Reservoir Fluids Composition

CONTENTS

1 INTRODUCTION
2 HYDROCARBONS
2.1 Chemistry of Hydrocarbons
2.2 Alkanes or Paraffinic Hydrocarbons
2.3 Isomerism
2.4 Unsaturated Hydrocarbons
2.5 Napthene Series
2.6 Aromatics
2.7 Asphalts
3 NON-HYDROCARBON COMPOUNDS
4 COMPOSITIONAL DESCRIPTION FOR
RESERVOIR ENGINEERING
4.1 Definitions of Composition in Reservoir
Engineering
5 GENERAL ANALYSIS
5.1 Surface Condition Characterisation
5.2 Refractive Index
5.3 Fluorescence of Oil

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LEARNING OBJECTIVES
Having worked through this chapter the Student will be able to:

Describe briefly the origin, nature and appearance of petroleum fluids

Be aware that the principal components of petroleum fluids to be hydrocarbons.

Draw a diagram illustrating the classification of hydrocarbons and to identify;

paraffins (alkanes ), aromatics and cyclic aliphatics ( napthas).

List the non- hydrocarbon compounds which might be present in small qualities
in reservoir fluids.

Define the black oil model description of the composition of a reservoir fluid.

Explain briefly what PNA analysis is and its application.

Describe briefly the concept of pseudo components in fluid composition

characterization.

Be aware of general analysis descriptors for petroleum fluids e.g. oAPI,

refractive index and flourescence.

Be able to calculate the API gravity given the specific gravity

Reservoir Fluids Composition

1 INTRODUCTION
Petroleum deposits vary widely in chemical composition and depending on location
have entirely different physical and chemical properties. The very complex characteristics are evident from the many products which can be produced from oil and gas.
What is petroleum? Petroleum is a mixture of naturally occurring hydrocarbons
which may exist in the solid, liquid or gaseous states, depending on the conditions of
temperature and pressure to which it is subjected.1
Petroleum deposits occurring as a gaseous state are termed natural gas, in the liquid
state as petroleum oil or crude oil and in the solid state as tars, asphalts and waxes.
For a mixture with small molecules it will be a gas at normal temperature and pressure
(NTP). Mixtures containing larger molecules will be a liquid at NTP and larger
molecules as a solid state, for example, tars and asphalts.
The exact origin of these deposits is not clear but is considered to be from plant, animal
and marine life through thermal and bacterial breakdown.
The composition of crude oil consists mainly of organic compounds, principally
hydrocarbons with small percentages of inorganic non-hydrocarbon compounds.
such as carbon dioxide, sulphur, nitrogen and metal compounds. The hydrocarbons
may include the lightest (C1 methane ) to napthenes and polycyclics with high
molecular weights.
The appearance varies from gases, through very clear liquids, yellow liquids to a dark,
often black, highly viscous material, the variety obviously being a function of
composition. Although the principal elements are carbon (84-87%), and hydrogen
(11-14%), crude oil can vary from a very light brown liquid with a viscosity similar
to water to a very viscous tar like material .
Water is always present in the pore space of a reservoir, since the original depositional
environment for the rocks was water. This water has subsequently been displaced by
the influx of hydrocarbons but not totaly since surface tension forces acting in the rock
pore space cause some of the water to be retained.
For reservoir engineering purposes the description of the composition is an important
characterisation parameter for the determination of a range of physical parameters
important in various reservoir volumetric and flow calculations. It is not the concern
of the reservoir engineer to determine the composition with respect to understanding
the potential to separate the material to a range of saleable products. For this reason
therefore simplistic characterisation approaches are used.
The two compositional characterisation approaches used are the compositional model
and the black oil model. The basis of the compositional model is a multicomponent
description in terms of hydrocarbons and the black oil model is a two component
description in terms of produced oil, stock tank oil and produced gas, solution gas. The
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compositional model is the topic covered in this chapter and the black oil model is
covered in the liquid properties chapter.

2 HYDROCARBONS
2.1 Chemistry of Hydrocarbons
The compositional model uses hydrocarbons as the descriptor since hydrocarbons
represent the largest proportion in petroleum fluids. It is important to review briefly
the chemistry of hydrocarbons.
The hydrocarbon series is represented in figure 1 below
Hydrocarbons
Aliphatic

Alkanes
(Paraffins)

Aromatics

Alkenes

Alkynes

Cyclic Aliphatics
(Napthenes)

The hydrocarbons divide into two groupings with respect to the arrangement of the
carbon molecules and the bonds between the carbon molecules. The arrangement of
the molecules are open chain or cyclic and the bonds between the carbon are saturated
(single) bonds or unsaturated or (multiple) bonds.

2.2 Alkanes or Paraffinic Hydrocarbons

The largest series is the alkanes or paraffins which are open chain molecules with
saturated bonds. Carbon has a valance of four and therefore the formula for these
compunds is CnH2n+2. These saturated hydrocarbons include all the paraffins in which
the valence of the carbon atoms is satisfied by single covalent bonds. This type of
structure is very stable. Unsaturated hydrocarbons are those where the valence of
some of the carbon atoms is not satisfied with single covalent bonds so they are
connected by two or more bonds which make them less stable and more prone to
chemical change.
The paraffin series begins with methane (CH4), and its basic formula is CnH2n+2.
Pentane to pentadecane are liquids and the chief constituents of uncracked gasoline.
Its higher members are waxy solids. In a given bore hole the wax may clog the pore
space next to the hole as gas expands and cools.
The paraffins are the largest constituent of crude oil and are characterised by their
chemical inertness. Clearly they would not have remained as they are if this were not so.

2.3 Isomerism
From methane to propane there is only one way to arrange the branched chains
however above propane there are alternative arrangements and these are called
isomers.
Structural formulae do not represent the actual structure of the molecules. Isomers are
substances of the same composition that have different molecular structure and
4

Figure 1
Classification of
Hydrocarbon.

Reservoir Fluids Composition

therefore different properties, for example, normal butane and isobutane.

normal butane CH3CH2CH2CH3

B.Pt. 31.1F

isobutane

B.Pt. 10.9F

CH3CH CH3
CH3

Pentane has three structures (isomers). Clearly the number of isomers increase as the
number of carbon atoms increases. Hexane has 5 isomers and heptane 9.
Table 1 below gives some of the basic physical properties of the more common
hydrocarbons of the paraffin series and Table 2 lists the state of the various pure
components demonstrating that components which might be solid on their own
contribute to liquid states when part of a mixture. Figure 2 gives some structural
formula for three paraffin componds.

Name

Table 1
Physical properties of
common hydrocarbons.

Chemical
Formula

Molecular
Weight

Boiling Point
(C) at normal

Critical
Temp C

Density
Gas
Liquid
(air = 1)
(water = 1)
conditions
sp.gr.

Methane

CH4

16.04

-161.4

-82.4

0.554

0.415 (-614)

Ethane

C2H6

30.07

-89.0

32.3

1.038

0.54 (-88)

Propane

C3H8

44.09

-42.1

n-butane

C4H10

58.12

0.55

Isobutane

C4H10

58.12

-11.72

134.0

2.006

0.557

n-pentane

C5H12

72.15

36.0

197.2

2.491

0.626

Isopentane

C5H12

72.15

27.89

187.8

2.491

0.6197

n-hexane

C6H14

86.17

60.30

228.0

2.975

0.6536

96.8

1.522

0.585 (-44.5)

153.1

2.006

0.601 (0)

ALKANES or PARAFFIN HYDROCARBONS

Cn H 2n+2

Table 2
Alkanes or Paraffin
Hydrocarbons Cn H 2n + 2

No of carbon
atoms
1
2
3
4
5
6
7
8
9
10
C5-C17
C18+

Name

State (ntp)

Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
Decane

Gas
Gas
Gas
Gas
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Solid

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PARAFFINS

H
H
H

H
H

C H

C H
H

H C

C H

H
Methane

H
H C

H H H

H H H H

C C

H H H

C C

H H H H

Figure 2
Gives some standard
formula for saturated
hydrocarbons

n-octane

Iso-butane

2.4 Unsaturated Hydrocarbons

These are hydrocarbons which have double or triple bonds between carbon atoms.
They have the potential to add more hydrogen or other elements and are therefore
termed unsaturated. There are termed the olefins, and there are two types, alkenes, for
example ethylene, CH2=CH2, which have a carbon-carbon double bond and alkynes,
for example acetylene,CH=CH which have a carbon carbon triple bond. Both
compound types being unsaturated are generally very reactive and hence are not
found in reservoir fluids.

2.5 Napthene Series

The napthene series (CnH2n) sometimes called cycloparaffins or alicyclic hydrocarbons
are identified by having single covalent bonds but the carbon chain is closed and is
saturated. They are very stable and are important constituents of crude oil. Their
chemical properties are similar to those of the paraffins. A crude oil with a high
napthene content is referred to as an napthenic based crude oil. An example is
cyclohexane C6H12. Figure 3 gives the structural formula for two napthenic compounds.
NAPHTHENES
H
H

H
H

H
H

H
H

H
H

H
H

H
H

H
Methyl
Cyclopentane

Figure 3
Structural formula for two
naphenic compounds.

Cyclohexane

2.6 Aromatics
The aromatic series (CnH2n-6) is an unsaturated closed-ring series, based on the benzene
compound and the componuds are characterisied by a strong aromatic odour. Various
aromatic compounds are found in crude oils. The closed ring structure gives them
a greater stability than open compounds where double or triple bonds occur. Figure
4 gives the structural formula for two aromtic compounds.

AROMATICS
H

C
H C
H C

C H

H C

C H

H C

C
C

C H

Benzene

Naphthalene

Figure 4
Structural formula for two
aromtic compounds.

Reservoir Fluids Composition

The aromatic-napthene based crudes are usually associated with limestone and
dolomite reservoirs such as those found in Iran, the Arabian Gulf and Borneo.
Some crude oils used to be described, more from a refining perspective, according to
the relative amount of these non paraffin compounds. Crude oils would be called
paraffinic, napthenic or aromatic. It is not a classification of value in reservoir
engineering.

Physical Properties of some Common Petroleum

Reservoir Fluid Constituents
Component

Table 3
Physical properties of some
common petroleum
reservoir fluid constituents

Paraffins
Methane
Ethane
Propane
n-Butane
Iso-Butane
n-Pentane
n-Hexane
Iso-octane
n-Decane
Naphthenes
Cyclopentane
Methyl cyclo-pentane
Cyclohexane
Aromatics
Benzene
Toluene
Xylene
Naphthalene

Formula

Melting Point
(C)

Normal Boiling Point

(C)

Density (g/cm3)
at 1 atm and 15C

CH4
C2H6
C3H8
C4H10
C4H10
C5H12
C6H14
C8H18
C10H22

-184
-172
-189.9
-135
-145
-131.5
-94.3
-107.4
030

-161.5
-88.3
-42.2
-0.6
-10.2
36.2
69.0
99.3
174.0

0.626
0.659
0.692
0.730

C5H10
C6H12
C6H12

-93.3
-142.4
6.5

49.5
71.8
81.4

0.745
0.754
0.779

C6H6
C7H8
C8H10
C10H8

5.51
-95
-29
80.2

80.1
110.6
144.4
217.9

0.885
0.867
0.880
0.971

2.7 Asphalts
Asphalt is not a series by itself. Asphalts are highly viscous to semi-solid, brownblack hydrocarbons of high molecular weight usually containing a lot of sulphur and
nitrogen, which are undesirable components, and oxygen. Asphalts are closely
related to the napthene series and because of their high nitrogen and oxygen content
they may be considered juvenile oil, not fully developed.

3 NON-HYDROCARBON COMPOUNDS
Although small in volume, generally less than 1%, non-hydrocarbon compounds
have a significant influence on the nature of the produced fluids with respect to
processing and the quality of the products.
The more common non-hydrocarbon consituents which may occur are:
sulphur, oxygen, nitrogen compounds, carbon dioxide and water.
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Sulphur and its associated compounds represent 0.04% - 5% by weight. These
corrosive compounds include sulphur, hydrogen sulphide (H2S ),which is very toxic,
and mercaptans of low molecular weight ( these are produced during distllation and
require special metals to avoid corrosion). Non-corrosive sulpher materials include
sulphides. Sulphur compounds have a bad smell and both the corrosive and noncorrosive forms are undesirable. On combustion these products produce S02 and S03
which are undesirable from an environmental perspective.
Oxygen compounds, up to 0.5% wt., are present in some crudes and decompose to
form napthenic acids on distillation, which may be very corrosive.
Nitrogen content is generally less than 0.1% wt., but can be as much as 2%. Nitrogen
compounds are complex . Gaseous nitrogen reduces the thermal quality of natural gas
and needs to be blended with high quality natural gas if present at the higher levels.
Carbon Dioxide is a very common consituent of reservoir fluids, especially in gases
and gas condensates. Like oxygen it is a source of corrosion. It reacts with water to
form carbonic acid and iron to form iron carbonate. Carbon dioxide like methane has
a significant impact on the physical properties of the reservoir fluids.
Other compounds. Metals may be found in crude oils at low concentration and are of
little significance. Metals such as copper, iron, nickel, vanadium and zinc may be
present. Produced natural gas may contain helium, hydrogen and mercury.
Inorganic compounds The non-oil produced fluids like water will clearly contain
componds arising from the minerals present in the rock, their concentration will
therefore vary according to the reservoir. Their composition however can have a very
significant effect on the reservoir behaviour with respect to their compatibility with
injected fluids. The precipitation of salts, scale, is a serious issue in reservoir
management.
Many of these salts need to be removed on refining as some generate HC1 when
heated with water.

4. COMPOSITIONAL DESCRIPTION FOR RESERVOIR ENGINEERING

4.1 Definitions of Composition in Reservoir Engineering
In petroleum engineering, and specifically in reservoir engineering, the main issue is
one of the physical behaviour and characteristics of the petroleum fluids. The
composition of the fluid clearly has a significant impact on the behaviour and
properties. In petroleum engineering therefore the description of the composition is
a key to determine the physical properties and behaviour.
For the oil refiner or chemical manufacturer the composition of the fluid is the key to
determine what chemical products can be extracted or processed from the material.
The petroleum engineer is not concerned with the fact that the oil might contain, albeit
in small concentrations, hundreds of different components. The petroleum engineer
wants as simple a description as possible which still enables the determination of the
physical properties and behaviour under different temperature and pressure conditions.
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Reservoir Fluids Composition

Two models are used in this industry to describe the composition for physical property
prediction purposes, the black-oil model and the compositional model.
The black-oil model is a 2 component desription of the fluid where the two
components are, the fluids produced at surface, stock tank oil and solution gas.
Associated with this model are black-oil parameters like solution gas-oil ratio and the
oil formation volume factor. These parameters are discussed in the chapter on liquid
properties.
The compositional model is a compositional description based on the parafin series
CnH2n+2. The fluid is described with individual compositions of norman paraffins up
to a limiting C number. Historically C6, more common now to go up to C9, or even
higher. Components greater than the limiting C number are lumped together and
defined as a C+ component.
Isomers, normal and iso are usually identified up to pentane. Non paraffinic
compounds are assigned to the next higher paraffin according to its volatility. The
material representing all compounds above the limiting carbon number are called the
C+ fraction , so C7+ for a limiting value of C6 and C10+ for a limiting value of C9.
The physical properties of paraffins up to the limiting C number are well known and
documented. The C+ component is however unique to the fluid and therefore two
properties are used to characterise it, apparent molecular weight and specific gravity.
The behaviour of some fluids are complex and the paraffin based description may
have difficulty in predicting properties under certian conditions. Consideration may
be required to also identify napthenic and aromatic compounds, (PNA analysis),which
could be contributing to complex behaviour. This is particularly the case for gas
condensates existing at high pressures and high temperaures.
Figure 4 illustrates the compositional model and its application as reservoir fluids are
produced to surface. Although the individual components contribute to a single liquid
reservoir phase for an oil, when the fluids are produced to surface they produce a gas
phase, solution gas, and a liquid phase, stock tank oil. The distribution characteristics
of the individual components is complex and not just a function of temperature and
pressure. For reservoir fluids the compostion is also an influence on the distribution.
This makes it a difficult task to predict this distribution perspective since reservoir
fluid compositions are unique. This topic is further dealt with in the chapter on vapour
liquid equilibrium. Improved methods of chemical analysis make it possible to
describe the oil up to a C value of C29. Although such definitions provide a very
accurate description, the associated computer effort in using such a comprehensive
description does lead to the use of pseudo components. Pseudo components are
obtained by grouping the various C number compositions, thereby reducing the
description to 4 or 5 "pseudo components". A number of methods exist to group the
various C values and other components.

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Reservoir Fluid

Gas at Surface Conditions

Oil at Surface Conditions

C1

C2

C3

C4

C5

C6

C7+

The relative amounts of C1 - C7+ are a

function of :

Figure 4
Compositional Model

Temperature, Pressure, Composition (particularly at high temperature)

5. GENERAL ANALYSIS
5.1 Surface condition characterisation
Reservoirs as well as having unique compositions also exist at specific pressures and
temperatures. It is important therefore to provide a common basis for describing the
quantities of fluids in the reservoir and throughout the production process.
The basis chosen is the fluids at surface conditions, the surface conditions being 14.7
psia or 101.3 kPa and 60oF or 298K. These conditions are called standard conditions.
For gas therefore this yields standard cubic feet SCF or standard cubic meters SCM.
It is useful to consider these expression not as volumes but as mass, the volume of
which will vary according to density. For liquids we express surface conditions as
stock tank volumes either stock tank barrels STB or stock tank cubic meters STM3.
The relative amount of gas to oil is expressed by the gas-oil ratio GOR SCF/STB.
Since there are so many types of oil, each with a wide range of specific gravity, an
arbitrary non-linear relationship was developed by the American Petroleum Institute
(API) to classify crude oils by weight on a linear-scaled hydrometer. The observed
readings are always corrected for temperature to 60oF, by using a prepared table of
standard values.

Degrees API =

141.5
-131.5
Sp.Gr.at 60F

Sp.Gr = specific gravity relative to water ar 60oF.

10

(1)

Reservoir Fluids Composition

The API gravity of water is 10. A light crude oil would have an API gravity of 40,
while a heavy crude would have an API gravity of less than 20. In the field, the API
gravity is readily measured using a calibrated hydrometer.
There are no definitions for categorising reservoir fluids, but the following table 5
indicates typical GOR, API and gas and oil gravities for the five main types. The
compositions show that the dry gases contain mostly paraffins, with the fraction of
longer chain components increasing as the GOR and API gravity of the fluids
decrease.
In chapter 4 we give a classification for the various reservoir fluid types in the context
of phase behaviour.

Type

Dry Gas

Appearance Colourless
at surface
Gas

Initial GOR
(scf/stb)
API
Gas S.G.
(air=1)

WetGas

Gas Condensate

Volatile Oil

Black Oil

Colourless
Gas +
clear liquid

Colourless
+ significant
clear/straw
Colour

Brown liquid
Some
Red/Green
Liquid

Black
Viscous
Liquid

No Liquids

>15000

3000-15000

2500-3000

100-2500

60-70

50-70

40-50

<40

0.60-0.65

0.65-0.85

0.65-0.85

0.65-0.85

0.65-0.85

Composition (mol %)

Table 5
Typical values for different
reservoir fluids

C1

96.3

88.7

72.7

66.7

52.6

C2

3.0

6.0

10.0

9.0

5.0

C3

0.4

3.0

6.0

6.0

3.5

C4

0.17

1.3

2.5

3.3

1.8

C5

0.04

0.6

1.8

2.0

0.8

C6

0.02

0.2

2.0

2.0

0.9

C7+

0.0

0.2

5.0

11.0

27.9

5.2 Refractive index

The refractive index provides another indicator of the density of produced oils. The
general refractive index range for oil is 1.39 to 1.49. The heavier the crude, the higher
the refractive index and the lower the API gravity. This can be measured with a
refractometer or by the same methods used in optical mineralogy with reference
gravity oils.

5.3 Fluorescence of oil

The fluorescence of oil which is measured by its colour under ultraviolet light
provides another indicator, and is often used by those analysing the cuttings as the well
is drilled. The rock sample should be placed as quickly as possible under ultraviolet
light since fluorescence of oil subsides with evaporation and the activity of live oil
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decreases. If whole core is being examined then the whole core should be passed under
UV light to determine the fluorescent colour and the pattern of oil-in-place in the cored
interval.
When possible, pictures should be taken of the core showing the fluorescence. These
are very useful when accompanying reports to the head office which may be hundreds
if not a few thousand miles away.
The degree of flourescence is indicated below for different compositions as reflected
in the API gravity.
2
10
18
45

- 10
- 18
- 45
- above

API
API
API
API

non-fluorescent to dull brown

yellow brown to gold
gold to pale yellow
blue-white to white

It should be pointed out that most oils increase in API gravity with depth in a given
lithologic column with the reason being that younger juvenile oils, heavier with a
lower API gravity, have not yet been transformed from the initial formation conditions
to higher petroleum members. Two well-known exceptions to this pattern are found
in the Burgan sands of Kuwait and the shallow sands of the Bibi Eibat field in the
USSR where the high-gravity members are found higher up in the stratified column
than the low-gravity members.

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Reservoir Fluids Composition

EXERCISE 1
Calculate the Specific Gravity (SG) of a 38o API oil. What is its density in lbs/cu.ft?
(62.32 lbs/cu.ft equals an SG of 1.0 and 43.28 API)
Now convert an oil with an SG of 0.744 to Degrees API.

EXERCISE 2
A reservoir oil is quoted as having a Gas Oil Ratio (GOR) of 604 scf/bbl. Convert
this to Standard Cubic Meters (SCM)gas per Stock Tank Cubic Meters (SM3)
1 Foot = 0.3048m
1 barrel = 5.615 cu ft.
1 barrel = 0.159 M3

EXERCISE 3
A reservoir is said to contain an initial GOR of 11,000scf/bbl. What type of reservoir is described, and what API oil could be typically expected from such a field?

EXERCISE 4
Define the Black Oil Model and the Compositional Model

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Solutions to Exercises
EXERCISE 1
Calculate the Specific Gravity (SG) of a 38o API oil. What is its density in lbs/cu.ft?
(62.32 lbs/cu.ft equals an SG of 1.0 and 43.28 API)
Now convert an oil with an SG of 0.744 to Degrees API.
SOLUTION
Convert using the equation 1:
API = (141.5 / SG) -131.5
38= (141.5 / SG) -131.5
Sg= 141.5 / (131.5 + 38)
SG = 0.835
Similarly, to convert SG into API:
API = (141.5 / 0.744) -131.5
API = 58.7o

EXERCISE 2
A reservoir oil is quoted as having a Gas Oil Ratio (GOR) of 604 scf/bbl. Convert this
to Standard Cubic Meters (SCM)gas per Stock Tank Cubic Meters (SM3)
1 Foot = 0.3048m
1 barrel = 5.615 cu ft.
1 barrel = 0.159 M3
SOLUTION
604 scf/bbl = 604 * 0.30483 STM/bbl = 17.09 SCM/bbl= 107.48 SCM/STM3

EXERCISE 3
A reservoir is said to contain an initial GOR of 11,000scf/bbl. What type of reservoir
is described, and what API oil could be typically expected from such a field?
SOLUTION
A reservoir with a GOR of 11,000 scf/bbl would be typically termed a Gas
Condensate Reservoir. The API gravity would probabally be in the low 50s.
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Reservoir Fluids Composition

EXERCISE 4
Define the Black Oil Model and the Compositional Model
SOLUTION
Black Oil Model.
Two component description of the reservoir fluid consisting of stock tank oil and
solution gas. Compositional changes with varying pressure and temperature are
ignored. Terms such as Gas Oil Ratio and Formation Volume Factor are black
oil model terms.
Compositional Model.
The compositional model is based on the parafin series CnH2n+2. To keep the number
of components in the model manageable, long chain members are grouped together
and given an average property. These compounds are termed collectively as the C+
fraction. Typically this covers the hydrocarbons above Heptane and therefore is
called the C7+ fraction, which is characterised using the terms Apparent Molecular
Weight and Specific Gravity.

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REFERENCES.
1.

16

Amyx,J.W.,Bass,D.M., and Whiting,R.L."Petroleum Reservoir Engineering",

McGraw-Hill Book Company, New York 1960