An Introduction to Wettability of Oil Reservoirs

Petrophysics and Surface Chemistry Group Petroleum Recovery Research Center New Mexico Tech

Outline
The big picture Microscopic view of oil reservoirs Capillary phenomena Surface chemistry in oil reservoirs

Outline
The big picture Microscopic view of oil reservoirs Capillary phenomena Surface chemistry in oil reservoirs

Geologic scale

Structural trap

Outline
The big picture Microscopic view of oil reservoirs Capillary phenomena Surface chemistry in oil reservoirs

Microscopic view of an oil reservoir

Typical sandstone.

Blue color is epoxy in interconnected pore spaces.

Less porous or less permeable?

More complicated sandstone

Early diagenetic spheroids in a fineto medium-grained subarkose, showing variations in internal patterns and typical radial-fibrous texture. St Bees Sandstone Formation (Triassic), Cumbria, UK. White - quartz; yellow - stained Kfeldspar; brown - iron oxide; blue - stained porosity. Scale bar: 100 microns.

from: STRONG, G. E. & PEARCE, J. M. 1995. Carbonate spheroids in Permo-Triassic sandstones of the Sellafield area, Cumbria. Proceedings of the Yorkshire Geological Society Vol. 50, Pt 3, 209-211.

Kaolinite (clay)
Authigenic kaolinite, Carter sandstone, Black Warrior basin, Alabama
Kugler, R.L. and Pashin, J.C., 1994, Reservoir heterogeneity in Carter sandstone, North Blowhorn Creek oil unit and vicinity, Black Warrior basin, Alabama: Geological Survey of Alabama Circular 159, 91 p.

Illite (clay)

"Hairy" illite clay found in the Coconino sandstone - 2000X The fine hair-like structure is actually crystalline mineral and is a diagenetic alteration product of other minerals in the subsurface.

http://www.creationresearch.org/vacrc/sem02.html

Outline
The big picture Microscopic view of oil reservoirs Capillary phenomena Surface chemistry in oil reservoirs

Common characteristics of oil-bearing rocks Pores in which oil is found are small
d < 100

Surface area is high

>> 1 m2/g

Fluid-fluid interfaces coexist. Capillary forces hold oil in place.

Capillary phenomena
Capillary rise Capillary pressure Interfacial tension Contact angles

Capillary rise
100 10 height of rise (meters) 1 0.1 0.01 0.001

1,000 2,000 tube radius (microns)

3,000

Capillary pressure
Pc = g h
h

Pc = 2 / r Pc = Pnw - Pw

r Pnw Pw

Interfacial tension,
1 1d 2d Liquid 1 12 = 1 + 2 2 Liquid 2 1d 2d

1d

2d

F.M. Fowkes, Attractive Forces at Interfaces, Ind. Eng. Chem. (Dec 1964) 56, 40-52.

Why is this interface curved?

Pnw

Pw

Water-wet (oil is non-wetting)

water

oil

= 0

Oil-wet (oil is spreading)

water

= 180

Partial wetting: 0 < < 180

water ow

oil os

ws

os = ws + ow cos

Crude oil contacting a clean surface

brine
crude oil

mica

Adhesion of crude oil under brine

A fresh drop of crude oil under water does not wet the surface.

After it contacts the surface, the area under the drop can become oil-wet.

If so, a drop of crude oil remains adhering to the surface.

AFM shows adsorption

clean mica A-93 treated mica

PB brine + A-93, 3 weeks, 80C, wash with cyclohexane

Contact angle on treated surface

decane

water

mica

Brine mediates crude oil/solid interactions

A-93 crude oil aged at 80C
Decane/water contact angle (deg) 180 150
NaCl (M)

120 90 60 30 0 0 10 20 30 40 Aging time in oil (days) 50

0.01 0.1 1.0

pH 4 pH 6 pH 8

Wettability affects oil recovery

100

Oil Recovery (%OOIP)

80

60

40

20

0 0 2 4 6 8 10 12 14

Pore Volumes Injected

Wettability of an oil reservoir?

There is not one simple answer. Measure properties of reservoir cores
preserved in original condition restored to original condition

Consider the underlying surface chemistry.

Outline
The big picture Microscopic view of oil reservoirs Capillary phenomena Surface chemistry in oil reservoirs

Crude oil fractions

Crude oil
dilute with n-alkane solution precipitate

Maltenes
adsorb on silica elute with: (1) alkane (2) toluene (3) toluene/methanol

Saturates

Aromatics

Resins

Asphaltenes

no direct effect on wetting

can adsorb -> alter wetting

Mechanisms of interaction
Polar (water absent) Ionic (water present)
acid/base ion binding

Surface precipitation

Mechanisms of interaction
Polar (water absent) Ionic (water present)
acid/base ion binding

Surface precipitation

Basic oil components

low pH
Base

high pH
R
oil

R N
water +

[NaCl] pH
10 8 6

0.01 M

0.10 M

1.0 M

2.0 M

N+ H

H+

- - - -glass / mica- - - -

Acidic oil components

low pH
Acid

high pH
R
oil

R C O O
water

[NaCl] pH
10 8

0.01 M

0.10 M

1.0 M

2.0 M

C O OH

H+

- - - -glass / mica- - - -

Examples of acid/base interactions

A-93 crude oil aged at 80C
Decane/water contact angle (deg) 180 150
NaCl (M)

120 90 60 30 0 0 10 20 30 40 Aging time in oil (days) 50

0.01 0.1 1.0

pH 4 pH 6 pH 8

Mechanisms of interaction
Polar (water absent) Ionic (water present)
acid/base ion binding

Surface precipitation

Ion binding
Acid:
water

R
oil

R C O O
2+

C O OH

H+

- - - - glass / - - - - mica
slow interactions can be very strong not very predictable

Ca

2+

Ca

Ca

2+

Mechanisms of interaction
Polar (water absent) Ionic (water present)
acid/base ion binding

Surface precipitation

S N S S S

One asphaltene molecule?

C: 81.0% H: 8.0% N: 1.4% O: 1.0% S: 7.3% V: 0.8%
N

Mol. Wt.: 6191 H/C: 1.18

S S= O S

N N

VO

N N

O O

Strausz et al., 1991

Asphaltene aggregation
RI
macromolecules

oil

PRI
heptane

colloids

precipitate

volume fraction of oil

Effects of asphaltenes on wetting

Advancing Contact Angle (deg) 180 150 120 90 60 30 unstable

Prudhoe Bay (A-93) plus n-heptane

pH 4

pH 8
0 0 0.2 0.4 0.6 Oil Volume Fraction 0.8 1

Al-Maamari and Buckley, SPE 59292

More examples
180
Lagrave

150 Advancing angle (deg) 120

Mars-Pink A-93

90 60 30 0

Tensleep

Mars-Yellow

0.2

0.4

0.6

0.8

Oil volume fraction (f v,oil)

High contact angles at onset

180
Lagrave

Advancing angle (deg)

150
A-93

120
Mars-Pink

90
Tensleep

60 30 0 -0.04
Mars-Yellow

0.04 RI = RI - P RI

0.08

0.12

Summary
Oil is found in the small pore spaces in rocks where it coexists with water (and possibly a gas phase). Capillary forces can hold oil in place. Magnitude of capillary forces depends on
pore size IFT wettability (contact angles)

Wettability is determined by surface chemistry