Petroleum University of Technology

Ahwaz Faculty of Petroleum Engineering,

The Properties of Petroleum Fluids

Instructor:
Mehdi Bahari Moghaddam

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 Course Outline

 Fundamental of the Behavior of Hydrocarbon Fluids

 Pure Component- Physical Properties
 Properties of Natural Gases
 Phase Behavior of Crude Oils
 Vapor- Liquid Phase Equilibrium
 An Introduction to Equation of States
 Sampling from Oil and Gas Reservoir
 References

• Properties of petroleum fluids- McCain

• Equations of State And PVT Analysis Tarek Ahmed
• Hydrocarbon phase behavior- Tarek Ahmad
• PVT and phase behavior of petroleum Reservoir fluids- Ali Danesh
 Course Grading:

- 30% Midterm examination

- 55% Final examination
- 15 % Home assignments
 Why Do We Study Phase Behavior?
 Natural gas and crude oil are naturally occurring hydrocarbon mixtures that are
found underground and at elevated conditions of pressure and temperature. They
are generally referred to as petroleum fluids.

 Petroleum fluids are principally made up of hydrocarbons; but few non-

hydrocarbon components may be present such as nitrogen, carbon dioxide and
hydrogen sulfide.
 Why Do We Study Phase Behavior?
 Phase Behavior has many implications in natural gas and petroleum engineering.
Pressure, volume, temperature (PVT) relations are required in:
 simulating reservoirs,
 evaluating reserves,
 forecasting production,
 designing production facilities and
 designing gathering and transportation systems.
 Why Do We Need PVT Data?
All Reservoir Engineering Calculations Require PVT Data. Amount of the Data
Required Depends on the Process
Reserves
Reservoir Simulation
Material Balance Calculations
Pressure Transient Testing
Enhanced Oil Recovery
Flow-line, Wellbore Hydraulics Calculations Well Completion
To Size and Design Facilities and Equipment
Production Test
To Anticipate Potential Operating or Environment Problems
Well Completion
 Field Development

Reservoir
Information Reservoir Simulator

PVT DATA
ROCK DATA
FLUID-ROCK DATA
RESERVOIR GEOMETRY DATA
WELL DATA
GEOLOGY DATA
SIESMIC DATA Production Forecast
.
.
. Economic Study and Decision
. Making for the Field
. Development
8 8 8
 PVT Models

Production of Oil and Gas from the Reservoir

A Series of Pressure and Temperature Changes

Change in the Volumetric and Transport Behavior of Reservoir Fluids

Q: How do we quantify the real oil and gas volumes under various pressures and
temperatures?
Typical Oil and Gas Separation System
 PVT Models
There are basically two models to predict phase behavior
of reservoir fluids:
1. Black Oil Models ( G+O)
2. Compositional Models (G, yi, O, xi)
 PVT Models- Black Oil Model

Black Oil models describe volumetric properties using

correlations in terms of measured macroscopic properties such
as API gravity, bubble point pressures, and gas gravities, pressure
and temperature.

1. Has only two components named as the phases: Gas (G) and
Oil (O).

2. The G component may be dissolved in the oil phase and this is

taken into account through the solution gas oil ratio (Rs).
However, the oil component (O), cannot dissolve in the gas
phase.

3. Volumetric properties are determined from separate

correlations for gas and oil phases.
 PVT Models- Compositional

Compositional models require compositional information in

addition to the primary variables: pressure and temperature.

1. Oil and gas are mixtures of several components

2. All components may be present in both phases (liquid and gas)

3. Volumetric properties of the phases are determined as a

function of pressure, temperature, and the phase compositions
using the same model – an Equation of State (EOS)- for all phases.
Hydrocarbon Chemistry

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 Elemental Composition of Crude Oils
 Fluids from many different reservoirs or wells are quite different from each other
but the relative amounts of carbon and hydrogen present in the crude vary only
within a limited range:

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 Hydrocarbon Families

Basis for Hydrocarbon Categorization:

1. molecular configuration and the pattern in which they are linked to each other
straight chains,
 branched
 cyclic or aromatic chains

2. the number of bonds between the carbon atoms

 single
 double
 triple bond

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 Hydrocarbons

Aliphatic Aromatic
 Hydrocarbons

Aliphatic Aromatic

Alkanes Alkenes Alkynes

 Hydrocarbons

Alkanes are
hydrocarbons in which
all of the bonds are
Aliphatic
single bonds.

H H
Alkanes H C C H

H H
 Hydrocarbons

Alkenes are
hydrocarbons that
contain a carbon-carbon
Aliphatic
double bond.

H H
Alkenes C C
H H
 Hydrocarbons

Alkynes are
hydrocarbons that
contain a carbon-carbon
Aliphatic
triple bond.

Alkynes

HC CH
 Hydrocarbons

The most common

aromatic hydrocarbons
are those that contain a
benzene ring.
Aromatic
H
H H

H H

H
 Hydrocarbon Categorization

Hydrocarbon compounds can be grouped into a number of series. These

series are namely:
 Alkane,
 Iso-alkanes,
Cyclo-alkane
Aromatics

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 Alkanes; Cn H2n+2
The most common hydrocarbon compounds found in petroleum fluids are the
alkanes, which include methane, ethane, propane, n-butane, etc. They have
straight chain configurations of carbon and hydrogen atoms.

Crude oil consists of straight chain alkanes from one carbon atom (methane) to
molecules having hundreds of carbon atoms.

The alkanes are saturated – i.e. all the carbon atoms are connected with four
“single” bonds.

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 Alkanes Family
Physical Properties

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 Iso-Alkanes
If carbon atoms are arranged in a branched arrangements, the molecules are
called isomers. The possible number for these isomers ranges increase as the
number of carbon atoms increase. Typically isomers amount to about 15% to
20% of the crude oil.

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31
 Cyclo-alkanes; Cn H2n
Cyclo-alkanes(also called cyclo-paraffins or naphtenes)

Saturated hydrocarbons that form closed rings are known as cyclo-alkanes.

Cyclo-paraffins are relatively stable and exhibit chemical properties similar to

those of the alkanes.

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 Aromatics
C6H6 n(CH2)
Hydrocarbons that contain a special ring called benzene ring called aromatics
because many of them have fragrant odorous and are also known as arenas. This
group is made up of derivatives of benzene, whose formula is C6H6.

Benzene is relatively stable at the

conditions of pressure and
temperature under which the
hydrocarbon reservoirs are
produced. Arene hydrocarbons are
either liquids (toluene and xylene)
or solids under standard conditions
and are commonly found in crude
oil.

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No crude oil has ever been completely separated into its
individual components, although many components can be
identified.

Table 6.2 lists the more important compounds in a sample of

Oklahoma crude. A total of 141 compounds were identified in
this oil sample that account for 44% of the total crude volume.

Despite this complexity, several properties relevant to petroleum

engineers can be determined from black oil PVT correlations.
 API gravity

The petroleum industry uses API gravity as the preferred gravity scale, which is
related to specific gravity as
 Characterization factor

In 1933, Watson and Nelson introduced a ratio between the mean average boiling
point and specific gravity that could be used to indicate the chemical nature of
hydrocarbon fractions and, therefore, could be used as a correlative factor.
Characterization factors are calculated with
 Use of characterization factor

Characterization factors are useful because they remain reasonably constant for
chemically similar hydrocarbons.

A characterization factor of 12.5 or greater indicates a hydrocarbon compound

predominantly paraffinic in nature.

Lower values of this factor indicate hydrocarbons with more naphthenic or aromatic
components.

Highly aromatic hydrocarbons exhibit values of 10.0 or less;

Using work from Riazi and Daubert, [8] Whitson[5] developed the following
relationship in terms of molecular weight and specific gravity.

Crude oils typically have characterization factors ranging from 11 to 12.5

Relationship between crude oil gravity and characterization parameter

While not definitive, it can be observed that lower gravity crudes tend to be more
naphthenic, while higher-gravity crudes tend to be more paraffinic.
 Non hydrocarbon elements

Most common: CO2,N2,H2S

They lower the heating value of oil (Btu/lbm)

Nitrogen, Oxygen and Sulfur form part of heavy molecules present in the oil
(asphaltenes & resins)

Sulfur compounds poison catalysts used in refinery operations

Oils may have up to 10% of S on a weight basis
Very sour oils may be denser than water
H2S removal done with ethanolamines (sweetening process)

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 Non hydrocarbon elements
Trace elements
The trace elements most commonly encountered in hydrocarbon reservoirs are:
He Helium (in gas reservoirs)
V, Ni, Hg Metallic elements concentrated in the heavy end
 -C-metal Oregano-metallic compounds

Hg (Mercury)
The presence of mercury in the petroleum fluids contributes to corrosion, engine
wears and pollution. Safety is also an important aspect when dealing with
mercury. Gas streams may contain traces of mercury, which can be very
hazardous to the surface installations in terms of corrosion and dangerous when
supplied for domestic use.

In order to monitor any presence of mercury the gas stream, it is passed though a
quartz adsorption tube filled with gold wool or powder and Hg is allowed to
amalgam. These tubes are heated later for the recover the retained mercury and
subsequently analyzed in the laboratory using atomic absorption technique.

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 Non hydrocarbon elements
Ni (Nickel) and V (Vanadium)
Nickel and Vanadium are poisons for catalysts used in the refining processes.
Their presence in the crude can lower the commercial value of the crude oil.

Radio-active elements (Radon-222, Polonium-210)

Due to it high activity, rapid well site analysis is recommended for the
measurement of 222Ra although it can also be analyzed in the laboratory if the
test is performed within 48 hours. Any 210Po present in gas condensate samples
is deposited onto a silver disk by digestion with a strong acid and the activity is
measured using a photoactive plate.

Sulfur (Sour) compounds

Sulfur compounds commonly present in hydrocarbon reservoirs are:
 H2S Hydrogen Sulfide
 RSH Mercaptans
 RSR Alkyl Sulfides
 RSSR Alkyl Disulfides

The terms “sour” refer to fluids containing sulfuric compounds and “sweet” to
those not containing any.
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 Non Hydrocarbon Elements
H2S
H2S is a gas having a very unpleasant odor somewhat closer to that of a
rotten egg and is extremely dangerous to health. Therefore every safety
measures have to be taken while working with petroleum fluids, which contain
H2S. H2S also acts as a poison to catalysts during the refining.

Ethanol amines are utilized to absorb H2S from the gas before liquefaction.

On the other hand, sulfur as by-product can be extracted if the concentration
of H2S in the production gas is high enough.

Thiols (mercaptans)
These compounds are represented by the general formula RSH, where R is an
alkyl radical.

Alkyl Sulfides (R-S-R) and Alkyl Disulfides (RSSR)

Alkyl sulfides have less unpleasant odors than H2S or thiols, but do cause
respiratory and other health hazards.

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 Solids

Solid phases can be encountered in petroleum reservoirs or in the surface

separation units in the form of:

Wax,
Asphaltenes
Hydrates

The knowledge of conditions at which these solids particles precipitate in the

reservoir or at surface is of critical importance for efficient reservoir and
production management and the development of the processing and
transportation systems.
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 Wax
The wax present in petroleum oils primarily consists of paraffin hydrocarbons
(C18 - C36) known as paraffin wax and naphthenic hydrocarbons (C30 - C60).

Normal paraffin

Cyclo-paraffin (Naphtenes) Branched paraffin

 Molar Distribution of the Wax Fraction
The wax molecules range from C20- C50.

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 Resins & Asphaltenes
Resins are heavy sticky solids, which are soluble in other hydrocarbons,
whereas asphaltenes are assumed to be in a dispersed or suspended form.

Resins are known to solubilize the asphaltenes clusters and keep them in
solution.

Asphaltenes: They are complex compounds

composed mainly of polar cyclic and aromatic
molecules and exhibiting high molecular
masses. They are impure hydrocarbons often
referred to as NSO compounds because they
contain nitrogen, sulfur and oxygen heteroatoms
as well as metal atoms such as Ni, V. Their
molar masses may vary from x*100 to x*1000
g/g-mole. They can aggregate with molecular
mass distributions of 103 to 105.

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Asphaltene-resin micelles
 Asphaltenes

Asphaltenes stay in colloidal suspension and are defined as the fraction that
does not dissolve in n-heptane or npentane.

Asphaltenes when isolated are black dry powders and their deposition in the
wellbore or in the pores of the reservoir rock has to be closely monitored, since
they can significantly decrease the productivity index, causing damage to
downhole and surface equipment.

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 Hydrates
Gas hydrates are solid crystalline compounds stabilized by inclusion of small gas
molecules inside cavities formed by water molecules and form ice-like solid
matter. When free water is in contact with hydrocarbons, hydrates can be formed
under certain conditions of pressure and temperature. Hydrates are usually seen
in production stations, transport lines etc.

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