LS: 750 ppm

5

What is Smart Water?

Smart water can improve wetting properties of
oil reservoirs and optimize fluid flow/oil recovery
in porous medium during production.
Smart water can be made by modifying the ion
composition.
No expensive chemicals are added.
Environmental friendly.

Wetting condition dictates:

Capillary pressure curve; Pc=f(Sw)
Relative permeability; kro and krw = f(Sw)
6

Water flooding
Water flooding of oil reservoirs has been performed for a century
with the purpose of:
Pressure support
Oil displacement
Question:
Do we know the secret of water flooding of oil reservoirs??
If YES, then we must be able to explain why a Smart Water
sometimes increases oil recovery and sometimes not.
If we know the chemical mechanism, then the injected water can be
optimized for oil recovery.
Injection of the Smartest water should be done from day 1.

Outline
Discuss the conditions for observing EOReffecets by Smart Water in:
Carbonates
Sandstones

A very simplified chemical explanation

Wetting properties in carbonates

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

Bases (minor importance)

BN (mgKOH/g)

Ca2+

Ca2+

Ca2+

+ + + + + + +

Charge on interfaces
Oil-Water
R-COO Water-Rock
Potential determining ions
Ca2+, Mg2+,
(SO42-, CO32-, pH)

SO42-

- -

SO42-

- -

SO42-

Ekofisk
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

2028

2024

2020

2016

2012

2008

2004

2000

2007: Goal 55 %

1996

2002: 50%

1992

NPD;

1988

1984

1976: 18%
2001: Goal: 46%

1980

1976

Estimated recoveries

400

1972

Tor-formation: Preferential water-wet

Lower Ekofisk: Low water-wetness
Upper Ekofisk: Neutral to oil-wet

OIL RATE, MSTBD (GROSS)

Wettability:

10

Brine composition
Comp.

Ekofisk
(mole/l)

Seawater
(mole/l)

Na+
K+
Mg2+
Ca2+
ClHCO3SO42-

0.685
0
0.025
0.231
1.197
0
0

0.450
0.010
0.045
0.013
0.528
0.002
0.024

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

[Mg2+]~4 [Ca2+]

11

Effect of Sulfate in SW
Crude oil: AN=2.0 mgKOH/g
Initial brine: EF-water
Imbibing fluid: Modified SSW
Spontaneous imbibition at 100 oC
60

Oil Recovery , %OOIP

50
40

SW4S at 100C
SW3S at 100C
SW2S at 100C
SW at 100C
SWS at 100C
SW0S at 100C

30
20
10
0
0

10

20

Time, days

30

40

12

Is Ca2+ active in the wettability alteration?

Crude oil: AN=0.55 mgKOH/g

Swi = 0; Imbibing fluid: Modified SSW
Spontaneous imbibition at 70 oC

Oil Recovery , %OOIP

60

50
40
30
SW4Ca at 70C
SW3Ca at 70C
SW at 70C
SWCa at 70C
SW0Ca at 70C

20

10
0
0

10

20

30

Time, days

40

50

60

13

Co-Adsorption of SO42- and Ca2+ vs.

Temperature
1.00

C/Co SCN FL#7-1 SSW-M at 21C

0.75

A=0.174

C/Co

C/Co SO4 FL#7-1 SSW-M at 21C

C/Co SCN FL#7-2 SSW-M at 40C

A=0.199

C/Co SO4 FL#7-2 SSW-M at 40C

0.50
C/Co SCN FL#7-3 at 70C

A=0.297

C/Co SO4 FL#7-3 at 70C

C/Co SCN FL#7-4 at 100C

0.25

A=0.402

C/Co SO4 FL#7-4 at 100C

0.00
0.8

1.0

1.2

1.4

PV

A=0.547*(Extrapolert
2.0

2.2

C/Co

0.6

C/Co SCN FL#7-5 at 130C

2.6PV)
C/Co SO4 FL#7-5 at 130C
1.6
1.8

Method:
1.
Core saturated with SW
without SO422.
Core flooded with SW spiked
with SCN- (Chromatographic
separation of SCN- and SO42-)

1.0

0.5
C/Co Ca2+ Test #7/1 SW at 23C
C/Co Ca2+ Test #7/2 SW at 40C
C/Co Ca2+ Test #7/3 SW at 70C
C/Co Ca2+ Test #7/4 SW at 100C
C/Co Ca2+ Test #7/5 SW at 130C

0.0
0.5

1.0

1.5

2.0

2.5

PV

14

Affinities of Ca2+ and Mg2+ towards the

chalk surface
NaCl-brine; [SCN-] = [Ca2+] = [Mg2+]= 0.013 mole/l

T=23 oC

T=130 oC
2.00

1.00

1.75

1.50

0.75

0.50

1.25

C/Co

C/Co

C/Co SCN (Brine with Mg and

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

1.00

C/Co Ca2+ (Brine with Mg2+

and Ca2+) at 23C

0.75

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

at 130C
0.50

0.25

C/Co SCN (Brine with Mg and

Ca2+) at 23C [Calsium]
A=0.31

C/Co Mg2+ (Brine with Mg2+ and

Ca2+) at 130C
0.25

C/Co Ca2+ (Brine with Mg2+ and

Ca2+) at 130C
0.00

0.00
0.6

0.8

1.0

1.2

1.4

1.6 PV

1.8

2.0

2.2

2.4

2.6

0.6

0.8

1.0

1.2

1.4

1.6

1.8 PV

2.0

2.2

2.4

2.6

2.8

3.0

CaCO3(s) + Mg2+ = MgCO3(s) + Ca2+

15

Effects of potential determining ions and

temperature on spontaneous imbibition
Imbibition at 70 & 100oC (with/without Ca & Mg)

Recovery, %OIIP

25:SWx0CaMg(+Mg@43days)
26:SWx0Sx0CaMg(+Mg@ 53 days)

60

27:SWx2Sx0CaMg(+Ca@43 days)
28:SWx4Sx0CaMg(+Mg@53 days)

40

70C
20

100C

130C

0
0

20

40

60
80
Time, days

100

120

16

Suggested wettability mechanism

17

Can SO42- compensate for low Tres ?

oil recovery (%OOIP)

70
100C (Oil A, AN=2.07)
60
130C (Oil A, AN=2.07)
50

40

30

20

10

0
SSW-US

SSW-S

SSW

SSW2S

SSW4S

Imbibing fluids

Maximum oil recovery from chalk cores when different imbibing fluids
were used (SW with varying SO42- conc.). Oil: AN=2.07 mgKOH/g).
18

Ion composition in PW from Ekofisk

PW contained 73.6 vol% SW and 26.4 vol%FW
0.06

(PW)calc*

0.05

Concentration (mole/l)

(PW)exp
0.04

0.03

0.02

0.01

0
Ca2+

Mg2+

SO42-

Component

Fig. 3 Calculated and measured component concentration in

PW linked to substitution of Ca2+ by Mg2+ at the rock surface,
adsorption of SO42- onto the rock and precipitation of CaSO4.
19

Can modified SW be an even Smarter

EOR-fluid
Spontaneous imbibition: Tres=90 oC; Crude oil AN=0.5; Swi=10%

Formation water: VB
Seawater: SW
Seawater depleted in NaCl
Seawater depleted in NaCl and spiked with 4x sulfate
20

Effect of Salinity and Ion concentration

The access of potential determining ions to the calcite surface

is affected by the concentration of non active ions in the double layer
21

Forced displacement using Smart SW Water

Recovery, % OOIP

40

30

20
FW-0S
SW
SW-0NaCl

10

0
0

12

15

Injected PV

Oil recovery by forced displacement from the composite

limestone reservoir core. Successive injection of FW, SW and
SW-0NaCl. Ttest: 100C. Injection rate: 0.01 ml/min (0.6 PV/D).
22

Low salinity EOR-effects in carbonates

SPE 137634 Ali A. Yousef et al. (Saudi Aramco)

23

Codition for observing low salinity EOReffects in carbonates

The carbonate rock must contain anhydrite, CaSO4(s)
Chemical equilibrium:
CaSO4(s) Ca2+(aq) + SO42-(aq) Ca2+(ad) + SO42-(ad)
The concentration of SO42-(aq) depends on:
Temperature (decreases as T increases)
Brine salinity (Ca2+ concentration)

Wettability alteration process:

Temperature (increases as T increases)
Salinity (increases as NaCl conc. decreases)

Optimal temperature window

90-110 oC ?
24

Presence of CaSO4

Concentration profiles of Ca2+, Mg2+, and SO42- when flooding

reservoir limestone core with DI water, after aging with FW.
Ttest: 100C, Injection rate: 0.1 ml/min.
25

Low salinity EOR-effect

60

20

Sulfate concentration, mM

Recovery, % OOIP

FW-0S

18

50

40
22% of OOIP

30
20

10

FW-0S

100 dil. FW-0S

10 dil. FW-0S

16

100 dil. FW-0S

14

12
10
8
6

4
2

12

15

18

21

24

Injected PV

Oil recovery by forced displacement from a

reservoir limestone core containing anhydrite.
Successive injection of FW, and 100 diluted FW.
Ttest: 100C. Injection rate: 0.01 ml/min (1 PV/D).

50

100

150

Temperature, C

Simulated dissolution of CaSO4(s) when exposed to

FW-0S, 10 and 100 diluted FW at different
temperatures.

26

Smart Water in Sandstone

Some experimental facts
Porous medium
Clay must be present

Crude oil
Must contain polar components (acids and/or
bases)

Formation water
Must contain active ions towards the clay
(Especially divalent ions like Ca2+ and Mg2+)
27

General information

Adsorption onto clay

Local increase in pH important

Connate Brine
Low Salinity Brine-1
Low Salinity Brine-2
Low Salinity Brine-3

NaCl
(mole/l)
1.54
0.0171
0.0034
0.0

CaCl2 .2H2O
(mole /l)
0.09
0.0
0.0046
0.0

KCl
(mole /l)
0.0
0.0
0.0
0.0171

MgCl2 .2H2O
(mole /l)
0.0
0.0
0.0
0.0

Low Salinity Brine-4

0.0034

0.0

0.0

0.0046

30

Suggested mechanism

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 6
31

Clay minerals
Clays are chemically unique
Permanent localised negative charges
Act as cation exchangers
General order of affinity:
Li+ < Na+ < K+ < Mg2+ < Ca2+ << H+

32

Adsorption of basic material

Quinoline
Burgos et al.
Evir. Eng. Sci.,

Kaolinite

19, (2002) 59-68.

Nonsweeling(1:1 Clay)

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

33

Kaolinite: Adsorption reversibility by pH

Quinoline
Samples 1-6: 1000 ppm brine.
Samples 7-12: 25000 ppm brine
6,00

Adsorption pH 5
Desorption pH 8-9

Adsorption (mg/g)

5,00

Readsorption pH 5.5
Desorption pH 2.5

4,00
3,00
2,00
1,00
0,00

10

15

Sample no.

34

Adsorption of acidic components onto

Kaolinite
Adsorption of benzoic acid onto kaolinite at 32 C from a NaCl brine
(Madsen and Lind, 1998)

pHinitial
5.3
6.0
8.1

max
mole/m2
3.7
1.2
0.1

Increase in pH increases water wetness for an acidic crude oil.

35

Oil: Acidic or Basic

Total oil:

AN=0.1 and BN=1.8 mgKOH/g

Res 40:

AN=1.9 and BN=0.47 mgKOH/g

60

50

Recovery (%)

40

30

20

B-15

TOATL Oil

B-11

Res-40 Oil

10

0
0

10

12

14

PV Injection

36

Lower initial pH by CO2 increses the low

salinity effect
Core
No.

Swi
%

TAging
C

B18

19.7
6

B14

19.4

TFloodin

LS brine

Formation
Brine

TOTAL Oil
Saturated With CO2
at 6 Bars

NaCl: 1000
ppm

TOTAL FW
100 000
ppm

TOTAL Oil

NaCl:1000
ppm

TOTAL FW
100 000
ppm

Oil

60

40

60

40

80

10

Low Salinity
9

High Salinity
60

Low Salinity
8

50

High Salinity

High Rate

pH

Oil Recovery Factor (% OOIP)

70

40

30
6
B18-Cycle-1 CO2 Saturated Oil

20

B18-Cycle-1 CO2 Saturated Oi

B14-Cycle-1 Reference Curve

B14-Cycle-1 Reference Test

10
0

8
PV Injection

10

12

14

16

10

12

Brine PV Injected

CO2 + H2O H2CO3 + OH- HCO3- + H20 37

14

LS water increases oil-wetness

Adsorption of Quinoline vs. pH at ambient

temperature for LS (1000 ppm) and HS (25000
ppm) fluids.

Ref. Fogden and Lebedeva, SCA 2011-15

(Colloids and Surfaces A (2012)
Adsorption of crude oil onto kaolinite

It is not a decrease in salinity, which makes the

clay more water-wet, but it is an increase in pH
38

Snorre field
Lab work
Negligible tertiary low salinity effects after flooding
with SW, on average <2% extra oil.
Tres=90 oC

Single well test by Statoil

Confirmed the lab experiments

Question:
Why such a small Low Salinity effect after flooding
Snorre cores with SW ?
39

New study at UoS: Lunde formation

Table 1. Mineral composition
Core
13
14

Quartz
[wt%]
28.2
36.0

Plagioclase
[wt%]
32.1
35.2

Table 5. Properties of the oil.

AN
BN
[mgKOH/g oil] [mgKOH/g oil]
0.07
1.23

Calcite

Kaolinite

Illite/mica

Chlorite

[wt%]
1.4
2.4

[wt%]
2.6
3.9

[wt%]
9.3
7.4

[wt%]
3.6
2.9

Density (20C)
[g/cm3]
0.83653

Viscosity (30C) Viscosity (40C)

[cP]
[cP]
5.6
4.0

PS!! The oil was saturated with CO2 at 6 bar.

The core was flooded FW diluted 5x and the pH of the effluent stayed
above 10.
Plagioclase gives alkaline solution: pH: 7.5 to 9.5
40

Plagioclase
Anionic polysilicates give alkaline solution
Albite as example:
NaAlSi3O8 + H2O HAlSi3O8 + Na+ + OH-

At moderate salinities, the pH of FW will be

above 7, which means low adsorption of polar
components onto clay; negligible LS EOR-effect.
Due to buffer effects, the pH of FW was not
decreased significantly by adding CO2.

41

Snorre (Lunde) Core 13

CO2 was added

Fig. 3. Recovery vs. injected PVs for Core 13.

Flooding rate of 2 PV/D; Tres = 90 oC.

Low salinity effect of about 3-4 % of OOIP with SW as low

salinity fluid
42

Varg field: SPE 134459

Reservoir temperature: 130 oC

Salinity 201 000ppm
Brine composition;

Ta=90 , Tf=130oC

Ta=130 , Tf=130oC

43

Relationship: T and pH
Wettability alteration of clay by LS water:
Clay-Ca2+ + H2O Clay-H+ + Ca2+ + OH- + heat
Desorption of active cations from the clay surface is an
exothermic process, DH<0.
Divalent cations (Ca2+, Mg2+) are strongly hydrated in water, and as the
temperature increases the reactivity of these ions increases, and the
equilibrium is moved to the left.
The change in pH should decrease as the temperature increases.
Dissolution of anhydrite, CaSO4(s), will move the equilibrium to the left.
Gamage, P., Thyne, G. Systematic investigation of the effect of temperature during aging
and low salinity flooding of Berea sandstone and Minn, 16th European Symposium on
Improved Oil Recovery, Cambridge, UK, 12-14 April, 2011.
44

Temperatur pH screening
11
10

pH

9
8
7
40 C
90 C
130 C

6
5
0

12

16

20

24

Injected PV

Change in effluent pH versus PV injection fluid in core RC2 at

temperatures ranging from 40 C to 130 C. The brine flooding
sequence was HS-LS-HS.
45

Excellent LS EOR conditions

(Quan et al. IEA EOR Symposium 2012, Regina, Canada)

Minerals: Plagioclase 22%, Total clay 25% (mostly Illite and kaolinite)
FW: Ca2+ : 0.061 mole/l, Total salinity 57114 ppm
Tres = 65 oC
k = 1-2 mD, F=0.11
14.5% LS EOR-effect

46

Summary
Smart water EOR in Carbonates
Optimal brine composition
Modified SW: Depleted in NaCl and spiked with
SO42-: Active ions SO42-, Ca2+, Mg2+

Tres>70 oC
Conditions for LS EOR-effects
Formation must contain dissolvable anhydrite,
CaSO4.

47

Summary
Smart Water EOR effects in Sandstone
Formation water:
pH < 6.5
Reasonable high Ca2+ and total salinity.
Clay must be present (Illite and kaolinite)
Plagioclase can affect the pH both in a positive and negative
way LS EOR effects depending on initial salinity.
Combination of high Tres (>100 oC) and high conc. of Ca2+ can
make the formation too water-wet.
A pH-HS/LS scan can give valuable information of the potential
for LS-EOR effects.

48

Acknowledgement
Statoil,
ConPhil,
NFR
Total,
Talisman,
BP,
Maersk,
Shell,
Saudi Aramco,
DNO International.
49

EOR-group at UoS, 2010

50

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