Chapter 3 –Microscopic Efficiency

of Immiscible Displacement (Part I)

1
 Outline
• Single Phase Properties
– Porosity, Permeability, Permeability-porosity relations
• Two phase properties
– Saturation
– Capillary forces:
 Surface Tension and IFT
 Solid Wettability
 Capillary pressure
– Relative permeability
– Viscous Forces
– Phase Trapping
– Capillary Number
• Review and Homework

2
Single Phase Properties

3
Two Phase Properties

21
 Saturation
The formation saturation is defined fraction of its pore
volume (porosity) occupied by a given fluid.

where
Sw = water saturation
Sh = hydrocarbon
saturation
= So + Sg
Volume of a specific fluid So = oil saturation
Saturation = Sg = gas saturation
Pore volume

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 Fluid Saturation
• The ratio of the volume of a phase to
the pore volume of a core
• Fluid saturation in reservoir
– Sw + S0 + Sg =1 ?
– Usually, So>0, Sw>0 and Sg>0
– Under-saturated reservoir: Sg=0

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 Irreducible Water Saturation
Water that is held against the rock grains by surface
tension and that cannot be produced.

• The amount of
irreducible water
depends on the
grain size and on
the mixture of
grains.

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 U.S. Bureau of Mines Method to Measure Saturation
(an distillation/extraction method)

• Slowly boil the Solvent.

• The solvent vapor moves upwards to
water trap (A), extractor (B) through
outer tube (D), siphon tube (C)
• Core sample is engulfed in Solvent
vapor: over time, water/brine changes
from liquid to vapor
• Solvent/water vapor moves upwards to
condenser (E), where cold water turns
them into immiscible liquids
• Recondensed liquids soak into the core
sample
• Liquids go to water trap
• Minimum of 7 cycles

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 Solvent
• The number of cycles or amount of solvent which must be used
depends on the nature of the hydrocarbons being removed and the
solvent used.
• Often, more than one solvent must be used to clean a sample. The
solvents selected must not react with the minerals in the core.
• Toluene and benzene are most frequently used to remove oil
• commonly used solvents are:
- Acetone
- Benzene
- Benzen-methol Alcohol
- Carbon-tetrachloride
- Chloroform
- Methylene Dichloride
- Mexane
- Naphtha
- Tetra Chloroethylene
- Toluene
- Trichloro Ethylene 26
- Xylene
Surface Tension and
Interfacial Tension

27
 Everyday Life
•Water beading on a leaf

• Water dropping from a tap

http://en.wikipedia.org/wiki/Image:Water_
drop_animation_enhanced_small.gif 28
 Surface Tension
• Surface tension:
– The contractile tendency of a liquid surface exposed
to gases.
– caused by the attractions among intermoleculars

29
 BOUNDARY (INTERFACIAL) TENSION
• Imbalanced molecular forces at phase boundaries
• Boundary contracts to minimize size
GAS
• Cohesive vs. adhesion forces
θ
LIQUID
GAS
SOLID
Cohesive force
Adhesion force

Molecular
Interface
(imbalance
of forces)

LIQUID
(dense phase)

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SOLID
 Surface Tension
Mathematically, Surface tension is the force acting in the
plane of the surface per unit length of the surface.

F
δ =
L
Where
F = force, dynes
L = length, cm
δ = surface tension, dynes/cm

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Surface tension as a function of T and Composition

32
 Interfacial Tension
Interfacial tension (IFT): the contractile tendency at
the liquid-liquid interface when two immiscible liquids
are in contact.
• IFT between water and pure hydrocarbons are about 30
to 50 dynes/cm at room temperature.
• Mixtures of hydrocarbons such as crude oils will have
lower IFT’s that depend on the nature and complexity of
the liquids.
• IFT is relatively strong functions of temperature.

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Table 3.1 IFT between water and various crude oil (after Donaldson et al.)

34
 Surface and Interfacial Tension Measurement

Upward vertical force of surface

Capillary tube method
tension × wetted perimeter =
Downward gravitational force
acting on fluid column, or
rh( ρ w − ρ a ) g
σ=
2 cos θ
Where
r = capillary-tube radius, cm
h = height of water rise in the capillary, cm
ρw = water density, g/cm3
ρa = air density, g/cm3
g = gravity acceleration constant, 980 cm/s2
θ = contact angle between water and capillary
tube
35
 Maximum Bubble Pressure Method
to Measure Surface Tension

• Measure the surface tension using

the maximum bubble pressure
method

• Principle: Blowing a bubble

through a liquid and measure the
maximum pressure of the bubble

36
 Ring Tensiometer Method
Procedures:
1. A carefully cleaned
platinum/iridium ring is
pulled through the interface.
2. As this occurs, the interfacial
area increases (Figure 2 .6a),
and the surface is stretched
further until it finally breaks
(Figure 2. 6b).
3. The force on the ring is measured throughout the process. At
the breaking point of the surface, the force divided by the
circumference of the ring (corrected for a geometric factor) is
the δwo value at the experimental temperature.
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 Example 3-1
Calculation of Surface Tension From Rise in a
Capillary Tube. Calculate the surface tension of
water at 77°F if θ =38°, the capillary radius is 100
m and the height of the water column is 12 cm.
(Neglect the density of air compared with the
density of water)

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 Surface and Interfacial Tension
Measurement
• SenaDyne 6000 Surface Tensiometer
• DCA (Dynamic Contact Angle)
• Spinning Tensiometer

More methods:
http://www.kibron.com/company/science---technology/measuring-techniques/

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Wettability
 Solid Wettability
Wettability: Wettability or wetting is the actual process when
a liquid spreads on (wets) a solid substrate in the presence
of other immiscible fluids. Wettability can be estimated by
determining the contact angle.
 CONTACT ANGLE
The contact angle, θ,
measured through the denser
Oil liquid phase,

σow defines which fluid wets the

solid surface.

Oil θ Water Oil

σos σws σos

Solid
θ = contact angle between the oil/water/solid interface measured through the water, degrees

σos = interfacial energy between the oil and solid, milli-Newtons/m or dynes/cm

σws = interfacial energy between the water and solid, milli-Newtons/m or dynes/cm

σow = interfacial energy (interfacial tension) between the oil and water, milli-Newtons/m or dynes/cm
 Contact Angle

δ os − δ ws
cos θ =
δ ow
δ os − δ ws = δ ow cos θ

• water wet: 0° > θ > 70°

Types of
• Oil wet: 110° > θ > 180°
Wettability
• intermediate wet: 110° > θ > 70°
 WHY STUDY WETTABILITY?
•Understand physical and chemical interactions between
• Individual fluids and reservoir rocks
• Different fluids with in a reservoir
• Individual fluids and reservoir rocks when multiple
fluids are present

•Petroleum reservoirs commonly have 2 – 3 fluids

(multiphase systems)

• When 2 or more fluids are present, there are at least 3

sets of forces acting on the fluids and affecting HC recovery
 WATER-WET OIL-WET
Air
OIL Oil OIL
θ
θ

θ WATER θ WATER
θ < 90°
WATER WATER θ > 90°
SOLID (ROCK) SOLID (ROCK)
FREE WATER

OIL
GRAIN GRAIN

OIL
RIM
BOUND WATER FREE WATER
Ayers, 2001
Effect of Wettability on Saturation
 GENERALLY

• Silicate minerals have acidic surfaces

• Repel acidic fluids such as major polar
organic compounds present in some crude oils
• Attract basic compounds
• Neutral to water-wet surfaces
• Carbonate minerals have basic surfaces
• Attract acidic compounds of crude oils
• Neutral to oil-wet surfaces

Caution: these are very general statements and relations

that are debated and disputed by petrophysicists.

Tiab and Donaldson, 1996

 n = 30 silicate and 25 carbonates n = 161 ls., dol.

From Tiab and Donaldson, 1996 CONTACT ANGLE: Triber et al. CONTACT ANGLE:
-Water-wet = 0 – 75 degrees -Water-wet = 0 – 80 degrees
-Intermediate-wet = 75 – 105 degrees -Intermediate-wet = 80 – 100 degrees
-Oil-wet = 105 – 180 degrees -Oil-wet = 100 – 180 degrees
INTERFACIAL CONTACT ANGLES,
VARIOUS ORGANIC LIQUID IN
CONTACT WITH SILICA AND CALCITE

WATER

SILICA SURFACE

WATER

CALCITE SURFACE

From Amyx Bass and Whiting, 1960; modified from Benner and Bartel, 1941
WETTABILITY IS AFFECTED BY:

• Composition of pore-lining minerals

• Composition of the fluids

• Saturation history
 Reservoir Wettability Classification
• Strongly oil- or water-wet
• Neutral/intermediate wet – no preferential wettability to either
water or oil in the pores

• Fractional wettability
– reservoir that has local areas that are strongly oil-wet,
whereas most of the reservoir is strongly water-wet
- Occurs where reservoir rock have variable mineral
composition and surface chemistry
• Mixed wettability – smaller pores area water-wet are filled with
water, whereas larger pores are oil-wet and filled with oil
- Residual oil saturation is low
- Occurs where oil with polar organic compounds
invades a water-wet rock saturated with brine
Mixed Wet Reservoir
 Fractional Wettability

From Levorsen, 1967

 Example 3-2

A drop of oil was placed on a quartz crystal in air. If

the adhesive tension between the oil and the crystal is
42 dynes/cm and the interfacial tension between the
air and the oil is 60 dynes/cm, what is the wettability of
the crystal?

54
 Example 3-3
Sketch the side view of an oil drop that is trapped in a
strongly water wet capillary tube.

55
 Measurement of Wettability

• Direct measurement of Contact Angle

• Dynamic Contact Angle

• Amott methods

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Capillary Pressure

57
 DEFINITION of CAPILLARY PRESSURE

• The pressure difference existing across the

interface separating two immiscible fluids in
capillaries (e.g. porous media).
• Calculated as:
Pc = pnwt - pwt
Where:
• One fluid wets the surfaces of the formation
rock (wetting phase) in preference to the other
Pc = capillary pressure
(non-wetting phase).
• Gas is always the non-wetting phase in both Pnwt = pressure in nonwetting phase
oil-gas and water-gas systems.
• Oil is often the non-wetting phase in water-oil pwt = pressure in wetting phase
systems.

58
 Capillary Tube - Conceptual Model
Air-Water System

θ Air
∆h

Water

• Considering the porous media as a collection of capillary tubes provides useful

insights into how fluids behave in the reservoir pore spaces.
• Water rises in a capillary tube placed in a beaker of water, similar to water (the
wetting phase) filling small pores leaving larger pores to non-wetting phases 59
of
reservoir rock.
 CAPILLARY TUBE MODEL AIR / WATER SYSTEM
• The height of water in a capillary tube is a function of:
– Adhesion tension between the air and water
– Radius of the tube
– Density difference between fluids
2 σ aw cos θ
∆h =
r g ∆ρ aw
∆h = Height of water rise in capillary tube, cm
σaw = Interfacial tension between air and water,
dynes/cm
θ = Air/water contact angle, degrees
r = Radius of capillary tube, cm
g = Acceleration due to gravity, 980 cm/sec2
∆ρaw = Density difference between water and air, gm/cm3
Contact angle, θ, is measured through the more dense phase (water in this
case). 60
 CAPILLARY PRESSURE – AIR / WATER SYSTEM

• Combining the two relations results in the following expression for

capillary tubes:

2 σ aw cos θ
Pc =
r
∆h = Height of water rise in capillary tube, cm
σaw = Interfacial tension between air and water,
dynes/cm
θ = Air/water contact angle, degrees
r = Radius of capillary tube, cm
g = Acceleration due to gravity, 980 cm/sec2
∆ρaw = Density difference between water and air, gm/cm3

61
 CAPILLARY PRESSURE – OIL / WATER SYSTEM

• From a similar derivation, the equation for capillary pressure for an

oil/water system is

2 σ ow cos θ
Pc =
r
Pc = Capillary pressure between oil and water
σow = Interfacial tension between oil and water, dyne/cm
θ = Oil/water contact angle, degrees
r = Radius of capillary tube, cm

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 Applications of Capillary Pressure Data

• Determine fluid distribution in reservoir (initial conditions)

• Accumulation of HC is drainage process for water wet res.
• Sw= function of height above OWC (oil water contact)
• Determine recoverable oil for water flooding applications
• Imbibition process for water wet reservoirs
• Pore Size Distribution Index, λ
• Absolute permeability (flow capacity of entire pore size distribution)
• Relative permeability (distribution of fluid phases within the pore size
distribution)
• Reservoir Flow - Capillary Pressure included as a term of flow potential for multiphase
flow
ρw g Z
Φ w = po − − Pc,ow ; Z+ ↓, water wet
D

• Input data for reservoir simulation models

• Determine transition zone thickness 63
Determine w/o Transition Zones

64
Rise of Wetting Phase Varies with Capillary Radius

1 2 3 4

AIR

WATER

Ayers, 2001
65
DRAINAGE AND IMBIBITION CAPILLARY PRESSURE CURVES
DRAINAGE

• A fluid flow process in which the saturation

of the wetting phase decreases and the
nonwetting phase saturation increases
• Mobility of nonwetting fluid phase increases
as nonwetting phase saturation increases
Drainage
IMBIBITION

• A fluid flow process in which the saturation

Pc of the wetting phase increases
• Mobility of wetting phase increases as
Pd wetting phase saturation increase.

Imbibition Four Primary Parameters

Si Sm Si = irreducible wetting phase saturation
Sm = 1 - residual non-wetting phase saturation
0 0.5 1.0 Pd = displacement pressure, the pressure required to
Swt force non-wetting fluid into largest pores
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λ = pore size distribution index; determines shape
Modified from NExT, 1999, after …
67
 Effect of Permeability on Shape
20

16
Decreasing
Capillary Pressure

Permeability

12

A B
8

0
0 0.2 0.4 0.6 0.8 1.0

Water Saturation
68
Modified from NExT 1999, after xx)
 Effect of Grain Size Distribution on Shape

Poorly sorted
Well-sorted
Capillary pressure, psia

69
Modfied from NExT, 1999; after …) Water saturation, %
 Example 3-4
Using the drainage capillary pressure curve of the Venango Core
(shown below). How many feet above the free water table is the
water/oil contact? (1ft = 30.48 cm)
ρw=1 gm/cm3, ρo=0.75 gm/cm3, 1 cm of mercury= 13,322.2dyne/cm

70
 CAPILLARY TUBE MODEL
AIR/WATER SYSTEM

pa1
pw1 Air
∆h
pa2
pw2

Water

Water rise in capillary tube depends on the density difference of fluids.

Pa2 = pw2 = p2
pa1 = p2 - ρa g ∆h
pw1 = p2 - ρw g ∆h
Pc = pa1 - pw1
= ρw g ∆h - ρa g ∆h
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= ∆ρ g ∆h
 Example 3-5
a) Derive the expression for the pressure at the bottom of a capillary tube
containing oil and water and exposed to the atmosphere as shown below.
b) If σow=20dynes/cm, σao=70dynes/cm, θow=30° and θao=20°, and the radius of
the tube is 1cm. What is the value of the pressure at the bottom of the tube (Pw3)?
ho=5cm, hw=3cm, ρw =1gm/cc, ρo =0.7gm/cc.

72
 Review
• Definitions of wettability, contact angle,
drainage, imbibition, capillary pressure,
surface tension, interfacial tension
• Factors influencing wettability
• Factors influencing capillary pressure

73