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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

2
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
3
Example: ”Smart Water” in Limestone

Spontaneous imbibition at 130°C 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

40
Recovery (%)

30 Low Salinity
High Salinity

B15-Cycle-2
20

10

0
0 2 4 6 8 10
PV Inje ction

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.

7
 Outline
• Discuss the conditions for observing EOR-
effecets by «Smart Water» in:
– Carbonates
– Sandstones
• A very simplified chemical explanation

8
Wetting properties in carbonates
• Carboxylic acids, R-COOH
– AN (mgKOH/g) - - - -
• Bases (minor importance) Ca2+ Ca2+ Ca2+
– BN (mgKOH/g) + + + + + + +

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

9
 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

• Wettability:
– Tor-formation: Preferential water-wet
– Lower Ekofisk: Low water-wetness 400

OIL RATE, MSTBD (GROSS)

– Upper Ekofisk: Neutral to oil-wet
• Estimated recoveries
– 1976: 18%
– 2001: Goal: 46%
– NPD; 2002: 50%
0
– 2007: Goal 55 %
1972

1976

1980

1984

1988

1992

1996

2000

2004

2008

2012

2016

2020

2024

2028
10
 Brine composition

Comp. Ekofisk Seawater

(mole/l) (mole/l)
Na+ 0.685 0.450
K+ 0 0.010
Mg2+ 0.025 0.045
Ca2+ 0.231 0.013
Cl- 1.197 0.528
HCO3- 0 0.002
SO42- 0 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

50
Oil Recovery , %OOIP

40 SW4S at 100°C
SW3S at 100°C
30 SW2S at 100°C
SW at 100°C
20 SW½S at 100°C
SW0S at 100°C
10

0
0 10 20 30 40
Time, days

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

60

50
Oil Recovery , %OOIP

40

30
SW4Ca at 70°C
20 SW3Ca at 70°C
SW at 70°C
10 SW½Ca at 70°C
SW0Ca at 70°C
0
0 10 20 30 40 50 60
Time, days

13
Co-Adsorption of SO42- and Ca2+ vs.
Temperature
1.00

C/Co SCN FL#7-1 SSW-M at 21°C A=0.174 Method:

0.75 C/Co SO4 FL#7-1 SSW-M at 21°C

1. Core saturated with SW

C/Co

C/Co SCN FL#7-2 SSW-M at 40°C A=0.199

0.50
C/Co SO4 FL#7-2 SSW-M at 40°C

C/Co SCN FL#7-3 at 70°C A=0.297

without SO42-
0.25
C/Co SO4 FL#7-3 at 70°C

C/Co SCN FL#7-4 at 100°C A=0.402

2. Core flooded with SW spiked
C/Co SO4 FL#7-4 at 100°C with SCN- (Chromatographic
0.00
C/Co SCN FL#7-5 at 130°C A=0.547*(Extrapolert
2.6PV)
C/Co SO4 FL#7-5 at 130°C
separation of SCN- and SO42-)
0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
PV
C/Co

1.0

0.5
C/Co Ca2+ Test #7/1 SW at 23°C

C/Co Ca2+ Test #7/2 SW at 40°C

C/Co Ca2+ Test #7/3 SW at 70°C

C/Co Ca2+ Test #7/4 SW at 100°C

C/Co Ca2+ Test #7/5 SW at 130°C

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
C/Co SCN (Brine with Mg and
Ca2+) at 23C [Magnesium] 1.25
A=0.084

C/Co
C/Co

C/Co Mg2+ (Brine with Mg2+

1.00
0.50 and Ca2+) at 23°C

C/Co Ca2+ (Brine with Mg2+ 0.75

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

at 130°C
0.25
0.50
C/Co Mg2+ (Brine with Mg2+ and
Ca2+) at 130°C
0.25
C/Co Ca2+ (Brine with Mg2+ and
Ca2+) at 130°C
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

o
Imbibition at 70 & 100 C (with/without Ca & Mg)
25:SWx0CaMg(+Mg@43days)
26:SWx0Sx0CaMg(+Mg@ 53 days)
60
Recovery, %OIIP

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

40

70°C
20
100°C 130°C

0
0 20 40 60 80 100 120
Time, days

16
Suggested wettability mechanism

17
Can SO42- compensate for low Tres ?
70
oil recovery (%OOIP)

100°C (Oil A, AN=2.07)

60

130°C (Oil A, AN=2.07)

50

40

30

20

10

0
SSW-US SSW-½S SSW SSW×2S SSW×4S
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
(PW)exp
Concentration (mole/l)

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»

40

30
Recovery, % OOIP

20

FW-0S
10
SW
SW-0NaCl

0
0 3 6 9 12 15
Injected PV
Oil recovery by forced displacement from the composite
limestone reservoir core. Successive injection of FW, SW and
SW-0NaCl. Ttest: 100°C. 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 EOR-
effects 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: 100°C, Injection rate: 0.1 ml/min.

25
 Low salinity EOR-effect
60 20
FW-0S
18
50 10× dil. FW-0S

Sulfate concentration, mM
16
Recovery, % OOIP

100× dil. FW-0S

40 14
22% of OOIP 12
30 10
8
20
6

10 4
FW-0S 100× dil. FW-0S
2
0 0
0 3 6 9 12 15 18 21 24 0 50 100 150
Temperature, °C
Injected PV

Oil recovery by forced displacement from a Simulated dissolution of CaSO4(s) when exposed to
reservoir limestone core containing anhydrite. FW-0S, 10× and 100× diluted FW at different
Successive injection of FW, and 100× diluted FW. temperatures.
Ttest: 100°C. Injection rate: 0.01 ml/min (≈1 PV/D).

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
NaCl CaCl2 .2H2O KCl MgCl2 .2H2O
(mole/l) (mole /l) (mole /l) (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-4 0.0034 0.0 0.0 0.0046

30
Suggested mechanism
 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.,
19, (2002) 59-68.
Kaolinite
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
5,00
Readsorption pH 5.5
Adsorption (mg/g)

Desorption pH 2.5
4,00

3,00

2,00

1,00

0,00
0 5 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 Γmax
µmole/m2
5.3 3.7
6.0 1.2
8.1 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

40
Recovery (%)

30

20

B-15 TOATL Oil

B-11 Res-40 Oil
10

0
0 2 4 6 8 10 12 14
PV Injection

36
Lower initial pH by CO2 increses the low
salinity effect
TFloodin
Core Swi TAging Formation
g Oil LS brine
No. % °C Brine
°C

TOTAL Oil TOTAL FW

19.7 NaCl: 1000
B18 60 40 Saturated With CO2 100 000
6 ppm
at 6 Bars ppm
TOTAL FW
NaCl:1000
B14 19.4 60 40 TOTAL Oil 100 000
ppm
ppm

80 10
Low Salinity
70
High Salinity 9
Oil Recovery Factor (% OOIP)

60
Low Salinity
8
50 High Salinity
High Rate

pH
40 7

30
6
20 B18-Cycle-1 CO2 Saturated Oil B18-Cycle-1 CO2 Saturated Oi
B14-Cycle-1 Reference Curve 5 B14-Cycle-1 Reference Test
10

0 4
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14
PV Injection Brine PV Injected

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

 LS water increases oil-wetness

Adsorption of Quinoline vs. pH at ambient Ref. Fogden and Lebedeva, SCA 2011-15
temperature for LS (1000 ppm) and HS (25000 (Colloids and Surfaces A (2012)
ppm) fluids. 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
Plagioclase
Quartz Calcite Kaolinite Illite/mica Chlorite
Core
[wt%] [wt%] [wt%] [wt%] [wt%] [wt%]
13 28.2 32.1 1.4 2.6 9.3 3.6
14 36.0 35.2 2.4 3.9 7.4 2.9

Table 5. Properties of the oil.

AN BN Density (20˚C) Viscosity (30˚C) Viscosity (40˚C)
[mgKOH/g oil] [mgKOH/g oil] [g/cm3] [cP] [cP]
0.07 1.23 0.83653 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, ∆H<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

8
pH

6 40 °C
90 °C
130 °C
5
0 4 8 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, Φ=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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