Petrophysics Related to EOR

Lithology, Porosity, water saturation, and wettability

7/18/2010
Graduation Project, Mining Engineering Department
Mourad Hosni
Contents:

Introduction

Porosity

Factors Governing Sandstone Porosity

Classification of Pores

Engineering Porosity Classification

 Absolute Porosity
 Effective Porosity

Geological Porosity Classification

 Primary
 Secondary

Direct determination of porosity (laboratory)

 Bulk Volume Measurements

Indirect determination of Porosity

 Density Log
 One detector formation density tool
 Dual-spacing density logging tool
 Electron Density and Bulk Density

Typical Reservoir Porosity Values

Water Saturation

Resistivity Log

 Types of resistivity log

 Principal of electrical logs
 Types of electrode logs
 Normal log device
 Lateral log device
 Focused logs
 Laterolog

2
  Formation Resistivity factor
 Archie’s Formula

Lithology of the Formation

 Properties of gamma rays

 Theory
 Lithology Index

Volume of Shale

Porosity Correction

Water Saturation Correction

Wettability and interfacial phenomena

 Wettability
 Surface tension
 Interfacial tension

Surfactant and its use in EOR

 Mechanism of surfactant in decreasing the interfacial tension

3
Introduction

Almost all oil and gas produced today comes from accumulations in the pore
spaces of reservoir rocks –usually sandstones, limestones, or dolomites. The
amount of oil or gas contained in a unit volume of the reservoir is the product of
its porosity by the hydrocarbon saturation. In addition to the porosity and the
hydrocarbon saturation, the volume of the formation containing hydrocarbons is
needed in order to estimate total reserves and to determine if the accumulation is
commercial. Knowledge of the thickness and the area of the reservoir needed for
computation of its volume.
To evaluate the producibility of a reservoir, it is necessary to know how easily fluid
can flow through the pore system. This property of the formation rock, which
depends on the manner in which the pores are interconnected, is its permeability.

The main petrophysical parameters needed to evaluate a reservoir, then, are its
1- Porosity
2- Hydrocarbon saturation
3- wettability
4- Thickness
5- Permeability
6- Area
7- Reservoir geometry
8- Formation temperature and pressure, and lithology

Our goal is to discuss the three italic bolded petrophysical parameters…

4
Porosity

Void spaces within the rock needed for storage capacity.

Sand grains and particles of carbonate materials that make up sandstone and
limestone reservoirs usually never fit together perfectly due to the high degree of
irregularity in shape. The void space created throughout the beds between grains,
called pore space or interstice, is occupied by fluids (liquids and/or gases).

The porosity of a reservoir rock is defined as that fraction of the bulk volume of the
reservoir that is not occupied by the solid framework of the reservoir. This can be
expressed in mathematical form as:1

Percentage Porosity= x 100

Bulk Volume =the total volume of the rock

1 nd
Solved example. [Petrophysics, 2 Ed. Theory and Practice of Measuring Reservoir Rock and Fluid
Transport Properties. Pg.89

5
Classification of Pores:

1- Interconnected Pores: This type of pore has more than one throat
connected with other pores and extraction of hydrocarbon is relatively easy
from such pore, as shown

2- Connected or dead end: This type of pore has one throat connected with
other pores. It may yield some of the hydrocarbon by expansion as reservoir
pressure drops

6
3- Closed or isolated (blind) pore: This type of pore is closed. It does not have
throat and cannot connect with other pore. It is unable to yield
hydrocarbons in normal process as shown

7
Engineering Porosity Classification:

1- Total [absolute] porosity: it’s the ratio of total void space in the sample to
the bulk volume of that sample, regardless of whether or not those void
spaces are interconnected.
2- Effective porosity: is the ratio of effective void spaces in the sample to the
bulk volume of that sample, it’s affected by many factors, such as:
 Type, content, and hydration of the clays present in the rock.
 Heterogeneity of grain sizes.
 Packing, and cementation of the grains
 Weathering, and leaching.

Total Porosity = effective porosity + ineffective porosity

Note: Interconnected and connected pores constitute effective porosity because

hydrocarbons can move out from them. In the case of interconnected porosity, oil
and gas flowing through the pore space can be flushed out by a natural or artificial
water drive. Connected porosity is unaffected by flushing but may yield some oil or
gas by expansion, as reservoir pressure drops. Reservoirs with isolated porosity are
unable to yield hydrocarbons. Any oil or gas contained entered the pore spaces
before they’d been closed by compaction or cementation.

8
Geological Porosity Classification

This method of classification depends on whether pore spaces in which oil and gas
are found originated when the beds were laid down [primary or matrix porosity],
or if they were formed during a subsequent processes [secondary or induced
porosity].

1- Primary porosity
 Intercrystalline: voids between cleavage planes of crystals, voids
between individual crystals, and voids in crystal lattices.
 Intergranular or interparticle: voids between grains, i.e., interstitial
voids of all kinds in all types of rocks.

 Bedding planes: voids of many varieties are concentrated parallel to

bedding planes.
 Miscellaneous sedimentary voids: (1) voids resulting from the
accumulation of detrital fragments of fossils, (2) voids resulting from the
packing of oolites, (3) vuggy and cavernous voids of irregular and
variable sizes for at the time of deposition, and (4) voids created by
living organisms at the time of deposition.

9
10
2- Secondary porosity
 Solution porosity: channels due to the solution of rocks by circulating
warm or hot solutions; openings caused by weathering, such as enlarged
joints and solution caverns; and voids caused by organisms and later
enlarged by solution.

 Fracture porosity: openings created by structural failure of the reservoir

rocks under tension caused by tectonic activities such as folding and
faulting. These openings include joints, fissures, and fractures. In some
reservoir rocks, fracture porosity is important.

 Miscellaneous secondary voids: (1) saddle reefs, which are openings at

the crests of closely folded narrow anticlines; (2) pitches and flats, which
are openings formed by the parting of beds under gentle slumping; and
(3) voids caused by submarine slide breccias and conglomerates
resulting from gravity movement of seafloor material after partial
lithification

11
12
13
Factors Governing the Magnitude of Sandstone Porosity

1- Uniformity of grain size: is the gradation of grains, it depends on on at least

four major factors:
 Size range of material
 Type of deposition
 Current characteristics
 Duration of sedimentation process

e.g. if small particles of clay are mixed with larger grains of sand; the
effective porosity will be reduced, [they are called dirty, or shaly reservoirs]

2- Degree of cementation or consolidation: it’s filling the void spaces with

mineral materials. It occurs while alteration or lithification, by ground
water. The highly cemented sandstones have low porosities, and vice versa.

14
3- Amount of compaction during and after deposition: compaction tends to
lose voids and squeeze fluid out to bring the mineral particles close
together, especially the fine-grained sedimentary rocks

4- Method of packing: with increasing overburden pressure, poorly angular

sand grains show a progressive change from random packing to a closer
packing, some crushing and plastic deformation of the sand particles occur.
 Cubic packing has a porosity of 47.6%
 Hexagonal packing has a porosity of 39.5%
 Rhombohedral has a porosity of 25.9%

15
Determination of absolute and effective porosity

Three basic parameters are to determine porosity:

1- Bulk volume [Vb]
2- Pore volume [Vp]
3- Solid volume (rock matrix) [Vs]

Vb= Vp + Vs

For example: the mass (M) of a sample of rock with a bulk volume (Vb) of 15 cm3 is
30.3 grams; it was found to contain an absolute grain volume
(V,) of 11.25 cm3, an interconnected pore volume (Vp) of 3.0 cm3, an unconnected
(isolated) pore space (VI) of 0.75 cm3, and an irreducible water saturation (Si,)
equal to 6%.

Absolute Porosity:

To determine absolute porosity, the density of the solid portion of the rock (its
grain density) should be determined.

Density of the solid portion:

 The rock sample should be crushed using an impact crusher.

 An appropriate size pycnometer2, whose volume is known, is dried and
weighed, and then the volume and mass of a portion of the sand grains
is determined using the pycnometer.

1- Fill the pycnometer with a liquid (water or hydrocarbon), and obtain its
mass (Mpyc+ML)
2- Empty and dry the pycnometer
3- Place a sample of crushed rock in the pycnometer (about one-half the
volume of the pycnometer) and determine the mass (Mpyc + Mgrains)
4- Fill the pycnometer (containing the sand grains), then with the liquid used
in (1) above, and determine the mass (Mpyc + Mgmins + Ml).
5- The sand grain density is calculated from the data as follows:

2
Specific gravity bottle.

16
Empty and Full Pycnometers

17
Grain and Bulk Volumes

This step is concerned with determination of grain and bulk volumes of a rock
sample (core)

1- The core is dried and its mass is determined (Mcore)

2- The core is then saturated with liquid by first evacuating the core to remove
air and then admitting the liquid into the vacuum flask containing the core
to fill the pores with the liquid.
3- The bulk volume (Vb) of the core may be determined accurately using a
beam balance. Tie the core to a fine wire, attach it to the beam balance, and
then immerse the core in a beaker with the same liquid used for the
measurements above. The core should be immersed until it is just below the
surface of the liquid, and it should not touch the sides or the bottom.
Obtain the mass of immersed core (Mim).
4- Remove the beaker of liquid, carefully wipe the excess liquid from the
surface of the core, and obtain the mass of the saturated core (Mcorc-sat)

Effective Porosity

The effective porosity is the ratio of the interconnected pore space in the rock to
the bulk volume minus the irreducible saturation.

18
Summary

19
Indirect determination of porosity:

Porosity can be determined using well logs.

Well logs: the continuous recording of a geophysical parameter along a borehole.

The value of the measurement is plotted continuously against depth in the well.

Porosity can be determined using one of three logs:

1- Sonic log
2- Density log
3- Neutron log

We are concerned with density log here.

20
Density log

Theory

A radioactive source, applied to the borehole wall in a rays Shielded sidewall skid,
emits medium-energy gamma rays into the formations. These gamma rays may be
thought of as high-velocity particles that collide with the electrons in the
formation. At each collision a gamma ray loses some, but not all, of its energy to
the electron, and then continues with diminished energy. This type of interaction
is known as Compton scattering. The scattered gamma rays reaching the detector,
at a fixed distance from the source, are counted as an indication of formation
density.

The number of Compton-scattering collisions is related directly to the number of

electrons in the formation. Consequently, the response of the density tool is
determined essentially by the electron density (number of electrons per cubic
centimeter) of the formation. Electron density is related to the true bulk density,
ρb, which, in turn, depends on the density of the rock matrix material, the
formation porosity, and the density of the fluids filling the pores.

Gamma ray sources:

The most widely used are:
 60Cobalt which emits photons at energies of 1.17 and 1.33 MeV.
 I37Cesium that emits photons of energy 0.66 MeV

21
One detector formation density tool:

Schematic of the one detector formation density tool.

The first tools used only one detector. Although pushed against the borehole wall
by a spring, the measurement suffered from the effects of mud-cake, its type,
thickness and density.

22
In the Dual-Spacing Formation Density Logging Device, compensated formation
density tool, two detectors of differing spacing and depth of investigation are used
to eliminate the muudcake effect.

Schematic of dual-spacing density logging tool

23
Log information is presented as shown:

24
Starting from left to right:

 Track 1: shows the gamma ray log, which measures the natural gamma
radiation of the formation. Radioactive elements such as uranium,
potassium, and thorium tend to occur more in shales than in sands. As a
result, the gamma ray log is a lithology log that identifies shales from sands.

 The Caliper: it’s the dotted line in the same track that measures the
borehole diameter

 Track 2: Porosity, plotted on a scale ranges from 0 to 30%

 Track3: Bulk density plotted on a scale ranges from 2.0 to 3.0 gm/cc

 A correction shows how much density compensation has been applied to

correct for mudcake and borehole rugosity. The correction scaled from -0.5
to +0.5
But if the correction was ≥ ±0.15 gm/cc, the data in the main curve will not be very
reliable.

25
Electron Density and Bulk Density:

The density log responds to the electron density of the formations.

For a substance consisting of a single element, the electron density index, ρe, is
related to the bulk density, ρb:

Where:
ρe is the electron density index
ρb is the bulk density
Z is the atomic number of the element
A is the atomic weight of the element

For a molecular substance, the electron density index is related to the bulk density:

Where:
M is the molecular weight
Σz is the sum of the atomic numbers of the atoms making up the molecule, which
is equal to the number of electrons per molecule

ρe is the electron density index

ρb is the bulk density

The log tool reads apparent density (ρa) which is practically identical to actual
bulk density (ρb)

But for some substances such as: sylvite, rock salt, gypsum, anhydrite, coal, and
gas-bearing formations, a correction is needed to obtain bulk density values from
the density log reading (apparent density) as shown in the coming 3rd figure

26
Atomic Properties of common elements in the formation

27
Densities of Rock Formations and Fluids

28
Porosity determination from density logs:

For usual pore fluids and-for common reservoir matrix minerals, the difference
between the apparent density ρa read by the density log, and the bulk density ρb is
so trivial that it is disregarded

Φ is the porosity
ρm is matrix density
ρb is bulk density
ρf is fluid density

The density porosity is usually calculated assuming ρf = 1 gm/cc.

29
Typical Reservoir Porosity Values:

Sandstones have porosities that typically range from 8% to 38%, with an average of
18%. About 95% of sandstone porosity is effective porosity.

Carbonates have porosities that typically range from 3% to 15%, with an average of
about 8%. About 90% of carbonate porosity is effective porosity.

Less than 10%: poor, productivity doubtful

10- 15%: fair

15 ~ 25%: good, the most common range in productive reservoirs

Over 25%: excellent, but rare.

30
Water saturation:

Is the percentage of the pore volume of the reservoir rock that is filled with water.

It is generally assumed, unless otherwise known that the pore volume not filled
with water is filled with hydrocarbons.

Determining water and hydrocarbon saturation is one of the basic objectives of

well logging.

Water saturation can be measures by resistivity log.

Resistivity Log:

Resistivity is the degree to which a substance “resists” or impedes the flow of

electrical current. It is a physical property of the material, independent of size and
shape.

The resistivity unit used in well logging is ohm-meter2/meter, which is usually

shortened to ohm-meter.

Electrical conductivity is expressed in mhos per meter. In order to avoid decimal

fractions, in electrical logging, it is expressed in millimhos per meter.

Theory:

In reservoir rocks, the sedimentary minerals that make up the formation matrix
are non-conductors. Also, hydrocarbons such as gas and oil are non-conductors.
Therefore, current flow in sedimentary rocks is associated with the water in the
pore space.

Most of the waters encountered in well logging contain some sodium chloride
(NaCl) in solution. The current then is carried by the ions of the salt, which is
dissolved in the water. Therefore, conductivity is proportional to the salt
concentration (salinity) of the water.

31
The amount of water contained in the formation is directly related to the porosity
and, also, affects the formation resistivity. As the volume of water increases, the
capacity for ions increases and the conductivity increases. Thus, the formation
resistivity is affected by:

 Salt concentration in the water (salinity)

 Reservoir temperature
 Water volume (porosity)
 Hydrocarbon content.

32
Types of Resistivity Logs

1- Induction Electric Log (measures conductivity)

2- Electrode Log (measures resistivity)

Principle of Electrical Logs:

Currents were passed through the formation by means of current electrodes, and
voltages were measured between measure electrodes. These measured voltages
provided the resistivity determinations for each device.

Types of Electrode Log:

1- Normal Logs
2- Lateral Logs
3- Laterolog

33
Normal Log Device:
In the normal device, a current of constant intensity is passed between two
electrodes, A and B. The resultant potential difference is measured between two
other electrodes, M and N. Electrodes A and M are on the sonde. B and N are,
theoretically, located an infinite distance away. In practice, B is the cable armor,
and N is an electrode on the bridle (the insulation-covered lower end of the cable)
far removed from A and M. The distance AM is called the spacing (l&in. spacing
for the short normal, &in. spacing for the long normal), and the point of
inscription for the measurement is at 0, midway between A and M.

Normal Device, basic arrangement

34
Lateral Log Device:
In the basic lateral device, a constant current is passed between A and B, and the
potential difference between M and N, located on two concentric spherical
eqoipotential surfaces centered on A, is measured. Thus, the voltage measured is
proportional to the potential gradient between M-and N. The point of inscription
is at 0, midway between M and N. The spacing A0 is 18 ft 8 in. The sonde used in
practice differs from that shown in Fig. 7-2 in that the positions of the current and
measuring electrodes are interchanged; this reciprocal sonde records the same
resistivity values as the basic sonde described above. Also, all electrodes are in the
borehole, with N located 50 ft 10 in. above M.

Lateral Device, basic arrangement

35
Focused Logs:
Focused logs replaced Normal and Lateral logs since 1950

The responses of conventional electrical logging systems can be greatly affected by

the borehole and adjacent formations. These influences are minimized by a family
of resistivity tools that uses focusing currents to control the path taken by the
measure current. These currents are emitted from special electrodes on the
sondes.

The focused log used to obtain our data is: Laterolog

36
Laterolog:

The laterolog is a direct current (DC) tool based on Ohm's Law. The tools have
been designed to produce reliable resistivity measurements in boreholes
containing highly saline drilling fluids and/or when surrounded by highly resistive
rocks. The logging current is prevented from flowing up and down within the
drilling fluid by placing focusing electrodes (A1 and A2) on both sides of a central
measure electrode A0. The focusing electrodes force measure current to flow only
in the lateral direction, perpendicular to the axis of the logging device.

The laterolog electrode arrangement consists of a center current electrode placed

symmetrically between three short-circuited pairs of electrodes. A controlled
current is emitted from the short-circuited outer pair of electrodes in such a
manner that the voltage difference between the two inner short-circuited pairs of
electrodes is essentially zero. These electrode arrangements focus the formation
current into a thin disc, which flows perpendicularly to the borehole.

37
Formation Resistivity Factor:

It has been established experimentally that the resistivity of a clean, water-bearing

formation (i.e., one containing no appreciable amount of clay and no
hydrocarbons) is proportional to the resistivity of the brine with which it is fully
saturated. The constant of proportionality is called the formation resistivity factor,
F. Thus, if R0 is the resistivity of a non-shaly formation rock 100% saturated with
brine of resistivity Rw then

F: Formation resistivity factor

Rw: the resistivity of the formation water
Ro: the resistivity of the formation saturated 100% by the formation water of
resistivity Rw

a is an empirical constant

m is a cementation factor that varies from 1.3 for unconsolidated sands to 2.5 for
consolidated sandstones.

Φ is the porosity

F= 0.81/φ2 for consolidated sandstone

38
Archie’s Formula

Archie determined experimentally that the water saturation of a clean formation

can be expressed in terms of its true resistivity as:

Sw=

Where:

Sw is water saturation
n: Is water saturation exponent
Rt: the true resistivity of the formation partially saturated with water of resistivity
Rw and hydrocarbon.

F: Formation resistivity factor

Rw: the resistivity of the formation water
Ro: the resistivity of the formation saturated 100% by the formation water of
resistivity Rw

Where n in mostly all cases = 2

Ro can’t be measured, so it’s substituted by FRw

Rt is extracted from the resistivity log

F is calculated as mentioned before

39
Different resistivities and salinities of water (fresh & saline)

40
Lithology of the Formation:

The GR3 log is a measurement of the natural radioactivity of the formations. In

sedimentary formations the log normally reflects the shale content of the
formations. This is because the radioactive elements tend to concentrate in clays
and shales. Clean formations4 usually have a very low level of radioactivity, unless
radioactive contaminant such as volcanic ash or granite wash is present or the
formation waters contain dissolved radioactive salts.

Properties of Gamma Rays:

Gamma rays are bursts of high-energy electromagnetic waves that are emitted
spontaneously by some radioactive elements. Nearly all the gamma radiation
encountered in the earth is emitted by the radioactive potassium isotope of atomic
weight 40 (K44 and by the radioactive elements of the uranium and thorium series.
Each of these elements emits gamma rays; the number and energies of which are
distinctive of each element.
The coming figure shows the energies of the emitted gamma rays: potassium (K40)
emits gamma rays of a single energy at 1.46 MeV, whereas the uranium and
thorium series emit gamma rays of various energies.

3
Gamma Ray
4
Formations without shale

41
Theory:

In passing through matter, gamma rays experience successive Compton-scattering

collisions with atoms of the formation material, losing energy with each collision.
After the gamma ray has lost enough energy, it is absorbed, by means of the
photoelectric effect, by an atom of the formation. Thus, natural gamma rays are
gradually absorbed and their energies degraded (reduced) as they pass through the
formation. The rate of absorption varies with formation density. Two formations
having the same amount of radioactive material per unit volume, but having
different densities, will show different radioactivity levels; the less dense
formations will appear to be slightly more radioactive.

42
So the lithology of the reservoir must be determined to know the volume of shale
(Vsh), because it affects the resistivity and porosity calculations

It produces more porosity readings, and low resistivity ones.

To calculate Vsh, first we must obtain the gamma ray index (IGR)

Schlumberger formula to calculate IGR:

IGR: Gamma ray index

GRlog: Gamma ray log (

GRmin: Gamma ray minimum (clean sand)

GRmax: Gamma ray maximum (shale zone)

Calculating Vsh using Dresser-Atlas formula:

 For consolidated rock

Vsh = 0.33 [2(2xIGR) – 1.0]

After calculating Vsh, it’s needed to correct the previously calculated porosity and
water saturation

43
Porosity correction:

For porosity calculated using density log, we apply Dresser-Atlas formula:

Water saturation Correction:

For water saturation calculated using resistivity log we apply Schlumberger

formula

44
Calculating IGR using data obtained from well (A):

GR max= 120.79 at depth=8308 ft

GR min=25.632 at depth=8437.5 ft

GR log=64.496 at depth= 8277.5 ft

. .
IGR= = 0.387
. .

45
Interfacial Phenomena and Wettability

Introduction

The pore space in a petroleum reservoir rock is usually occupied by more than one
fluid. In an oil reservoir, water and oil occupy the pore space. In some oil
reservoirs, at some stage of depletion, water, oil and gas may occupy the pore
space.

When more than one fluid occupies the pore space of a porous medium, new set of
problems arise. Interfacial forces (surface forces) between the immiscible fluids
and between the fluids and the rock surface come into play. Further, the rock
surface can show a marked affinity for one of the fluids. Such an affinity is
characterized by the concept of wettability.

46
Surface and Interfacial Tensions

Surface Tension

Surface tension is the contractile force that exists at the interface of a liquid and its
vapor (or air). Surface tension makes the surface of a liquid drop act like a
membrane. The force is caused by unequal molecular attractions of the fluid
particles at the surface as shown in figure. The force per unit length ( =
Force/Length) tending to contract the surface of a liquid is a measure of the
surface tension of the liquid. It is a property of the liquid and is usually expressed
in units of dynes/cm.

Factors that affect the surface tension of a liquid include pressure, temperature
and solute concentration.

The effect of solute concentration on the surface tension of a liquid depends on

the liquid and the nature of the solute.

Liquids having fairly close values of surface tension. Generally, the surface tension
of the mixture varies approximately linearly with the composition.

Liquids having widely different values of surface tension.

In general, the surface tension of a liquid is reduced substantially by addition of a

liquid of lower surface tension, but is only slightly increased by addition of a liquid
of higher surface tension.

47
Solutions of colloidal (long chain) electrolytes.

In general, the surface tension decreases with solute concentration but is followed
by a region over which the surface tension is virtually unchanged by solute
concentration. For example, the surface tension of water at 25° C will be reduced
by addition of sodium lauryl sulfate from 72 dynes/cm to 40 dynes/cm at a
concentration of 0.01 moles per liter of solution. The surface tension remains
constant above this concentration.

48
Interfacial Tension

Interfacial tension is the contractile force per unit length that exists at the
interface of two immiscible fluids such as oil and water. The forces acting on the
surface molecules are similar to those in the liquid-vapor system, but the mutual
attraction of unlike molecules across the interface becomes important.

Chemicals that adsorb at interfaces are usually referred to as surface active agents
or surfactants. Such chemicals form a monolayer at the interface. The monolayer
is in a state of compression which reduces the contractile tendency of the
interface, thereby reducing the interfacial tension. The presence of the adsorbed
molecules creates a surface or spreading pressure which reduces the interfacial
tension. In fact,

Where  is the reduced interfacial intension,  is the original interfacial tension

and  is the spreading pressure. Surfactants are often used to reduce the
interfacial tension between oil and water in order to improve oil recovery.

The interfacial tensions between reservoir water and crude oils have been
measured for a number of reservoirs and found to range from 15 to 35 dynes/cm at
70 °F, 8 to 25 dynes/cm at 100 °F, and 8 to 19 dynes/cm at 130 °F.

49
Measurement of Surface and Interfacial Tensions

Ring Method

The ring method of determining surface or interfacial tension depends on

measuring the force required to pull the ring free of the interface as shown in
Figure. Theoretically, the surface or interfacial tension is given by

Where  is the surface or interfacial tension, F is the force required to pull the ring
free of the interface and L is the circumference of the ring. The factor of 2 accounts
for the fact that there are two surfaces around the ring. In practice, corrections are
needed to account for the mass of liquid lifted by the ring in breaking through the
interface as shown in Figure. Such corrections are made available with the
instrument. Figure shows a typical instrument, known as the du Nouy
tensiometer, which employs the ring method for surface or interfacial tension
determination.

50
51
52
Experiment A: (applying the Ring Method by using Dodecylbenzene
Sulfonic Acid)

Molecular Formula: C18 H30 O3 S

Typical Properties: Density (g/ml, 20 °C) 1.08

Standard Applications: DDBSA is suitable for use in the manufacturing of liquid

detergents over a wide range of concentrations and viscosities. Used in the
manufacturing of soapless detergent powders and pastes.

F 2L
Conc. (dyne) (cm)
0 904.32 12.56 72
0.003 904.32 12.56 72
0.03 542.592 12.56 43.2
0.3 542.592 12.56 43.2
3 542.592 12.56 43.2

DDBSA
80
70
60
 (dyne/cm)

50
40
30
20
10
0
0 0.1 0.2 0.3
Conc.

53
Experiment B: (applying the Ring Method by using Sodium Lauryl Sulfate)

STANDARD APPLICATIONS: SLS is a concentrated, high purity surfactant

developed for systems requiring high activity. SLS is an exceptional foamer,
dispersant and wetting agent and finds use in oral care products and powdered
detergents of all types.

F 2L
Conc. (dyne) (cm)
0 904.32 12.56 72
0.003 904.32 12.56 72
0.03 542.592 12.56 43.2
0.3 542.592 12.56 43.2
3 542.592 12.56 43.2

SLS
80
70
60
 (dyne/cm)

50
40
30
20
10
0
0 0.1 0.2 0.3
Conc.

54
Wettability

Wettability is defined as the tendency of one fluid to spread on or adhere to a solid

surface (rock) in the presence of other immiscible fluids.

50% of all sandstone reservoirs are oil-wet.

Strongly water-wet reservoirs are quite rare.

Rock wettability can affect its relative permeability to water and oil and thus
influence fluid injection rates, flow patterns of fluids within the reservoir, and oil
displacement efficiency.

Alteration of rock wettability by adsorption of polar materials, e.g. surfactants and

corrosion inhibitors, or by the deposition of polar crude oil components, can
strongly alter the behavior of the rock.

When water is injected into a water-wet reservoir, oil is displaced ahead of the
injected fluid. Injection water preferentially invades the small- and medium sized
flow channels or pores. As the water front passes, unrecovered oil is left in the
form of spherical, unconnected droplets in the center of pores or globules of oil
extending through interconnected rock pores. In both cases, the oil is completely
surrounded by water and is immobile. There is little oil production after injection
water breakthrough at the production well.

In an oil-wet rock, water resides in the larger pores, oil exists in the smaller pores
or as a film on flow channel surfaces. Injected water preferentially flows through
the larger pores and only slowly invades the smaller flow channels resulting in a
higher produced water/oil ratio and a lower oil production rate than in the water-
wet case.

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Contact angles

(a) The surface is preferentially oil wet

(b) The surface is of neutral wettability
(c) The surface is water wet
(d) The surface is totally water wet

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Surfactants and its use in EOR

Definition: they’re surface active agents in which their molecules are composed of
two portions called lipophilic and lipophopic.

Lipophilic group has sufficient solubility in the solvent and always tends to bring
the entire molecule into solution, whereas the lipophopic group is rejected by the
solvent, because it has less affinity for the solvent molecules and tends to expel
entire molecules from the solution.

Composition:

Mechanism of the surfactant in the EOR process

The surfactant is used to lower the interfacial tension between the flooding water
and the oil in the reservoir to increase the flooding recovery efficiency.

This is done since the polar group is soluble in the flooding water where the non
polar group is soluble in oil which leads to the decrease of the interfacial tension
between the two fluids increasing the flooding efficiency

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EFFECT OF SURFACE ACTIVE AGENTS ON ELECTROKINETIC AND
WETTABILITY CHANGES OF RESERVOIR ROCKS

When a solid particle is in tangential motion relative to a liquid phase, an electric

field is induced. As a result of the tangential motion along the slip plane, the
equilibrium of charges within the interface is disturbed and this disturbance is
counteracted by a flow of charges attempting to restore the electrical balance
across the whole interface. The overall phenomenon of interfacial flow and the

58
associated charge redistribution is known as the electrokinetic effect. The charge
gradient at the slip plane in solution is known as the electrokinetic potential.

Zeta potential is the difference between the potential at the slip plane and the
potential in the bulk solution, the latter being taken as the reference and equal to
zero. Whenever mobile charges are present, the interfaces become charged; the
exceptions are those specific conditions, which lead to a mutual compensation of
charges, resulting in a point of zero charge. Zeta potential is the most easily
accessible parameter to experimentally determine the sign and magnitude of the
potential at the solid-liquid interface.

Surface charge is an important property of a solid in contact with fluid since it can
determine what can adsorb, penetrate or adhere from the liquid phase. Indeed,
processes such as adsorption, particularly of surfactants or macromolcules, can
alter the interfacial behavior of the solids markedly. Surface charge of a solid
particle contacted with liquid phase is determined by the concentration of the
“potential determining ions” in solution; the potential determining ions in the case
of sand (quartz) are H+ and OH-. Other inorganic species, surfactants as well as
polymeric reagents can also affect the interfacial charge, this can in turn be
important in controlling transport of ions through the surface layers, but these
secondary effects are controlled by the potential determining ions.

The adsorption of surface active agents at the interface of a solid and a liquid
phase is a fundamentally important phenomenon. The adsorption is controlled by
the chemical nature of the species being adsorbed, including the nature of the
head group (anionic, cationic or nonionic) and that of the hydrophobic
characteristics, also the nature of the solid surface onto which the surfactant is
being adsorbed. Increasing the negativity in Zeta potential of silica is reported to
occur as a result of the adsorption of anionic surfactants.

This work is devoted therefore, to the evaluation of the effect of some surface
active agents on the electrokinetic and wettability changes, obtained as the result
of contact between sandstone and fluid. Surface charge measurements were
performed using an electrophoresis technique; wetability measurements
were carried out by the contact angle method. Elecrtrokinetic measurements with
other possible interfacial techniques will assist in understanding surface behavior
and explaining different mechanisms of surfactant adsorption.

EXPERIMENTAL

ELECTROPHORETIC MEASUREMENTS

59
The Zeta potential of sand particles exposed to various chemical environments was
measured using the Zeta Meter. The Zeta potential was measured after
conditioning the minerals in water in the absence and presence of inorganic and
organic surfactants at varying concentrations. pH was adjusted using diluted HCl
and/or NaOH. Zeta potential measurements were made on a Zeta Meter model
ZM3-83. The sample is loaded in a cell that contains an anode and a cathode at
opposite ends. A narrow tube, which connects the two, allows the sample to flow
between the electrodes. The cell is placed under a microscope, which is focused on
the stationary layer inside the tube. When an electrical field is applied through the
electrodes, the charged particles flow to either the anode or the cathode
depending on the polarity. The velocity of a particle can be measured by
monitoring the time required to traverse one interval on the micrometer. For each
sample, ten particles were tracked.

CONTACT ANGLE MEASUREMENTS

Contact Angle measurement is considered one of the most usual methods of

evaluating wettability. The oil droplet was placed on the bottom of a highly
smoothed surface of a Sandstone sample immersed in an aqueous solution. The
equilibrium contact angle was then measured from the photographs. All
measurements were carried out at 25 °C. The contact angle measured in the water
phase was determined by making a tangent to both sides of the oil droplet.
Contact angle of less than 90°, measured through the water phase, indicates
preferentially water-wet condition; whereas a contact angle greater than 90°
indicate preferentially oil-wet condition. A contact angle of 90° would indicate that
the rock surface has equal performance for water and oil.

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References used:

 Schlumberger - Log Interpretation Principles & Applications

 Ekwere J. Peters, Petrophysics, , University of Texas.
 George Asquith, Basic well Log Analysis for Geologists.
 M. Naser Khan, Introduction To Wireline Log Interpretation
 Alkhatha’ami Mohammed, Permeability, Porosity, and Skin Factor.
 Erle C. Donaldson, Petrophysics, Second Edition Theory and Practice of
Measuring Reservoir Rock and Fluid Transport Properties
 Experimental Reservoir Engineering Laboratory Workbook, Norwegian
University Of Science and Technology.
 Fundamental of Well-Log Interpretation I, the acquisition of logging
data

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