Key Parameters Affecting Reservoir

Wetting in Carbonate and Sandstone

Reservoirs
Tina Puntervold and Skule Strand
University of Stavanger
Initial reservoir wetting is dictated by reservoir chemistry

Initial wetting is generated through chemical interactions between:

Crude oil Brine Rock

• Polar organic acids • Formation water salinity • Carbonate rock minerals
• Polar organic bases • Formation water • Sandstone rock minerals
composition • Mineral surface
reactions

Chemical reactivity is temperature dependent

EOR by Smart Water injection – wettability alteration

EOR by wettability alteration requires a reservoir that is not completely

water-wet.

Otherwise: no Smart Water EOR potential!

 Need to understand the initial wetting of the reservoir!

What is Smart Water and how does it work?

• Smart Water is an injection brine with modified ionic composition.

• No expensive chemicals are added
• Environmentally friendly
• Composition is dependent on
reservoir mineralogy
• Smart Water works in both carbonates and
sandstones.
• BUT: Mechanism for wettability alteration
is different.

2σ𝑐𝑐𝑐𝑐𝑐𝑐θ
𝑃𝑃𝑃𝑃 =
𝑟𝑟
 Chalk
CaCO3

Limestone
Rock chemistry Carbonate
CaCO3

Dolomite
CaMg(CO3)2
Carbonates: Other Anhydrite
Normally positively charged, slightly alkaline pH minerals CaSO4

Quartz
Kaolinite
Reservoir SiO2
Sandstones: rock

Normally negatively charged, slightly acidic pH Clays Illite

Chlorite

Albite
Large variety in reservoir rock mineralogy Sandstone Na-Feldspars

Anorthite
Feldspars
Ca-Feldspars
Different chemistry is involved in:
Microcline
 Initial wetting K-Feldspars
 Wettability alteration
Anhydrite
CaSO4
Other
minerals
Carbonate
CaCO3
Brine chemistry

• For EOR:
• Injection water ≠ Formation water
• Chemical equilibrium between crude oil, brine and rock must be disturbed
• Must «unstick» the oil on the rock surface! How?

Different Smart Water composition in sandstone and carbonate

reservoirs!
Crude oils

Crude oil is not a homogeneous phase

 Polar organic acids and bases with affinity to the rock surface influence the
reservoir wetting.
 Crude oil anchor molecules at the rock surface.

Low pH High pH
Organic Bases:
𝑅𝑅3 𝑁𝑁𝐻𝐻 + ⇄ 𝑅𝑅3 𝑁𝑁: + 𝐻𝐻 +
pKa~4.9
Quinoline

Carboxylic Acids : Low pH High pH

𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 ⇄ 𝑅𝑅𝑅𝑅𝑅𝑅𝑂𝑂− + 𝐻𝐻 +
pKa~4.2
Benzoic acid
Carbonates
Adsorption of crude oil acids and bases on chalk
Crude oil injected into Stevns Klint chalk cores at 50 °C
o15 PV crude oil ( AN = 0.40 and BN = 0.35 mgKOH/g oil)

Adsorption of polar components, Swi = 10%

Carbonates:
• Alkaline pH due to some carbonate
dissolution:
• Negatively charged carboxylates, RCOO-
• Neutrally charged bases, R3NH:

Low pH High pH
𝑅𝑅3 𝑁𝑁𝐻𝐻 ⇄ 𝑅𝑅3 𝑁𝑁: + 𝐻𝐻 +
+

pKa~4.9

Low pH High pH
Mjøs et al. (2017) 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 ⇄ 𝑅𝑅𝑅𝑅𝑅𝑅𝑂𝑂− + 𝐻𝐻 +
SPE 190414 pKa~4.2
Carbonate reservoirs – effect of carboxylic acids on wetting
oStevns Klint chalk cores saturated and aged in crude oils with different AN, Swi =0
oSI at 40 °C, ( 44 940 ppm brine)

Standnes and Austad

JPSE 28(2000) 111-121

 Water wetness decreases with increasing AN in Crude Oils

Carbonate reservoirs – effect of crude oil bases on wetting
o Stevns Klint cores saturated and aged in crude oils with different AN/BN ratios, Swi = 10 %
− constant AN = 0.50 mg KOH/g oil
− BN varied (< 1.6 mg KOH/g oil)
o SI at 70°C with FW brine

 At constant AN, water wetness increases

with increasing BN

 Reduced reactivity of acidic material

 Reduced adsorption of acidic components

towards mineral surfaces. Puntervold et al.
E&F 21 (2007)1606-1616
Smart Water mechanism in chalk/limestone

Seawater and modified seawater are Smart Water brines in carbonates.

 Ca2+ and SO42- are necessary for wettability alteration

 Reactivity affected by non active ions in the double layer
 Sandstone mineralogy

Sandstones
Initial wetting in sandstone reservoirs
Clays:
o Are the main wetting material in Sandstone
o Contribute with most of the rock surface
o Permanent localised negative surface charges
o Act as cation exchangers (CEC)
General order of cation affinity:
Li+ < Na+ < K+ < Mg2+ < Ca2+ << H+

Feldspars can influence pH by cation exchange!

Competition between ions from water and polar organic acids and bases for the surface.
Affected by:
o Type of ions Low pH High pH
o Salinity 𝑅𝑅3 𝑁𝑁𝐻𝐻 ⇄ 𝑅𝑅3 𝑁𝑁: + 𝐻𝐻+
+

pKa~4.9
o pH (normally 5-6 because of sour gases)
o Temperature Low pH High pH
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 ⇄ 𝑅𝑅𝑅𝑅𝑅𝑅𝑂𝑂− + 𝐻𝐻 +
pKa~4.2
 Adsorption of basic components
Quinoline
Adsorption reversibility by pH change
Low pH - 𝑅𝑅3𝑁𝑁𝑁𝑁+ ↔ 𝑅𝑅3𝑁𝑁: - High pH

20 m²/g

pH=pKa=4.85

0.2 m²/g
3 m²/g

(Aghaeifar et al. 2015)

Adsorption depends on pH, surface area and CEC

15
Adsorption of quinoline onto illite clay mineral
Ambient temperature
HS1 brine (25 000 ppm) and LS1 brine (1000 ppm) Quinoline

Adsorption is highest in LS brine

Adsorption decrease by
increased pH
EOR by Smart Water injection in sandstone reservoirs
Remove oil components from the surface by injecting modified injection water (LS Smart
Water):
 Increase pH:
Clay-Ca2+ + H2O = Clay-H+ + Ca2+ + OH- + heat

 Wettability alteration:

Basic material
Clay-NHR3+ + OH- = Clay + R3N: + H2O

Acidic material
Clay-RCOOH + OH- = Clay + RCOO- + H2O
 • Initial wetting – adsorption of different crude
oil components
Concluding • Acids for carbonate wetting
remarks • Bases for sandstone wetting
• Crude oil amount affects wettability in core
restoration.
 Thank you

Questions?

Advances in EOR/IOR Technologies