2.6.

2 RESERVOIR ROCKS
Ankleshwar, Kalol and Kadi Formations reservoir have most of the oil and gas reserves of the
basin. Rao (1969), suggest that the Lower Ankleshwar formation has been deposited in a
transitional (deltaic) environment. Based on fossils assemblage, an open marine neritic
environment is some part of the basin is suggested by Wickenden and Sastri (1968). Mehrotra
(1977) suggest that the sand units of Ankleshwar formation represent littoral depositional and the
clastics were presumably contributed by the proto-Narmada River.

2.6.3 CAP ROCKS

In northern part of the basin Tarapur shale is the principal cap rock whereas in southern part,
Kanwa Shale and Telwa Shale of Ankleshwar Foramtion act as cap rocks.

According to Sarraf et al., (2000), the excellent cap rock properties of Kanwa Shale in the south,
probably responsible for poor hydrocarbon availability for Ardol and overlain Dadhar Formation.

In the South Cambay basin, the lower part of Dadhar formation have a wide transgressive phase
characterized mainly by Nummulites-Discocyclina assemblage indicating inner-middle shelf
environment with warm water conditions. Large input of coarser clastics sediments was
reworked by marine agencies and was deposited as widespread sandstones sheet in the Proto
Narmada river system. Thus, the major part of Dadhar Formation represents the sediments
deposited during the destructive phase of Proto-Narmada delta system. The upper part of this
formation as represented by the Reticulate Nummulites assemblage has short regressive span of
minor sea encroachment in this regime.

CHAPTER 3
PHYSICO-CHEMICAL PROPERTIES OF
 CRUDE OILS

3.1 INTRODUCTION
Petroleum or Crude Oil is a naturally occurring, inflammable liquid consisting of a complex
mixture of hydrocarbons of various molecular weights, and other organic compounds, that are
found in geologic formations beneath the earth's surface.

The term "petroleum" was first used in the treatise De Natura Fossilium, published in 1546 by
the German mineralogist Georg Bauer, also known as Georgius Agricola.

In its stricto senso, petroleum includes only crude oil, but in common usage it including both
crude oil and natural gas, both as mixture of hydrocarbons. Under surface pressure and
temperature conditions, the lighter hydrocarbons methane, ethane, propane and butane occur as
gases, while the heavier ones from pentane and up occurs in the form of liquids or solids.
However, in the underground oil reservoir, the proportion which is gas or liquid varies depending
on the subsurface conditions, and on the phase diagram of the petroleum mixture.

3.2 ORIGIN OF PETROLEUM

Although there is a sound evidence to support the formation of hydrocarbons due to natural
physical and chemical processes within the deep crust or mantle. These abiogenic formations are
rare and do not yield commercially viable sources of petroleum. The petroleum we drill for today
is of biogenic origin and formed by the thermal maturation of organic matter.

The key to the transfer of inorganic carbon to hydrocarbons is photosynthesis. Plants and algae
take carbon from the atmosphere, mainly from carbon dioxide, and combine it with water to
form glucose. Glucose is the starting point for conversation into more complex organic
compounds and formation of higher life forms. Under most common circumstances, when plants
and animals die, the organic matter is oxidized to form carbon dioxide and water, thus
completing the water cycle. However, under some circumstances, if the organic matter is buried
rapidly, it may be preserved, leading in time to the formation of petroleum.
The amount of matter buried depends on the ratio of organic productivity and destruction. The
organic matter dies and rain down on the sediment below. Gradually subsequent layers during
the process of sedimentation bury this sediment, and eventually form potential source rocks. The
organic matter must be preserved in order to lithify and form source rocks. Oxidation or
predation can destroy organic matter. The following conditions are necessary for preservation: -

1) A high sedimentation rate and a rapid burial process.

2) Fine grain size of sediment so that oxygen cannot penetrate and oxidises the material.
3) Anoxic bottom water conditions.

These conditions are most often found in shales and the fine grained limestones, which are
common sources rocks. The kind and amount of petroleum that is generated from these deposits
depends on the three main factors: -

1) The nature of the remains of living organism preserved in the sediments.

2) The abundance of the organic matter.
3) The extent to which organic matter has been cooked and matured.

Once organic deposit buried and preserved, certain physical and chemical processes must also
take place for the transformation of organic matter into petroleum. These processes are a
consequence of increasing burial depth with time, which exposes the organic deposits to both
increasing temperature and pressure. There are three major phases involved in the maturation or
cooking of the organic matter to form oil and gas. These phases are (a) Diagenesis involves
formation of kerogen, (b) Catagenesis involves maturation of kerogen; and (c) Metagenesis
involves liberation of oil.

3.3 KEROGEN AND KEROGEN CHEMISTRY

Kerogen is the term applied to disseminated organic matter in sediments that is insoluble in
normal petroleum solvents such as carbon bisulphide. Kerogen can be regarded as thermally
reactive organic material.
Chemically, kerogen contains hydrogen, carbon and oxygen with minor quantities of sulphur and
nitrogen. Based on the original organic matter deposits, three types of Kerogenes are
recognizable (Fig. 3.1), each type ultimately forms different hydrocarbons. They are as follows:-

Type 1: It involves fine algae in fresh water lakes, particularly in warm areas of high
productivity. After burial and heating it produces high quality waxy oils. In this type H:C ratio
ranges between 1.6 - 1.8. This kerogen has a higher proportion of H to O than other types, H:O
ratio ranges between 1.2 - 1.7, and it is rich in aliphatics compounds.

Type 2: It involves single celled plankton, algae, and bacteria abundant in marine environment as
type 1. This kerogen is rich in aliphatic compounds and is responsible for most of the world‟s oil.
In this type, the H:C ratio ranges between 1.4 - 1.0.

Type 3: It involves material derived from land vegetation, spore, pollen and plant fragments. It
generates coal and dry gas. In these type H:C ratio is < 1.0. Chemically, type 3 kerogen is low in
aliphatic compounds but high in aromatic compounds.

Figure No. 3.1: Types of Kerogen (Courtesy: www.google.com).

Identification of organic matter origin within a source rock is therefore important for assessing
its potential for hydrocarbon generation.

3.4 THEORIES OF ORIGIN

Theories concerning the origin of liquid fuels (petroleum) typically falls into two major
categories: Biogenic (Organic) theories and Abiogenic (Inorganic) theories. These theories are as
following: -

3. 4. 1 BIOGENIC (ORGANIC) THEORY

The biogenic (organic) theories claim that fossil fuels were formed from the remains of the
plants and animals that live long ago. The various theories on the origin of petroleum are as
follows:

(A) ENGLER’S ANIMAL THEORY

According to Engler‟s, Petroleum is formed by a process of putrefaction of animal remains.
Nitrogen thus eliminated and residual fats converted by earth‟s heat and pressure into petroleum.
Activity of anaerobic bacteria thought to play a part in the reactions.

SUPPORTING EVIDENCE
Oils resembling petroleum can be distilled from sediments containing fish remains. Many
petroleum deposits associated with marine sediments contain an abundance of foraminifera.

(B) HOFER’S VEGETABLE THEORY

According to Hofer‟s, Petroleum is formed by decay of accumulated vegetable refuse under
conditions which prevent oxidation and evaporation of the liquid products formed.

SUPPORTING EVIDENCE
Deposits of petroleum found in close association with sedimentary deposits containing diatoms,
seaweed, peat, lignite, coal and oil shale of known vegetable origin. Oils closely resembling
petroleum can be distilled from these substances.
(C) HYDROGENATION OF COAL OR OTHER CARBONACEOUS MATERIALS
Solid organic materials are converted into liquid hydrocarbons by combination with free
hydrogen at high pressures and temperatures in the presence of suitable catalysers i.e. nickel.

SUPPORTING EVIDENCE
Hydrogenation of coal in the laboratories and is in commercial plants. The ash of some
petroleum is chiefly nickel. However, the existence of free hydrogen in the nature is yet to be
demonstrated.

3.4.2 ABIOGENIC (INORGANIC) THEORY

The abiogenic (inorganic) theories assume that some combination of chemical reactions occur
naturally to form crude oil or natural gas. The various theories of inorganic origin are as
follows:-

(A) BARTHELOT’S ALKALINE CARBIDE THEORY

According to Barthelot‟s, the deep-seated deposits of alkaline metals in the free-state, reacts with
CO2 at high temperature, forming alkaline carbides. These, on contact with water, liberate
acetylene, which through subsequent process of polymerization and condensation, forms
petroleum.

SUPPORTING EVIDENCE
Evidences are lacking. Neither free alkaline metals nor carbides found in nature.

(B) METAL CARBIDE THEORY

Mendeleev (1877) proposed that the petroleum deposits of the world are seem to be controlled
more by large scale tectonic features than by the ages of sedimentary rock. To explain these
observations, he proposed the metal carbide theory. Iron carbides within the Earth‟s crust, on
contact with percolating waters form acetylene, which escapes through fissures to overlying
porous rocks and after there condensation forms petroleum.

SUPPORTING EVIDENCE
Magnetic iron oxides would also be formed as a product of these reactions. Magnetic
irregularities have been noted in the vicinity of some of the oil fields.

(C) MOISSAN’S VOLCANIC THEORY

Moissan‟s suggest that volcanic explosions may be caused by the action of water on subterranean
carbides.

SUPPORTING EVIDENCE
Small quantities of petroleum noted in volcanic lavas near Etna in Japan. Petroleum also
associated with volcanic rock in Mexico and Java.

(D) NEBULAR CONDENSATION THEORY

In 1890, Sokolov proposed that „bitumen‟, at that time meaning the whole range of hydrocarbons
from petroleum to tar, precipitated as rain onto the newly forming earth from the original nebular
matter from which the solar system was formed. In modern terminology he simply suggested that
petroleum originated from meteorites. Later he claimed that petroleum was ejected from the
earth‟s interior into the surface sediments. Recently this idea has been supported by F. Hoyle,
who proposes that not only oil, but life itself has extra-terrestrial origins.

SUPPORTING EVIDENCE
Small quantities of hydrocarbons occasionally found in meteorites.

(E) LIMESTONE, GYPSUM AND HOT-WATER THEORY

According to this theory, reaction between carbonate and sulphate of lime in the presence of
water at high temperatures sufficient to dissociate the water theoretically may form
hydrocarbons.

SUPPORTING EVIDENCE
Practically, it has been found impossible to demonstrate this reaction in the laboratory.

3.5 OCCURRENCE OF CRUDE OIL

The occurrence of petroleum is widespread but very uneven. Petroleum occurs on all the
continents of the world, although some continents are much richer in petroleum than others.
Crude oil occurs in all the geologic systems from Pre-Cambrian to Recent, though some systems
are notably more prolific than others. The occurrence of crude oil is as follows:-

(A) SURFACE OCCURRENCES

Petroleum occurs at the surface of the ground in the variety of ways. Some of these are (1)
Seepages, spring and bitumen exudates, (2) Mud volcanoes and mud flows, (3) Bitumen
impregnated sediments, (4) Vug and cavity fillings and (5) Kerogen shale and oil shale.

(B) SUBSURFACE OCCURRENCES

The subsurface occurrences of crude oil are (1) minor showing and (2) pool, field and province.

(1) MINOR SHOWING

During the drilling of a test well, oil and gas may be seen directly and also by means of test for
various physical properties, indirectly. In fact, fields and laboratory techniques as have been
developed to testify the well data which can yield fairly reliable information in regards to a
reservoir‟s gas, oil and water content, its thickness, porosity, permeability and its capacity to
produce oil and gas.

(2) POOLS, FIELD AND PROVINCES

The term “pool”, “field” and “province” are useful to define and locating various oil and gas
accumulations and occurrences.
“Pool” is the simplest unit of commercial occurrences. A pool may be small, underlying only a
few acres, or it may extend over many square miles. The term major pool is arbitrarily taken to
mean a pool that produce around 50 million barrels or more oil.

When lots of small or major pools are related to as single geological feature, it may be structural
or stratigraphic known as ―Field‖.

Several numbers of oil and gas pools and field make a region which is known as petroleum
―province‖.

3.6 FORMATION OF OIL POOL

The dispersed droplets of oil ultimately go to form oil pools which depend under following
necessary conditions.

3.6.1 MIGRATION AND ACCUMULATION OF CRUDE OIL

According to Durand (1987), Migration is the movement of oil and gas within the subsurface
and it occurs in three stages, i.e., primary, secondary and tertiary. Primary migration is known
for the migration of hydrocarbons within and out of the fine grained source rock. It is short
distance migration which ends with continuous permeable drainage system. The movement of
hydrocarbons through faults and carrier beds to the trap is called secondary migration. Leakage
through impermeable cap rock is termed tertiary migration.

Due to thermal expansion of pore water, rapid burial, tectonic stress and generation of
hydrocarbons (Durand, 1988; Ungerer et al., 1983) became main driving forces for expulsion
(primary migration) of hydrocarbon. Secondary migration is mainly regulated by the buoyant
rise of oil and gas in water saturated porous rocks, hydrodynamics and capillary pressure.
Whenever capillary pressure becomes dominant over buoyant force, the hydrocarbons stop
moving (Tissot and Welte, 1984).
The migration of dispersed droplet of oil generated within the source rock is due to compaction,
capillarity, buoyancy, its lower specific gravity than water, and current of sub-surface water.

Migration of Oil is shown in Fig. 3.2 and 3.3.

Figure No. 3.2: Migration of Oil.

Figure No. 3.3: Migration of Oil by Buoyancy.

3.6.2. SUITABLE RESERVOIR AND CAP-ROCKS

The migration of oil through porous and permeable suitable reservoir rocks lead to its
accumulation. Clay is not appropriate for the accumulation of oil owing to high porosity but low
permeability. The most appropriate reservoir rocks are sands and sandstones because of high
porosity and permeability (Fig. 3.4). Porous and cavernous limestone and dolomite and other
fissured and jointed rocks may also serves as a suitable reservoir rocks. The greater the porosity
causes greater the amount of oil yield, since rocks with small grains and small pores create more
friction to flow. Further, in the reservoir rock, a good impervious cap rock is necessary to hold
oil. The most suitable cap rock is clay and shale. Scanty petroleum migration could have been
occurred in a gaseous form along with the highly impermeable micro-fractures and micro-pores
towards the lower pressure areas.

Figure No. 3.4: Oil accumulation in porous and permeable Sandstone.

In Cambay basin, sandstones or siltstones are the main hydrocarbon reservoir rocks. Besides
these, there are other subsidiary reservoirs as fractured coals, fractured shales, and sideritic
marls. The reservoirs in different stratigraphic levels in Cambay basin are as following: -

Paleocene- Siltstones in Olpad formation

Lower Eocene- Lenticular sands in Cambay Shale, and sands and silts in Kadi clastic wedge in
Mehsana block
Middle Eocene- Sandstones in Ankleshwar Formation and siltstones, fractured coals and
sandstones in Kalol Formation
Upper Eocene-Oligocene- Lenticular sands in Tarapur Shales and sandstones-sands in Dadhar
Formation
In Ankleshwar, Kalol and Kadi formations, sandstones and siltstones are the main reservoirs.
The Ankleshwar and Dadhar sandstone formations deposited in Narmada-Tapti and Jambusar-
Broach blocks are the reservoirs in Ankleshwar, Kosamba, Gandhar, Nada, Dabka, Motwan-
Sisodara and Elao fields. These sandstones were fed into the basin during Middle Eocene-
Oligocene period along Palaeo-Narmada River, deposited in a deltaic to shallow marine
environment and were widely distributed to cover Broach and Narmada blocks. The Ankleshwar
and Dadhar sands in general have good porosities and permeabilities and make very good
reservoirs.

The principal cap rocks are Tarapur shales of Upper Eocene-Oligocene age in northern Cambay
basin. The Telwa and Kanwa shales of Middle Eocene to Oligocene age and the shales
intercalated with sandstones in Dadhar Formation constitute the principal cap rocks in the
southern Cambay basin.

3.6.3. SUITABLE TRAPS / STRUCTURES

The migrating oil required to be detained in some suitable traps or structures, where it
accumulates to form an oil pool. Being lighter than water, the gas and oil are stored in the highest
part of the container; in order to prevent their run off, the upper contact of the porous rock with
an impervious cover must be concave, as viewed from below. Such a container is called Trap,
and the portion of the trap that holds the pool oil or gas is called Reservoir. Anticlines and domes
are the commonest type of traps where the up-dip migration of oil is arrested when it reaches to
the top of the arch. Commercial deposit of crude oil and natural gas are always found
underground, where they nearly always occur in the water coated pore spaces of sedimentary
rocks. The classification divides the trap into three basic types: -

(A) STRUCTURAL TRAPS

A trap whose upper boundary is concave, as viewed from below, either by some local
deformation, such as folding or faulting or both, of the reservoir rocks is termed as Structural
Traps. Salt domes also have a great importance in most of the oil accumulation. The structural
traps are of following types: -
(I) ANTICLINE TRAP
An anticline is a structure in the rocks which were previously flat, but have been bent into an
arch. Oil that finds its way into a reservoir rock that has been bent into an arch will flow to the
crest of the arch, and get stuck (provided, of course, that there is a trap rock above the arch to
seal the oil in place) (Fig. 3.5).
(II) FAULT TRAP
Fault traps are formed by movement of rock along a fault line (Fig. 3.6). In some cases, the
reservoir rock has moved opposite a layer of impermeable rock. The impermeable rock thus
prevents the oil from escaping. In other cases, the fault itself can be a very effective trap. Clays
within the fault zone are smeared as the layers of rock slip past one another. This is known as
fault gouge.

(III) SALT DOME TRAP

Salt is a peculiar substance. If you put enough heat and pressure on it, the salt will slowly flow,
much like a glacier that slowly but continually moves downhill. Unlike glaciers, salt which is
buried kilometers below the surface of the Earth can move upward until it breaks through to the
Earth's surface, where it is then dissolved by ground- and rain-water. To get all the way to the
Earth's surface, salt has to push aside and break through many layers of rock in its path. This is
what ultimately creates the oil trap (Fig. 3.7).

(B) STRATIGRAPHIC TRAP

Stratigraphic traps include angular unconformity, pinch-out, etc.

(I) ANGULAR UNCONFORMITY

An angular unconformity might form a suitable oil trap if the layers above the unconformity are
impermeable and permeable rocks which are sandwiched between impermeable layers in the
inclined strata below the unconformity (Figure No. 3.8). This type of trap is more difficult to
locate because the unconformity may not be exposed at the Earth's surface.
Figure No. 3.5: Anticline Trap.

Figure No. 3.6: Fault Trap

Figure 3.7: Salt Dome Trap

 Figure No. 3.8: Angular
Unconformity.

(II) PINCH OUT

This occurs where the porous limestone reservoir loses its porosity and becomes impermeable
limestone, or the porous sandstone reservoir simply thins and pinches out (Fig. 3.9).

Layers of sand often form lens like bodies that pinch out. If the rocks surrounding these lenses of
sand are impermeable and deformation has produced inclined strata, oil and natural gas can
migrate into the sand bodies and will be trapped by the impermeable rocks. This kind of trap is
also difficult to locate from the surface, and requires subsurface exploration techniques.

Figure No. 3.9: Pinch Out.

(C) COMBINATION TRAPS
Both structural and stratigraphic elements form combination traps. A combination traps generally
have two or three stage history.
(I) A stratigraphic element caused the edge of permeability of the reservoir rock.
(II) A structural element caused the deformation that combines with the stratigraphic element
to complete the rock portion of the trap.
(III) A down dip flow of formation water increased the trapping effect.

3.7 PHYSICAL AND CHEMICAL PROPERTIES

The physical and chemical properties of crude oils are as following: -

3.7.1 CHEMICAL COMPOSITION OF CRUDE OIL

The branch of chemistry in which the organic compounds are studied is called Organic
Chemistry whereas the branch in which the inorganic compounds are studied is termed
Inorganic Chemistry. Crude oil is constituted of 99.9% of organic compounds & elements and
0.1% of inorganic compounds and organo-metallic compounds. Organically, crude oil is a
complex mixture of hydrocarbons and non-hydrocarbons. The simplest organic compounds are
those that contain only carbon and hydrogen and are known as Hydrocarbons. Minor elements
such as sulphur, nitrogen and oxygen are present in most petroleum, but they are generally
combined with organic carbon and hydrogen in complex molecules and are known as Non-
hydrocarbons. Both constitute bulk of the compounds found in most petroleum- natural gas,
crude oil and natural asphalt. The composition is schematically shown in fig. 3.10: -
Figure No. 3.10: Schematic flow chart of Composition of Crude Oil.

(A) HYDROCARBON SERIES

Hydrocarbons are the simplest organic compounds which are formed by the hybridization of
only carbon and hydrogen. In nature, hydrocarbons are found in three forms i.e. gaseous, liquid
and solid which are shown in Table No. 3.1.

Table No. 3.1: Classification of Hydrocarbons. (After, Amyx, Bass and Whiting, 1960)
DRY GAS MARSH GAS

GASEOUS WET GAS NATURAL GAS

PETROLEUM CRUDE OIL

VISCOUS OR SEMI SOLID MINERAL TAR

LIQUID
BITUMEN UREA

ASPHALTITE GILSONITE

COAL LIGNITE
SUB-BITUMINOUS
SOLID BITUMINOUS
SEMI-BITUMINOUS
ANTHRACITE
KEROGEN
BITUMINOUS SHALE PETROLIFEROUS
In present endeavour, hydrocarbons of crude oil have been divided into Paraffins
Hydrocarbons, Cyclo-paraffins or Naphthenes, Aromatics Hydrocarbons and Mixed
Hydrocarbons.

The naphthenes include the complex residue of the high-boiling range (750o F. and above) of all
petroleum; if the residues consist largely of asphalts, the crude is known as Asphaltic.

(I) PARAFFIN (ALKANE) SERIES

The paraffin series of hydrocarbons are a saturated straight chain (aliphatic) series have the
general composition CnH2n+2. The paraffin hydrocarbons- sometimes called the Methane Series-
are chemically inactive; in fact, the name ―Paraffin‖ means ―having little affinity‖. Methane
(CH4) is the simplest of all the hydrocarbons and is also the most stable.

Members of the paraffin series are generally the most abundant hydrocarbons present in both
gaseous and liquid petroleums. All the members below pentane (C5H12) are gaseous at ordinary
temperature and are the chief constituents of natural gas. Paraffin up to pentadecane (C15H32) is
liquid and are the chief constituents of straight run gasoline. Gasoline is generally composed of
the hydrocarbons that boil within the temperature range from 40o to 200o C. (from approx. 100o
to 400o F.) and its composition varies with the crude oil from which it is obtained. The higher
members of the paraffin (above pentadecane) series are waxy solids. Some crude oils contain
paraffin waxes, both amorphous and microcrystalline, which are obtained from the higher
boiling-point fractions.

Paraffins Hydrocarbons are of Straight Chains or Branched Chains types.

(a) Straight chain / normal paraffins

Straight chain or normal paraffins are found in all crude and particularly in the light types.
According to Mair (1964), the members of C1-C35 group have been separated and identified from
crude‟s. In crude oil, total content of n-paraffins may reach up to 25%, in heavy distillates it
ranges from 0 to 25% while in light gasoline fractions can have n-paraffins 80%.
(b) Branched chain paraffins
Branched chain paraffins are generally present in petroleum particularly in light and middle
boiling fractions. According to Bendoraitus (1962), the isoparaffins above C14 possessing
isoprenoid structures have lately been discovered in notable quantities in crude. Their
distribution, like n-paraffins, drops as a function of molecular weight in different fractions of
crude oil. 50% of the branched chain paraffins are generally found in the gasoline fraction.

(II) NAPHTHENE (CYCLOPARAFFIN) SERIES

The naphthene series of hydrocarbons are also known as the Cycloparaffin Series. It is saturated
(single covalent bond), closed-ring series (5 or 6 member rings). The members have the general
formula as CnH2n. It is isomers with the alkene series are structurally open chain and unsaturated.

All over the world, the hydrocarbons of naphthene series are the chief constituents of crude‟s.
However the total content varies from 30-60%, but the individual content of cyclo-paraffin show
less variation in different boiling fractions.

(III) AROMATIC (BENZENE) SERIES

The aromatic (benzene) series of hydrocarbons so named because many of its members have a
strong or aromatic odour, is an unsaturated, closed ring (carbocyclic) series having the general
formula CnH2n—6. Aromatics generally occur in crude as mono, bi, tri, or poly-nuclear
molecules. Benzene a colourless, volatile liquid is the parent and most common member of the
series found in petroleum as toluene (methylbenzene C6H5CH3) and xylene (dimethylbenzene,
C6H4CH3CH3).

The structure of benzene, called a Kekule Structure, is a ring with alternating single and double
bonds between the six carbon atoms, and with each carbon atom linked to one hydrogen atom.
The benzene structure has the hexagonal pattern.
The relative proportions of these hydrocarbons are quite close in all oils. Monocyclic aromatics
are present in light fractions, while number of rings increases with an increase of molecular
weight of the fraction.

(IV) MIXED MOLECULES

Mixed molecules are mostly naphtheno-aromatic hydrocarbons alongwith naphthene
hydrocarbons which form the major content of higher boiling petroleum fractions.

In studied Ankleshwar oils, carbon content varies between 40.37% and 81.26% whereas
hydrogen content varies between 6.81% and 14.06%.

Table No. 3.2: Chemical Properties of Crude Oil of Ankleshwar Oilfield.

S. No. Well No. Carbon Hydrogen Sulphur Oxygen Nitrogen Mineral

% % % % % Matter %

1 AW- 310 81.26 14.06 Nil Nil Nil 4.68

2 AW- 311 61.28 10.32 Nil Nil Nil 28.4

3 AW- 234 46.71 9.52 Nil Nil Nil 43.77

4 AW- 293 63.06 10.86 Nil Nil Nil 26.08

5 AW- 12 65.87 10.59 Nil 7.89 Nil 15.65

6 AW- 110 58.37 10.06 Nil 2.97 Nil 28.6

7 AW- 173 40.37 6.81 Nil 3.68 Nil 49.14

8 AW- 230 63.30 10.55 Nil 3.50 Nil 22.65

Average 60.02 10.34 Nil 2.25 Nil 27.37

(B) NON-HYDROCARBON SERIES

Non-hydrocarbon series includes the following compounds: -
(I) SULPHUR COMPOUNDS
Sulphur is important hetero-aromatic constituents of crude oils and occurs to some extent (0.1-
5.5% by weight) in each of the fractions that make up the oil. It may be any one or more of the
following form: (1) free sulphur (S); (2) hydrogen sulphide (H2S); (3) organic sulphur
compounds such as thiols or mercaptans. Many sulphur hydrocarbons are found in cracked
distillates, but it is not known whether they are formed during the high temperature distillation or
originally present in the crude oil.

The presence of sulphur and sulphur compounds in gasoline causes corrosion, bad odour, and
poor explosion. Crude oils of low API gravity (high specific gravity) generally contain more
sulphur than others. Many asphalt and bitumen seepages and oil shales have high sulphur
content. Sulphur content in crude varies from traces to 5% whereas compounds of sulphur may
even go up to 40%. Crude oils carrying less than 0.5 % sulphur called “low sulphur crude,”
whereas those carrying more than 0.5 % called high sulphur crude‟s.

In studied Ankleshwar oils, sulphur content is totally absent.

(II) NITROGEN
Nitrogen (N) is a colourless, tasteless, odourless gas, composing about 78% of dry air. It is found
in natural gases in amounts up to 99% by volume. There are at least two possible sources for the
nitrogen in natural gas. The first possible source suggests that the nitrogen of natural gases
merely represent the nitrogen content of air that has been trapped in the sediments, perhaps in the
additions from igneous sources and from the decomposition of the nitric organic compounds. A
second possible source is suggested by the high nitrogen content in gases rich in helium.

Nearly all crude oils contain small quantities of nitrogen, varies between 0.01 to 2%. The
nitrogen compounds in the distillates are known as Pyridines (C5H5H) and Quinolines (C9H7N).
Since nitrogen is common, inert constituent of natural gas, it may be associated with the crude oil
as dissolved gas.

In studied Ankleshwar oils, nitrogen content is totally absent.

(III) OXYGEN
Oxygen is found in crude oil in various forms such as free oxygen, phenols, fatty acids and their
derivatives, naphthanic acids and generally ranging between 0.1 and 4.0 %. Resin and
asphaltenes are also classified as oxygen compounds, because oxidation reactions seem to be
involved in their genesis.

In studied Ankleshwar oils, oxygen content varies between Nil to 7.89%.

(C) MINERAL CONSTITUENTS

The elements that have been identified in crude oil ash include silicon, iron, aluminium, calcium,
magnesium, copper, lead, tin, arsenic, antimony, zinc, silver nickel, chromium, molybdenum and
vanadium. Clay minerals sometimes come up along with crude oil. They settle out with the water
that accompanies with crude oil, and this indicates that they are probably associated with water
rather than with the oil. The metal content of crude oils varies from 0.1 to 100 ppm. According to
Melver (1962), about 30 metals have been found in which chief of them being nickel and
vanadium. Triebs (1935) confirmed the presence of vanadium and nickel in porphyrine
complexes.

In studied Ankleshwar oils, metallic content varies between 4.68 to 49.14%.

3.7.2 PHYSICAL PROPERTIES OF CRUDE OIL

(A) COLOUR
In transmitted light, the colour of petroleum varies from light yellow to red and dark or black oils
are opaque. Oils having high specific gravity are dark in colour. The cause of the colour is
related to the aromatic series of compounds. In reflected light, crude oil is usually show green
colour, because of its fluorescence.
In present investigation, all oil samples show brown to black colour (Table No. 3.3).
(B) ODOUR
The odour of any substances is determined by its composition. In Crude oils, the agreeable odour
is due to paraffin‟s and naphthalene, on the other hand unsaturated hydrocarbons, nitrogen and
sulphur compounds are responsible for disagreeable odour.

In present investigation, all oil samples show disagreeable odour (Table No. 3.3).
Table No. 3.3: Physical Properties of Crude Oils of Ankleshwar Oilfield.

S. Well Sand Colour Order Viscosity Specific API

No No. No. (cp) Gravity Gravity
(gm/cc)
1 310 1 Black Disagreeable 0.31 0.6653 45.4
2 293 2 Black Disagreeable 0.33 0.6775 45.8
3 110 3 Black Disagreeable 0.36 0.6710 45.3
4 211 4 Black Disagreeable 0.41 0.6120 45.4
5 173 5 Brown Disagreeable 0.36 0.6808 45.3
6 16 6 Black Disagreeable 0.46 0.7068 47.6
7 233 7 Brown Disagreeable 0.48 0.6412 47.6
8 300 8 Brown Disagreeable 0.41 0.6609 47.8
9 230 9 Black Disagreeable 0.36 0.6725 47.2
10 234 10 Black Disagreeable 0.42 0.6789 48.2

(C) SPECIFIC GRAVITY

Specific gravity is the ratio of the weights of equal volumes of the substance and pure water.

API gravity does not have a straight line relationship with specific gravity, but in Petroleum
industry, API (American Petroleum Institute) gravity is the preferred property. High values of
API gravity correspond to low specific gravity and low specific gravity corresponds to high API
gravity. So the scale cannot be used directly in engineering calculation.

A similar scale is the European Baume gravity scale. These two arbitrary scales are related to
specific gravity by the following formula.

Degree API = 141.5 / Sp. Gr. at 60º F – 131.5

Degree Baume = 140 / Sp. Gr. at 60º F – 130

The specific gravity of petroleum usually ranges from 0.8 gm/cc (45.3º API) for the lighter
crude oils to over 1.0 gm/cc (10º API) for the asphaltic crude oils.
In present investigation, specific gravity ranges between 0.6120 and 0.7068 gm/cc and API
gravity ranges between 45.3º and 48.2º API (Table No. 3.3).

(D) VISCOSITY
Viscosity is an inverse measure of the ability of a substance to flow, i.e. greater the viscosity of a
fluid, the less readily it flows. The unit of viscosity is the poise or centipoises (0.01P). Natural
gas and light oils are very mobile whereas heavier oils are highly viscous and grade into the
semi-solid petroleum‟s.

The viscosity of a liquid decreases with an increases in temperature due to increase of the
molecular agitation, which in the absence of confining pressure maintaining a fixed volume,
increases the intermolecular distance and the volume.

The most simple and most widely used instruments for the determination of viscosity are
capillary types, and the viscosity is derived from the equation: -

π r4 P
µ= ----------------------
8nl
Where r is the tube radius, l the tube length, P the pressure difference between the ends of a
capillary, n the “coefficient of viscosity” and µ the quantity discharged in unit time.

In present study, viscosity of crude oils falls between 0.31 and 0.48P (Table No. 3.3).

(E) OPTICAL ACTIVITY

Most of the oils have optical activity i.e. the power to rotate the plane of polarization of polarized
light. This is measured with the help of polaroscope in degrees per millimeter, and the average
range is from 0 to 1.2 degrees. If the plane is rotated to the right, the substance is said to be
dextrorotatory; if the plane is rotated to the left, the substance is said to be levorotatory. All
crudes either are optically active or contain distillation fractions, particularly in the intermediate
range (250-300 C, at 12mm.Hg), that are optically active. Optical activity is commonly argued in
support of the origin of petroleum from plant or animal remains, because, as far as we know,
optically active substance cannot be synthesized inorganically.

In present study, plane polarized light rotate to right (rotation value1-50) in oil samples AW-
310, AW-234, AW-110 and show dextrorotatory activity whereas plane polarized light rotate to
left (rotation value 0.5-2) in oil samples AW-311, AW-293, AW-12, AW-273, AW-230 and
show levorotatory activity (Table. No.3.4 .

Table No. 3.4: Optical Properties of Crude Oils of Ankleshwar Oilfield.

S. No Sample No. Rotation [ἀ]Dt in degree Solubility

(+) (-)

1 AW 310 1 Nil Hexane

2 AW 311 Nil 2 Hexane
3 AW 234 50 Nil Hexane
4 AW 293 Nil 0.5 Hexane
5 AW 12 Nil 1 Hexane
6 AW 110 1 Nil Hexane
7 AW 273 Nil 2 Hexane
8 AW 230 Nil 2 Hexane

(F) CLOUD AND POUR POINT

Cloud point is the temperature at which the first cloud appears in the oil. It is due to settling out
of the solid paraffins wax; wax free naphthanic oil shows no cloud point.

Pour point is the temperature 2º to 5º C lower than the cloud point. At this temperature oil is the
last fluid and will not flow. High pour point shows the presence of high wax content in crude oil.
In present investigation, cloud point varies between 31.5º and 35.8º C and pour point varies
between 29.3º and 32.4º C (Table No. 3.5).

(G) FLASH POINT AND BURNING POINT

Flash point is temperature at which the vapours rising off the surface of the heated oil will ignite
with a flash of very short duration when a flame is passed over the surface.

When the oil is heated to a higher temperature, it will ignite and burn with a steady flame at the
surface. The lowest temperature at which this will occur is known as the Burning point.

In present investigation, flash point varies between 80º and 99º C and burning point varies
between 80.63º and 127.4º C (Table No. 3.5).

Table No. 3.5: Thermal Properties of Crude Oil of Ankleshwar Oilfield.

S. No. Well No. Sand No. Cloud Pour Flash Burning

Point (ºC) Point (ºC) Point (ºC) point (ºC)
1 310 1 32.1 29.3 92 127.4
2 293 2 33.7 31.7 95 108.8
3 110 3 32.2 30.2 99 121.1
4 211 4 33.6 31.3 85 123.9
5 173 5 32.1 30.8 80 107.5
6 16 6 35.8 32.4 82 114.1
7 233 7 33.4 32.1 89 80.63
8 300 8 34.6 32.3 93 103.2
9 230 9 31.5 29.8 98 90.31
10 234 10 31.8 29.3 94 120.25

(H) RESERVOIR TEMPERATURE

The temperature of the rocks and the fluids increases with depth. The rate of temperature
increase with depth is due to the geothermal gradient. It is expressed in degrees Fahrenheit per
100 feet of depth or number of feet per Fahrenheit increase. In an individual well, temperature is
measured with a temperature bomb that is lowered into the well. This is done after the well has
been left for several days to come to thermal equilibrium. By subtracting the mean annual
surface temperature from the formation temperature and dividing by the depth of the formation
from the surface, the geothermal gradient of that well can be calculated. Oil, as it is pumped out
of a well, is hot. The deeper the well, the hotter will be the oil.
In present investigation, reservoir temperature varies between 70.5º and 84º C (Table No. 3.6).

(I) RESERVOIR PRESSURE

In a subsurface reservoir, there is one pressure on the fluid in the pores of the rock and another
pressure on the rock itself. The pressure on the fluid is generated by the weight of overlying
fluids. The deeper the reservoir, the greater will be the pressure. The fluid pressure increase with
depth is the hydrostatic pressure gradient and is expressed in pounds per square inch (psi) per
100 feet. It depends on the density of the overlying fluid, usually water.
In present investigation, reservoir pressure varies between 70 and 113 kg/cm2 (Table No. 3.6).

Table No. 3.6: Reservoir Properties of Crude Oil of Ankleshwar Oilfield.

S. No Well No. Sand No. Reservoir Pressure Reservoir Temp.

(kg/cm2) (ºC)
1 310 1 108.8 83.5ºC
2 293 2 109 82ºC
3 110 3 109.1 80ºC
 4 211 4 107.3 78ºC
5 173 5 113 80.5ºC
6 16 6 87 70.5ºC
7 233 7 70 71.5ºC
8 300 8 98 84ºC
9 230 9 93 73.5ºC
10 234 10 93.8 74ºC

3.8 GAS CHROMATOGRAPHY (GC) ANALYSIS

Gas-liquid chromatography (GLC), or simply gas chromatography (GC), is a common type of
chromatography used in organic chemistry for separating and analyzing compounds that can be
vaporized without decomposition. Typical uses of GC include testing the purity of a particular
substance, or separating the different components of a mixture (the relative amounts of such
components can also be determined). In some situations, GC may help in identifying a
compound. In microscale chemistry, GC can be used to prepare pure compounds from a mixture.

Gas Chromatographic analyses are mainly carried out on the saturated-hydrocarbon fractions of
crude oils and bitumens. Gas chromatography of saturated hydrocarbon is mainly done to look at
n-alkane and isoprenoid distributions (pristane/phytane ratios and C15 to C20 isoprenoid profiles)
and both of which are mainly related to diagenetic history. It also gives useful information about
steranes and triterpanes.

3.8.1 METHODOLOGY
A gas chromatograph is a chemical analysis instrument for separating chemicals in a complex
sample. A gas chromatograph uses a flow-through narrow tube known as the column, through
which different chemical constituents of a sample pass in a gas stream (carrier gas, mobile
phase) at different rates depending on their various chemical and physical properties and their
interaction with a specific column filling, called the stationary phase. As the chemicals exit the
end of the column, they are detected and identified electronically. The function of the stationary
phase in the column is to separate different components, causing each one to exit the column at a
different time (retention time) (Fig. 3.11 & 3.12). Other parameters that can be used to alter the
order or time of retention are the carrier gas flow rate and the temperature.

In a GC analysis, a known volume of gas or liquid is injected into the "entrance" (head) of the
column, usually using a micro syringe (or, solid phase micro extraction fibers, or a gas source
switching system). As the carrier gas sweeps the analyze molecules through the column, this
motion is inhibited by the adsorption of the analyze molecules either onto the column walls or
onto packing materials in the column. The rate at which the molecules progress along the column
depends on the strength of adsorption, which in turn depends on the type of molecule and on the
stationary phase materials. Since each type of molecule has a different rate of progression, the
various components of the analyzed mixture are separated as they progress along the column and
reach the end of the column at different times (retention time). A detector is used to monitor the
outlet stream from the column; thus, the time at which each component reaches the outlet and the
amount of that component can be determined. Generally, substances are identified (qualitatively)
by the order in which they emerge (elute) from the column and by the retention time of the liquid
analyze in the column.

Figure No. 3.11: Gas Chromatograph.

Figure No. 3.12: Flow chart showing the process and principal of Gas Chromatograph.

3.8.2 IDENTIFICATION AND INTERPRETATION OF COMPOUNDS

Identification of the compounds represented by the various peaks is carried out by comparison of
retention times (times required for components to emerge from the column) with authentic
standards. Quantification is performed either by measuring peak heights (if all peaks in question
are the same shape) or, more correctly, by measuring the areas under the peaks using an
automatic integrator attached to the detector.

The gas chromatogram of oil samples of Ankleshwar oilfields are shown in plot 3.13, 3.14, 3.15
and 3.16 and their identification and interpretation are also shown by table 3.6.
Figure No. 3.13: Gas Chromatograph Plot of Oil of Well No. 293.

Peak Time Area Peak Time Area Peak Time Area

# min % # Min % # Min %
1 9.567 0.16 24 27.994 4.16 47 46.381 1.2
 2 10.156 1.11 25 28.913 0.08 48 47.449 4.68
3 11.061 2.69 26 29.513 0.4 49 47.965 2.34
4 11.961 0.01 27 30.585 0.51 50 49.332 0.79
5 12.911 0.26 28 31.714 4.95 51 50.109 4.58
6 13.368 0.56 29 32.564 0.71 52 50.684 0.27
7 13.805 1.78 30 33.448 0.13 53 51.384 0.08
8 14.863 2.74 31 33.837 0.02 54 51.892 0.02
9 16.456 0.48 32 34.17 0.3 55 52.602 4
10 17.793 0.37 33 34.614 0.89 56 54.247 0.04
11 19.055 0.4 34 35.229 5.3 57 54.98 3.79
12 19.559 2.62 35 35.888 0.38 58 56.155 0.05
13 19.886 0.22 36 37.137 0.21 59 56.614 0.03
14 20.469 0.05 37 37.569 0.33 60 57.524 4.19
15 20.967 0.27 38 38.126 0.54 61 58.782 0.01
16 21.427 0.35 39 38.56 5.49 62 60.503 3.71
17 22.505 0.54 40 39.615 0.78 63 64.158 3.54
18 23.474 0.51 41 40.437 0.84 64 68.723 3.13
19 23.967 3.47 42 40.483 1.42 65 74.472 2.88
20 24.686 0.11 43 41.694 5.84 66 81.722 2.36
21 25.247 0.67 44 43.023 0.01
22 26.729 0.22 45 43.695 0.43
23 27.707 0 46 44.667 5.01
Figure No. 3.14: Gas Chromatograph Plot of Oil of Well No. 110.

Peak Time Area Peak Time Area Peak Time Area

# min % # Min % # Min %
1 9.96 3.07 24 26.569 0.58 47 43.004 0.13
2 10.84 5.1 25 26.606 0.12 48 43.713 0.49
 3 12.002 0.04 26 27.282 0 49 44.117 0.19
4 12.699 1.38 27 27.84 5.04 50 44.813 3.78
5 13.15 1.13 28 28.815 0.21 51 46.446 0.69
6 13.65 3.15 29 29.471 0.57 52 47.602 3.3
7 14.56 5.44 30 30.527 0.6 53 48.04 1.29
8 16.277 1.72 31 31.263 0.32 54 49.378 0.38
9 16.625 0.49 32 31.654 5.1 55 50.256 2.62
10 17.59 3.88 33 32.526 0.64 56 50.753 0.13
11 18.195 0.23 34 33.427 0.26 57 51.444 0.05
12 18.739 1.2 35 34.152 0.43 58 51.992 0.02
13 19.287 5.33 36 34.598 0.8 59 52.758 2.25
14 20.361 0.11 37 35.22 5.32 60 54.33 0.02
15 20.844 0.3 38 35.873 0.53 61 55.126 2
16 21.216 0.12 39 37.12 0.29 62 56.258 0.01
17 22.301 1.6 40 37.577 0.31 63 57.626 1.7
18 22.712 0.25 41 38.136 0.45 64 60.628 1.44
19 23.328 1.07 42 38.614 5 65 62.262 0.11
20 23.727 5.13 43 39.623 1.18 66 64.329 1.3
21 24.556 0.25 44 40.449 0.85 67 68.938 1.16
22 25.117 0.89 45 40.872 0.91 68 74.735 0.94
23 26.125 0.17 46 41.789 4.31 69 82.092 0.05

Figure No. 3.15: Gas Chromatograph Plot of Oil of Well No. 230.

Peak Time Area Peak Time Area Peak Time Area

 # min % # Min % # Min %
1 8.276 1.25 25 26.542 0.22 49 43.098 0.24
2 8.797 0.34 26 26.729 0.14 50 43.808 0.58
3 9.08 0.26 27 27.331 0 51 44.189 0.23
4 9.532 0.36 28 27.614 0.01 52 44.914 3.69
5 10.119 2.06 29 28.042 6.55 53 46.557 0.62
6 11.056 3.83 30 28.913 0.19 54 47.696 2.95
7 12.866 0.82 31 29.54 0.62 55 48.148 1.12
8 13.337 0.85 32 30.645 0.64 56 49.474 0.27
9 13.797 2.49 33 31.387 0.19 57 50.346 2.39
10 14.822 4.92 34 31.852 6.31 58 50.892 0.14
11 16.421 0.85 35 32.65 0.67 59 51.522 0.03
12 17.753 2.97 36 33.501 0.25 60 52.076 0.15
13 18.358 0.36 37 34.263 0.43 61 52.845 2.02
14 18.995 1.04 38 34.724 0.86 62 53.643 0.02
15 19.517 5.78 39 35.424 6.11 63 54.425 0.01
16 20.458 0.13 40 35.972 0.47 64 55.21 1.7
17 20.948 0.54 41 37.197 0.3 65 56.345 0.01
18 21.391 0.63 42 37.689 0.36 66 57.727 1.66
19 22.471 1.86 43 38.252 0.49 67 60.756 1.12
20 22.848 0.29 44 38.788 5.44 68 64.485 1.5
21 23.454 1.04 45 39.711 0.98 69 69.162 0.75
22 23.948 6.39 46 40.259 0.91 70 71.12 0
23 24.655 0.2 47 40.989 1.04 71 75.011 0.54
24 25.252 0.97 48 41.945 4.81 72 82.468 0.04

Figure No. 3.16: Gas Chromatograph Plot of Oil of Well No. 310.
Peak Time Area Peak Time Area Peak Time Area
# min % # min % # Min %
1 10.111 4.09 25 25.086 0 49 40.446 0
2 10.692 0 26 25.231 0.01 50 40.781 0 CHAPTER
3 10.977 0.59 27 25.257 0.02 51 40.792 0
4 11.046 1.8 28 25.364 0.06 52 41.128 0.14 –4
5 11.309 0.01 29 25.411 0.03 53 42.045 9.9
6 19.766 1.58 30 27.821 0.03 54 43.671 0.17
PETRO-
7 21.167 0.01 31 28.238 10.3 55 44.998 8.93
8 21.205 0 32 30.185 0 56 46.214 0.22
9 21.252 0 33 30.868 0.01 57 46.296 0.01
PHYSICS
10 21.596 0 34 32.033 9.55 58 46.528 0.02
11 21.61 0.01 35 32.835 0.14 59 46.606 0.04
OF
12 21.624 0.01 36 34.546 0 60 46.809 0.01
13 21.81 0.01 37 34.897 0.14 61 47.757 6.17 ROCKS
14 22.249 0 38 35.57 9.09 62 48.064 0.11
15 22.272 0 39 37.045 0.01 63 48.215 3.02
16 22.332 0 40 37.16 0.01 64 50.406 6.99 4.1
17 22.363 0.01 41 37.711 0.01 65 52.899 0.35
INTRODUC
18 22.378 0 42 38.388 0.05 66 55.259 6.1
19 22.647 0 43 38.424 0.02 67 57.489 0.01 TION
20 22.796 0 44 38.907 9.55 68 57.774 1.63
21 22.882 0.01 45 39.684 0.01 69 60.819 0.39 Petro-physical
22 22.97 0 46 40.342 0.01 70 64.567 0.29
properties of a
23 24.205 8.69 47 40.388 0.01 71 70.968 0.01
24 24.845 0 48 40.427 0 72 79.35 0.01 rock have
special significance in terms of their reservoir characters, migration properties and others related
to fluidity. The important common sedimentary reservoir rocks are sandstones, limestones and
clays along with conglomerates. Clay, when it occurs between grains is referred to as clay
matrix. It may have been deposited as clay size fraction material during the depositional event or
it may have formed as the result of a diagenetic process such as devitrification of volcanic glass;
hard to tell in thin section how it has formed; not all the cements as pore filling material. The
quartz outside of the dust rim (overgrowth) on a detrital quartz grain is authigenic quartz cement.
Calcite, gypsum, anhydrite, dolomite, and barite are all common cementing minerals. The
sedimentary units as reservoir rocks are sandstone and shale dominantly in the area under
investigation.
4.2 INTRODUCTION OF SANDSTONE
Sandstone, a clastic sedimentary rock, grains are predominantly quartz with little amount of
feldspar and accessories of mica and iron oxides. The relatively high porosity and permeability
of sandstones make them good reservoir rock.