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"OIL AND GAS PROCESSING PLANT DESIGN 2004

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"APPLIED THERMODYNAMIC
DGEP/SCR/ED/ECP TO OIL AND GAS PROCESSING"

"APPLIED THERMODYNAMIC

TO OIL AND GAS PROCESSING"

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"OIL AND GAS PROCESSING PLANT DESIGN 2004
AND OPERATION TRAINING COURSE"
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"APPLIED THERMODYNAMIC
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SCOPE 4

REFERENCES 4

GENERAL 5

WELLHEAD FLUID CHARACTERISTICS 6


1. CONSTITUENTS OF WELLHEAD STREAM 6
2. WELLHEAD STREAM COMPOSITION 8
3. RESERVOIR FLUID CHARACTERISATION 11
3.1. Types of reservoir fluid 11
3.2. Identification of reservoir fluid type 12
4. PRODUCED WATER AT TEST SEPARATOR 15
5. FLUID TERMINOLOGY 16

DETERMINATION OF THE RESERVOIR FLUID CHARACTERISTICS 16


1. EVALUATION OF RESERVOIR FLUID BEHAVIOUR 16
2. SAMPLING MEASURE ON FIELD 17
2.1. General 17
2.2. Sampling requirements 17
2.3. Sampling carrying out 18
3. LABORATORY ANALYSIS OF RESERVOIR-FLUID SAMPLES 19
3.1. PVT studies objectives 19
3.2. Physical properties definitions of "black oils" 20
3.3. Laboratory analysis of reservoir fluid samples 23
3.4. Remark about differential liberation of gas and flash liberation of gas 26

USE OF EQUATIONS OF STATE TO DETERMINE THE BEHAVIOUR AND


THE CHARACTERISTICS OF PETROLEUM FLUIDS 27
1. INTEREST OF EQUATION OF STATE (EOS) 27
2. EQUATIONS OF STATE (EOS) FOR PETROLEUM MIXTURES 27
2.1. Equation of state for pure components 27
2.2. Equation of state for mixtures 29

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2.3. Input data required for cubic EOS use 30


2.4. Thermodynamic model tuning 32

APPENDIX 33
1. EXPRESSION OF SPECIFIC CONSTANTS IN VAN DER WAALS, SRK AND PR EQUATIONS
OF STATE 33
2. EXAMPLE OF CORRELATIONS USED TO DETERMINE PHYSICAL AND CRITICAL
PROPERTIES 35
2.1. Relation between molecular weight, specific gravity, normal boiling
temperature 35
2.2. Critical properties correlations 35
2.3. Acentric factor correlation of Lee-Kesler (for fluids having Tbr > 0.8) 36
2.4. Binary interaction coefficient ( d ij ) 36

Figure III-A.1 - Typical process flow diagram of a test separator

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AND OPERATION TRAINING COURSE"
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"APPLIED THERMODYNAMIC
DGEP/SCR/ED/ECP TO OIL AND GAS PROCESSING"

SCOPE

This section gives indications on :

wellhead fluid characteristics : constituents, analysis composition, types of fluid reservoir,


methods used to determine the reservoir fluid characteristics : sampling, PVT studies,
equations of state used to determine the behaviour and the characteristics of petroleum
fluids.

REFERENCES

D.L. KATZ R.L. LEE Natural gas engineering


Mc Graw Hill Publishing Company

W. D. Mc CAIN The properties of petroleum fluids


Penn Well Books, Penn Well Publishing Company, Tulsa, Oklahoma

W.C. EDMISTER
Applied Hydrocarbon Thermodynamics
Gulf Publishing Company Book Division. Houston, London, Paris, Tokyo

F. MONTEL Equilibria Needs for Petroleum Exploration and Petroleum Industry Fluid
Phase Equilibria, 84 (1993) 343-367
Elsevier Science Publishers B.V. Amsterdam

D.L. KATZ, A. FIROOZABADI Predicting Phase Behavior of Condensate/Crude-Oil


Systems using methane interaction coefficients
Journal of Petroleum Technology November 1978 p. 1649-1655

G. DE GHETTO, F. PAONE, M. VILLA


Reliability analysis on PVT correlations
SPE 28904 - European Petroleum Conference London 25-27 October 1994 p. 375-
393

M. ANDERSON, R.C. DIMMER Analyse trace sulfur compounds in hydrocarbon gas


streams Hydrocarbon Processing April 1997 p. 73-80

J.W. AMYX, D.M. BASS, R.L. WHITING Petroleum Reservoir Engineering Physical
Properties Mc GRAW HILL Book Company

W.D. Mc CAIN Reservoir Fluid Property Correlations State of the Art.


SPE Reservoir Engineering, May 1991

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P.L. MOSES Engineering Applications of phase behaviour of Crude Oil and Condensate
Systems Journal of Petroleum Technology July 1986

Technical Data Book Petroleum Refining American Petroleum Institute

P.G. CONRARD, J.F. GRAVIER


Peng-Robinson equation of state checks validity of PVT experiments.
Oil and Gas Journal Apr. 21, 1980, pp. 77 to 86.

GENERAL

Oilfield and gasfield processing are defined as the processing of oil and gas for safe and
economical storage and transport by pipeline, tanker and truck. Oilfield and gasfield processing
includes water treatment, whether produced waters for disposal and/or reinjecting, or additional
injection waters used for formation flooding or reservoir pressure maintenance.

Production facilities with any reservoir fluid, vary widely. Configuration and method of operation of
fluid separation and liquid extraction equipment depend on many factors, including :

reservoir recovery mechanism depletion, gas and water injection,


composition and PVT behaviour of reservoir fluid,
compression staging,
location of production facilities (offshore platform, ),
gas sales contract provisions,
pipeline operating conditions,
crude oil transportation method,
wellhead flowing conditions and ambient temperatures.

Subject to these constraints, the objective in surface handling of reservoir fluid is to maximise liquid
yield from the wellstream mixture of oil and free gas. In many cases this can involve multi-stage
separation of oil and liquid extraction from the gas.

Successful oil or gas field processing and treatment units design requires :

1. a good knowledge of the wellhead fluid characteristics, related to the reservoir's fluid
characteristics,

2. a good calculated determination of liquid-vapor equilibria for natural hydrocarbon mixtures.

Knowledge of the wellhead fluid characteristics is obtained by successfully reservoir fluid sampling
and PVT laboratory measurements.
The use of a numerical model of a thermodynamical simulator allows to check the consistency of
experimental results, as well as to get extra data needed to predict performance of a reservoir or to
define phase separation characteristics in oil or gas field processing and treatment units.

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In this case, if the model is properly fitted with available experimental data, it will give accurate
determination for different operating conditions, thus avoiding expensive laboratory experiments.

On an other hand the pressure and temperature range within which the oil and gas- condensate
properties must be known coupled with the fact that the overall composition of two-phase mixtures
varies constantly during their displacement, either inside reservoirs or inside production
installations, make it obvious that it is important to be able to compute these properties without
having to have recourse to complicated laboratory investigations.

To solve these problems equations of state (EOS) have been developed. In petroleum
engineering, the most commonly used are cubic polynomials in volume such as Peng-Robinson
(P.R.), Soave-Redlich-Kwong (SRK), Whatever the equation of state selected for the
thermodynamic simulation, equation constants are to be determined for a fluid in "n" components
to obtain a fluid behaviour and fluid characteristics consistent with the measurements. The
procedure used to adjust the calculated values with the measurement values is called
"thermodynamic model tuning". The knowledge of reservoir fluids today makes the fitting
procedure almost always necessary and its implementation always difficult.

Now, the oil and gas companies are facing a new challenge with the deep offshore discoveries.
Due to the low temperature of the sea bottom, the reservoir temperature could be very low under
high pressure, in some extreme cases the trap could be sealed by hydrates. For such development
projects the main concern is the risk of solid phase deposition, wax, asphaltene and hydrates
directly from reservoir fluid and not only in the process facilities or in the transportation lines. In
order to be able to deal with such fluid systems, it is an urgent need for data acquisition and
modelling of the solid/liquid/gas equilibria under high pressure.

WELLHEAD FLUID CHARACTERISTICS

1. CONSTITUENTS OF WELLHEAD STREAM

INERT GASES Nitrogen (N2)


Helium (He)
Argon (A)

ACID GASES Hydrogen Sulfide (H2S)


Carbon Dioxyde (CO2)

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Methane (C1 )

Ethane (C 2 )

Propane (C 3 ) LIGHT ENDS
i - Butane (i - C 4 )

PURE HYDROCARBONS n - Butane (n - C 4 )
i - Pentane (i - C 5 )

n - Pentane (n - C 5 )
HEAVY ENDS
Cyclopentane
Hexanes, benzene and heaviers (C 6+ )

ORGANIC COMPOUNDS Hydrocarbons with oxygen, nitrogen, sulphur

SULPHUR COMPOUNDS Mercaptans (R-S-H)


Sulfides (R-S-R')
Disulfides (R-S-S-R')
Thio-compounds

INORGANIC COMPOUNDS Hydrocarbons with metals (Nickel, Vanadium, Potassium,


Copper, Zinc, Iron)
Arsenic Compounds (Arsenes)

MERCURY

NATURALLY OCCURING RADIOACTIVE MATERIAL (NORM)


Radon, Radium

SOLIDS Millscale and rust


Iron Sulfide (Fe S)
Reservoir fines
Solid Sulphur

CORROSION INHIBITORS

HYDRATE INHIBITORS Methanol (MeOH)


Diethyleneglycol (DEG) or Monoethylene glycol (MEG)

WATER AND SALTS

For details about particularities of some constituents listed above see PRODEM Section VI
Chapter : "Undesirable constituents contained in wellhead stream".

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2. WELLHEAD STREAM COMPOSITION

A typical wellhead stream (natural gas with associated condensate, crude oil with associated gas)
contains thousands of different chemical compounds, and trying to separate or identify it into
different chemicals is impractical.

Consequently wellhead stream composition is defined with a finite number of components :


constituents and oil cuts.

Constituents are identified and determined pure components.

They consist of :

non hydrocarbon components of petroleum such as :


nitrogen, helium, carbon dioxide, hydrogen sulfide ;

light ends hydrocarbon components such as :


methane, ethane, propane, isobutane, n-butane, isopentane, n-pentane.

Oil cuts or crude fractions (or pseudo-components or hypotheticals) are a set of compounds
globally determined and of identical behaviour with a respect to a given analysis method.

For instance the C7 cut can represent all hydrocarbons boiling between 1C above the normal
boiling temperature of n-hexane to 1C above the normal boiling temperature of n-heptane. All
components with a normal boiling temperature contained in this range are grouped in a single
pseudo-component named C7 cut.

Taking into account that the number of isomers becomes large for higher molecular weights : 18
isomeric for octanes, 75 isomeric for decanes, 360 000 isomeric for C20, , the advantage is
obvious. This allows to simplify the well effluent compositions and to save analysis and
thermodynamic simulation time.

All analyses have a limited number of components : constituents and oil cuts, usually listed in the
growing order of normal boiling temperature or number of carbons in the molecule. The last oil cut
corresponds to the constituents group of highest normal boiling temperature or highest number of
carbons in the molecule. It is named "heavy end component" or "Cn plus" (Cn+). This means that
this group contains all constituents with "n" atoms of carbons in their molecule and all constituents
with a number of carbons higher.

Be careful : there is no universal definition for an oil cut.


For instance the C6 cut may be defined in two manners :
either by a range of normal boiling temperature or by a number of carbon atoms
in the molecule. The following example illustrate that.

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Normal boiling temperature (Teb)


Number of carbon atoms in the molecule
36.5C < Teb < 69.2C

Constituent mol % Constituent mol %

Cyclopentane 0.089 2.2. dimethyl butane 0.009


2.2. dimethyl butane 0.009 2.3. dimethyl butane 0.030
2.3. dimethyl butane 0.030 2. methyl pentane 0.263
2. methyl pentane 0.263 3. methyl pentane 0.158
3. methyl pentane 0.158 normal hexane 0.519
methylcyclopentane 0.263
normal hexane 0.519
benzene 0.297
cyclohexane 0.455

C6 cut 1.068 C6 cut 1.993

Note molar percent of C6 cut is definition depending

Usually each laboratory uses its analytical process and issues its own description.
Consequently, the oil "cuts" presented in an analysis report may correspond to one
criterion or several criteria.

For example :

CRITERIA ANALYSIS PROCESS

Boiling-point temperature Distillation or gas chromatography


Molecular weight Gel permeation chromatography
Chemical family Liquid chromatography
Functional group Absorption spectrometry

Differences may appear from one analysis to the other for the main constituents (light ends), but
they may be more important for cuts. The linking of the different analytical methods still sets an
overlap problem since they do not include the same criteria.

These problems explain why these analyses are not accompanied with an uncertainty evaluation
method. Moreover, the conversion of mass fractions into molar fractions introduces coupling
effects leading to errors.

The final result of analysis is expressed by the molar fraction values of a set of identified pure
components followed by the molar fraction values of a set of oil cuts.

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AND OPERATION TRAINING COURSE"
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Examples of wellhead stream composition :

Components (mole fraction) CRUDE OIL NATURAL GAS

Nitrogen 0.10 6.03


Carbon dioxide 5.73 0.21
Hydrogen sulfide 2.50 -
Methane 23.32 83.72
Ethane 5.56 6.76
Propane 6.32 2.09
Isobutane 2.85 0.39
N-butane 2.51 0.43
Isopentane 1.12 0.10
N-pentane 1.21 0.12
C6 cut 2.75 0.15 (C6+)
C7 cut 3.17 -
C8 cut 3.81 -
C9 cut 3.32 -
C10 cut 2.57 -
C11+ cut 33.16 -

Remarks :

1. Typical wellhead stream composition does not indicate all constituents that can be
encountered in wellhead streams in particular :

sulphur compounds (Mercaptans, sulfides, disulfides, thio-compounds),


organic compounds (hydrocarbons with oxygen, nitrogen),
inorganic compounds,
(hydrocarbons with metals (Nickel, vanadium, )),
mercury,
NORM,
solids,
water with salts.

They are not usually provided.


To obtain values of some particular components or transport behaviour (viscosity, pour
point temperature, asphalten settling ), specific sampling and analyses techniques are
required. They must be ordered.

BE AWARE ! Some components like H2S, mercury, NORM, present in very small
amounts (traces) in a well effluent cannot be detected in a PVT laboratory, because
some are adsorbed by the sample bottle wall, or appear in the well effluent sometime
after reservoir depletion has begun.

In such case measurements at field with the effluent leaving the wellhead are essential.

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2. Wording "oil cut" or "crude fraction" are used by refiners to define the products extracted
from crude oil. In such case oil cut or crude fraction correspond to the range of boiling
points or the carbon number in the molecules of compounds included in each fraction.
The following table gives a list of typical fractions separated from crude oil.

TYPICAL CRUDE OIL FRACTIONS

NORMAL BOILING CARBON NUMBER IN


CRUDE FRACTION USES
POINT RANGE C THE MOLECULES

GASOLINE 40 175 C5 C10 Motor fuel, Solvent

KEROSENE 175 230 C11 C12 Jet fuel

LIGHT GAS OIL 230 300 C13 C17 Diesel fuel

HEAVY GAS OIL 300 400 C18 C25 Lubricating oil, bunker
fuel

LUBRICANT AND 400 510 C26 C38 Lubricating oil, paraffin


WAXES wax

RESIDUUM 510+ C38+ Tars, paving asphalts

3. RESERVOIR FLUID CHARACTERISATION

3.1. Types of reservoir fluid

There are roughly five type of reservoir fluids. These are usually called black oil, volatile oil,
retrograde gas, wet gas, and dry gas. The five types of reservoir fluids have been defined because
each requires different approaches by reservoir engineers and production engineers.

The petroleum engineer should determine the type of fluid very early in the life of his reservoir.
Fluid type is the deciding factor in many of the decisions which must be made regarding the
reservoir. The method of fluid sampling, the type and sizes of surface equipment, the calculation
procedures for determining oil and gas in place, the techniques of predicting oil and gas reserves,
the plan of depletion, and the selection of enhanced recovery method are all dependant on the
type of reservoir fluid.

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3.2. Identification of reservoir fluid type

3.2.1. General

Reservoir fluid type can be confirmed only by observation in the laboratory. Yet, readily available
production information usually will indicate the type of fluid in the reservoir. Rules of thumb will be
given for identification of each of the reservoir fluid types. Three properties are readily available :
the initial producing gas-oil ratio, the gravity of the stock-tank liquid, and the colour of the stock-
tank liquid. Initial producing gas-oil ratio is by far the most important indicator of fluid type. The
colour of stock-tank liquid alone is not a good indicator of fluid type. However, stock-tank liquid
gravity and colour are useful in confirming the fluid type indicated by the producing gas-oil ratio.

Note The legal or regulatory definitions of oil, crude oil, gas, natural gas, condensate, etc. ,
usually do not bear any relationship to the engineering definitions : they are often contradictory.

3.2.2. Gas-Oil Ratio (G.O.R.) or producing gas-oil ratio or total gas-oil ratio

In a first approach gas-oil ratio may be defined as the total amount of associated gas released by
crude oil during production. It is the sum of the amount in volume expressed at standard conditions
of the gas released by equipment between the wellhead and the storage tank oil divided by the
corresponding amount in volume expressed at standard conditions of the remaining crude oil in the
storage tank oil.

Usual units are :

Standard cubic feet of gas per standard barrel of stock tank oil or atmospheric pressure oil
(scf/bsto) or (Scf/Stbo) in english units.
Standard conditions are : 60F ; 14.696 psia

Standard cubic meters of gas per standard cubic meter of stock tank oil (Sm3/Sm3) in
metric units.
Standard conditions are : 15C ; 101.325 kPa

1 Sm3/Sm3 = 5.62 scf/Stbo

The total G.O.R. depends of the number of gas separation steps used in the separation sequence,
as well as the operating conditions of each separation step (in particular pressure and temperature
values).

A G.O.R. standard determination does not exist. The G.O.R. value corresponds only to an order of
magnitude of the amount of gas which can be released by a crude oil. To appreciate a crude oil
behaviour the best is to associate to the G.O.R. value the process scheme with the operating
conditions used for the G.O.R. determination.

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Usually G.O.R. value is calculated with the measured data from a separator test directly connected
to a wellhead. Operating pressure of the separator test is field depending, operating temperature
correspond to the wellstream temperature without any temperature control. Operating pressure
and temperature values are measured to determine evolved gas flowrate at standard conditions
and remaining crude oil at storage tank oil conditions.

When crude oil leaves the test separator it contains methane and other light hydrocarbon that are
released as gas when the pressure on the oil is reduced to atmospheric value. As the gas evolves,
the remaining crude-oil liquid volume decreases : this phenomenon is known as shrinkage.

Shrinkage is expressed in terms of standard cubic meter of stock tank-oil per cubic meter of oil at
actual separator conditions (shrinkage factor separator SFsep.).

G.O.R. is a parameter solely used by reservoir engineers with two definitions :

1. "Standard G.O.R."

Amount in volume expressed at standard conditions of the gas released leaving the test
separator divided by the corresponding amount in volume expressed at standard
conditions of the oil leaving the test separator after shrinkage.

2. "Total G.O.R."

Amount in volume expressed at standard conditions of the gas released in the test
separator plus the gas evolved during the shrinkage operation, divided by the
corresponding amount in volume expressed at standard conditions of the oil leaving the
test separator after shrinkage.

G.O.R. vary during reservoir depletion. It is one of the main parameters used by reservoir
engineers to manage the reservoir depletion.

Note : Care must be brought to the units used with the G.O.R. value. In some sampling or
laboratory reports G.O.R. may be defined as the amount in volume expressed at standard
conditions of the gas released leaving the test separator divided by the corresponding
amount in volume at actual conditions (pressure and temperature at test separator) of the
oil or condensate leaving the test separator.

Volume of separator gas at standard conditions


G.O.R.sep. =
Volume of separator oil at actual separator conditions

To obtain the G.O.R. standard it is necessary to divide the G.O.R.sep. by the measured
value of the separator shrinkage factor (SFsep.).

Volume of stock tank oil at standard conditions


SFsep. =
Volume of separator oil at actual separator conditions

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3.2.3. Identification of reservoir fluid types versus G.O.R.

G.O.R. may be used with parameters such as density expressed in API, viscosity to characterise
crude oils.

G.O.R. = 0
Crude oil is a "dead oil" (opposite : "live crude").
No gas is evolved when crude oil is reduced to atmospheric pressure.

G.O.R. < 2 000 Scf/Stbo (<350 Sm3/Sm3).


Crude oil is a "black oil".
The quantity of dissolved gas is not large.
Note : Misnomer "black oil" does not reflect the colour of reservoir fluids.

2 000 < G.O.R. < 3 300 Scf/Stbo (350 < G.O.R. < 600 Sm3/Sm3).
Crude oil is a "volatil oil" or "near critical oil".
The quantity of dissolved gas is large.
The oil existing in the reservoir is at a temperature near its critical temperature.

3 300 < G.O.R. < 50 000 Scf/Stbo (600 < G.O.R. < 9 000 Sm3/Sm3).
Well effluent is a "condensate reservoir gas".
Liquid is gas condensate and gas is often retrograde gas.
Retrograde gases contain fewer of the heavy hydrocarbons than do the oils.
Initially, the retrograde gas is totally gas in the reservoir. As reservoir pressure
decreases the retrograde gas exhibits a dew point and liquid condenses from the
gas to form a free liquid in the reservoir. This liquid will normally not flow and
cannot be produced.

G.O.R. > 50 000 Scf/Stbo (G.O.R. > 9 000 Sm3/Sm3).


Well effluent is a wet or a dry gas.
Wet gas and dry gas exist as gas in the reservoir before the depletion. As
reservoir pressure is reduced no liquid is formed in the reservoir.
Wet gases produce stock-tank liquids with the same range of specific gravities
as the liquids from retrograde gases.
However, the specific gravity of the stock-tank liquid does not change during the
life of the reservoir.
The stock-tank liquid is usually water-white and is called gas condensate.
Dry gas is primarily methane with some intermediates, but without enough of the
heavier molecules to form hydrocarbon liquid at stock-tank conditions or in other
surface equipment.

Notes :

1. The word "wet" in "wet gas" does not mean that the gas is wet with water but refers
to the hydrocarbon liquid which condenses at surface conditions.

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2. As reservoir wet and dry gas are normally saturated with water at reservoir
conditions, usually some liquid water is condensed at the surface equipment in wet
and dry gas production. In this context the terms "wet" and "dry" do not refer to
water or water vapour.

3. For gas condensate G.O.R. parameter is not used because values are too large.
Practically condensate gas ratio (C.G.R.) defined by relation as follows is preferred
:

1
C.G.R. =
G.O.R.
Usual units are :

Grams of liquid per standard cubic meter of gas at indicated pressure and
temperature values.

4. PRODUCED WATER AT TEST SEPARATOR

Usually three phases are recognised : gas, hydrocarbon liquid, free water. Gas
and hydrocarbon liquid volume flowrates are used to characterise a natural gas or
crude oil reservoir as describe previously.
Water or brine is present in crude oil as free water or as emulsions or both (some
drops of brine remain dispersed through the continuous crude-oil phase even after
field processing). Interstitial or connate water may contain more or less dissolved
salts. The amount of dissolved salts may vary from zero to saturation at reservoir
conditions. When they are produced these waters contribute to increase pressure
drop in gathering lines and to corrode carbon steel field equipment.

Amount of produced water is characterised by the water cut, the water oil ratio and
the basic and sediment water.

The water cut (W.C.) is the volume percent of water or brine present in the crude
oil-water mixture expressed in the same unit of volume.

volume of water
Water cut (%) = x 100
volume of water plus hydrocarbon liquids

The water-oil ratio (W.O.R.) is the ratio of the volume of the water to the volume
of liquid hydrocarbons expressed in the same unit of volume.

volume of water
W.O.R =
volume of liquid hydrocarbons

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Most crude oil sales contracts specify a maximum value for the amount of free
water with collodal particules, sediment and water (S & W) or, as formerly called,
basic sediment and water (BS & W) acceptable in a liquid volume.

The basic sediment and water (BS & W) is the percentage in volume of water
and sediments (sands, corrosion products, ) in a liquid volume expressed in the
same unit of volume.

volume of water plus sediments


B.S. & W. = x 100
volume of water plus sediments plus liquid hydrocarbons

5. FLUID TERMINOLOGY

Fluids refers to either a liquid or a gas or both.

Petroleum refers to either a liquid or a gas in the sense of naturally occurring and
predominately hydrocarbons.

Liquid means oil, crude oil, condensate, distillate, as the case may be.

Oil is used in phrases such as gas-oil ratio, stock-tank oil, oil formation volume
factor, and oil compressibility because of common use in the petroleum industry. In
this context, oil simply refers to a petroleum liquid which may be the result of the
production of reservoir liquid or condensation from the production of reservoir gas.

Surface liquid or stock-tank liquid are used to mean a petroleum liquid which
ends up in the stock-tank.

Water is used for liquid water. In the oil field, water is often usually highly saline
and can be called brine.

Natural gas means a naturally occurring gas which is predominantly hydrocarbon.

DETERMINATION OF THE RESERVOIR FLUID CHARACTERISTICS

1. EVALUATION OF RESERVOIR FLUID BEHAVIOUR

In order to evaluate the production performance of a reservoir, the volumetric behaviour of


reservoir fluids must be determined as a function of pressure and temperature.

This volumetric behaviour is related to various physical properties of the hydrocarbons composing
the fluids such as specific gravity, molecular weight, compositional analyses and other properties
easily subject to measurement.

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To obtain accurate estimations of the properties of the reservoir fluids, analyses on representative
samples of the reservoir fluids are required. To obtain truly representative samples of the reservoir
fluid, samples must be taken early in the life of the reservoir. They should be taken only after a
carefully planned well conditioning and testing program.

Samples are used in a laboratory to simulate first the reservoir operation and then to establish for
each sample the relation between pressure, volume, and temperature (PVT). This is why the major
tests performed during a reservoir fluid study are called PVT study and the laboratory used for
these tests PVT laboratory.

2. SAMPLING MEASURE ON FIELD

2.1. General

There are several manuals and instruction books available for sampling and analyses, such as
those of the ASTM, the Gas Processing Association and company procedures. Service
laboratories are frequently used for analyses.

Quality of work is essential. Field and reservoir engineers must be familiar with sampling
techniques and the various laboratory analyses available. The engineer involved must decide
when a sample is required, what sampling techniques should be used, and how the well should be
prepared for sampling. Direct supervision of the preparation and sampling of the well is essential.
Sampling methods must be understood in order to evaluate the accuracy of reported laboratory
data.

Reservoir fluids impregnate several km3 of rocks at high depths. Consequently the access to a
representative fluid quantity is a very difficult operation. The steps leading to reservoir fluid
characterisation constitute a chain in which each link is important to ensure the reliability of the
results supplied by thermodynamic modelling.

Sampling may be necessary at different stages of an oil field life, on an exploration or appraisal
well or after bringing it in production. Well equipment may differ and determine the selection of the
sampling method.

2.2. Sampling requirements

Samples can be obtained in two ways.


In one method the well is shut in, and the liquid at the bottom of the wellbore is sampled. This is
called a bottom-hole sample or a subsurface sample.

In the other method, production rate is carefully controlled, and separator gas and separator liquid
are sampled from a test separator. These are called separator samples or surface samples. The
gas and liquid are recombined at the producing ratio in order to obtain a sample representative of
the reservoir fluid. In this case, regardless of the reservoir fluid nature and of the selected test

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method, increasing or sequential successive flowrates, the down-hole and surface production
parameter stability will determine the correct moment for sampling.

An oil reservoir must be sampled before reservoir pressure drops below the bubble-point pressure
of the reservoir liquid.
If the flowing bottom-hole pressure is lower than the bubble-point pressure (fluid saturation
pressure), because of the difference in mobility of liquid and vapour phase in the porous medium, a
fluid representative of the reservoir fluid will not be obtained in the well. Bottom-hole samples
generally will contain less gas than the original liquid since some gas has evolved. Separator
samples will be recombined at the wrong ratio because free gas is produced from the reservoir
with the reservoir liquid.
In such conditions to obtain a more representative fluid sample it is necessary to reduce the
pressure drop and consequently the reservoir fluid flow in the oil-bearing layer of the reservoir (in
the vicinity of the well). This is achieved by the use of a coiled tubing which allows a well-lifting of
the liquid phase upwards to a mini-separator equipped with accurate metering devices.

More complex differences in the produced fluid compositions may occur in case of single-phase
production (such as black oil). There is actually a varying quantity of adsorbed heavy polar
components on the rock. This phase is in equilibrium with the reservoir fluid but the equilibrium can
be shifted if pressure changes. If the pressure drop generated by the production test brings the
fluid near the critical state, part of the adsorbed constituents can be mobilised. Because the
presence of a small quantity of heavy components has consequences on the phase behaviour, the
study of such phenomena is priority for the coming years. The main application cases are critical
fluids under high pressure that represent an increasing part of discoveries.

Two guidelines should be remembered for sampling :

1. the producing G.O.R. must be stable before samples are taken,


2. if possible, samples should be taken at close to the minimum G.O.R.

The tested well is flowed for a period of time to stabilise the producing gas-oil ratio at the surface.
This includes stable wellhead pressure, stable gas production, and stable liquid production.

These checks may be over 4 to 6 hours, whereas in others, it may be as high as 72 hours if
necessary, to obtain the desired stability of the producing gas-oil ratio.

Once the producing gas-oil ratio stabilises, the well is ready for sampling.

2.3. Sampling carrying out

Figure III-A.1 gives the representation of a typical process flow diagram of a test separator. A
typical test separator P.I.D. is given in section XXV PFD, PID, ESD LOGIC DIAGRAM (PID
TYPE/231).

Gas and liquid samples are collected from the same separator at the same flow conditions. The
manner of collecting these fluid samples varies with company and individual preference. Pressure
and liquid-level controls are attached to the test separator to maintain stabilised conditions.

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Regardless of the method of collecting the fluid samples, the following data should be recorded :

1. A shrinkage measurement to determine the standard G.O.R.


A separator oil sample is introduced in a shrinkage tester to compare the oil sample
volume at separator conditions to the volume of the same oil sample after flashing to
atmospheric pressure.

Temperature and specific gravity measurement of oil sample at atmospheric pressure


allows to determine, using correction tables, oil specific gravity at standard conditions
and separator shrinkage factor by field calculation.

2. The temperature and pressure of the separator.

3. The specific gravity of the separator gas obtained in field or laboratory to correct meter
measurements.

4. The flowing bottom-hole pressure and temperature.

5. The shut-in bottom-hole pressure and temperature.

With these data it is possible to obtain an analysis of the fluid entering the separator by properly
recombining the separator liquid and separator gas.

3. LABORATORY ANALYSIS OF RESERVOIR-FLUID SAMPLES

3.1. PVT studies objectives

PVT study is the study of phase behaviour and volumetric properties of the reservoir fluid.

Till now, PVT studies are used to determine the parameters values necessary to evaluate the
production performance of a reservoir. Today, PVT studies are more considered as the mean to
determine the parameters values necessary to adjust the thermodynamic model used to predict the
behaviour and characteristics of the reservoir fluid in more severe pressure and temperature
ranges encountered in new reservoirs and new surface operation conditions.

So far, most discoveries have been made between 1 000 and 4 000 meters, within a range of 50 to
150C and 100 to 500 bar but, thanks to improvements in drilling techniques and seismic studies,
an increasing number of discoveries are made at high depths. Drillings explore the subsurface,
down to approximately 7 kilometres. The pressure gradient being to 10 (hydrostatic) to 25 bar
(geostatic) per 100 meters and the average temperature gradient being 3C per 100 meters,
temperature and pressure conditions may exceed 200C and 1 000 bar.

High pressure condensate gas in the North Sea demonstrate that the equipment must allow phase
equilibria investigation to be pursued up to a pressure of almost one kilobar. Solid deposits are
also frequent on these fluids and make the necessary experimental devices even more
complicated.

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3.2. Physical properties definitions of "black oils"

Physical properties required for the reservoir engineering calculations known as material balance
calculations are :
Liquid Specific Gravity, Formation Volume Factor of oil, Shrinkage Factor, Solution gas-oil
ratio, Total Formation Volume Factor, Coefficient or Isothermal Compressibility of oil.

3.2.1. Specific gravity (Sp. Gr.) of a liquid (go)

Liquid specific gravity (go) of a liquid is defined as the ratio of the liquid (ro) to the density of water
(rw), both taken at the same temperature and pressure.

ro
go =
rw

go is non dimensional.

Very often specific gravity is given as Sp. Gr. 60F/60F which means that the densities of both the
liquid and the water were measured at 60F and atmospheric pressure.

Degrees API or API gravity is defined by relation as follows :

141.5
API = - 131.5
gO

where : go = Sp. Gr.60F/60F

3.2.2. Formation Volume Factor of Oil (Oil FVF), (Bo) or Reservoir Volume
Factor

Formation Volume Factor (FVF) is defined as the volume of reservoir oil required to produce one
volume unit of oil in the stock-tank conditions (Standard conditions) expressed in the same unit of
volume.

volume of oil at reservoir conditions


Bo =
volume of oil in stock - tank at standard conditions

English standard conditions : 60F ; 14.7 psia


Metric standard conditions : 15C ; 101.325 kPa

Formation Volume Factor may also be defined as the volume occupied by one volume of oil in
stock-tank at standard conditions at reservoir conditions plus the gas in solution in this volume of
oil at reservoir conditions (reservoir pressure and temperature).

The volume of reservoir oil required to produce a volume of oil at stock-tank oil conditions is
obtained multiplying the last value by the formation volume factor.

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3.2.3. Reservoir shrinkage factor (RSF), (bo)

The reservoir shrinkage factor is the reciprocal of the formation volume factor :

1
bo =
Bo

Reservoir shrinkage factor is defined as the volume of stock-tank oil produced at standard
conditions by one volume of reservoir oil at reservoir conditions (reservoir pressure and reservoir
temperature) expressed in the same unit of volume. In an other words the volume of stock-tank oil
at standard conditions produced by a volume of reservoir oil at reservoir conditions is obtained
multiplying this last value by the reservoir shrinkage factor.

3.2.4. Solution gas-oil ratio (Rs) or dissolved gas-oil ratio

Solution gas-oil ratio is the amount of gas that evolves from the oil as the oil is transported from the
reservoir to surface conditions.

volume of gas produced in surface equipment


RS =
volume of oil entering the storage tank oil

Volumes of both gas and liquid are referred to the same standard conditions. The gas considered
in the solution gas-oil ratio (Rs) definition correspond to the gas dissolved in the oil at reservoir
conditions and that evolves from the oil between the well bottom-hole and the stock-tank.

When the black oil pressure is above its bubble point pressure, it is said to be undersaturated. An
undersaturated oil could dissolve more gas if the gas were present. In such case total G.O.R. is
equal to the solution gas oil ratio.

(G.O.R.)T = Rs

When the black oil pressure is at its bubble point pressure, it is said to be saturated. A slight
decrease in pressure allows a release of some gas. When reservoir pressure is reduced below
bubble-point pressure, gas evolves in the reservoir, leaving less gas dissolved in the liquid. In such
case the solution gas-oil ratio decreases as reservoir pressure is reduced at constant temperature.
In such case produced saturated oil is accompanied by free gas and

RS < (G.O.R.)T

Note :

1. As (G.O.R.)T, Rs estimate depends of the number of gas separation steps used in the
separation sequence, as well as the operating conditions of each separation step.

2. (Rsb) is the solution gas-oil ratio when black-oil is at its bubble point. When the pressure
of an undersatured oil decrease at constant temperature the solution gas-oil ratio (Rs) of
this oil remains constant till its bubble point pressure is reached. If pressure continue to

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decrease gas evolves from oil and solution gas-oil ratio decreases. In such case
(Rs) < (Rsb).

The evolved gas is called free gas.


Formation volume factor of gas (Bg) is defined as the volume occupied by this gas in
reservoir conditions divided by its volume expressed in the same units at standard
conditions.

Ps. Tr
Bg = Z
Pr. Ts

Where :

Ps = gas pressure at standard conditions,


Pr = gas pressure at reservoir conditions,
Ts = gas temperature at standard conditions,
Tr = gas temperature at reservoir conditions,
Z = gas compressibility factor at reservoir conditions.

In such case for one standard volume of oil produced at stock-tank, the volume
occupied by the evolved gas in the reservoir is given by the following relation :

Volume of gas = Bg (Rsb Rs),

The volume occupied by the remaining oil in the reservoir is Bo. The corresponding total
volume is called total formation volume factor (Bt)

Bt = Bo + Bg (Rsb Rs)

All parameters must be expressed is consistent units.

3.2.5. Coefficient of isothermal compressibility of oil

At pressure above the bubble point, the coefficient of isothermal compressibility of oil is defined
exactly as the coefficient of isothermal compressibility of a gas.

At pressures below the bubble point an additional term must be added to the definition to account
for the volume of gas which evolves.

As with gases, the coefficient of isothermal compressibility of oil usually is called compressibility or,
in this case, oil compressibility.

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3.3. Laboratory analysis of reservoir fluid samples

3.3.1. Sample preparation

Laboratory analyses are the same regardless of the method used in collecting the sample. Before
any tests can be performed, it is necessary that a certain amount of preparation be made on the
field sample.

In the case of a bottom-hone sample it is necessary to raise the temperature and pressure of the
field sample to reservoir conditions. The sample is then transferred to an appropriate test cell for
analysis.

In the case of sampling with a test separator, the preparation of a recombination sample is more
complex. The gas and oil must be recombined in correct proportions dictated by the separator or
standard G.O.R. to obtain a representative reservoir-fluid sample. The resulting fluid is equivalent
to a bottom-hole sample, and it is only necessary to raise the pressure and temperature of the
sample to reservoir conditions for further analysis.

3.3.2. Oil reservoir fluid study

Reservoir fluid study consists of a series of laboratory procedures designed to provide values of
the physical properties required in the calculation method known as material balance calculations.

The reservoir fluid study on an ordinary oil (black oil or non critical oil) consist of five tests. The first
three tests as follows (a, b, c) are all conducted at reservoir temperature, and the results describe
the behaviour of the reservoir fluid as it exists in the reservoir.

a) Pressure/volume relations or flash liberation of gas

This is a constant-composition expansion of the reservoir fluid at the reservoir


temperature during which the bubble point is measured. Above the bubble point, the
compressibility of the single-phase fluid is measured.

Below the bubble-point, the two-phase volume is measured as a function of pressure.

As no hydrocarbon material is removed from the cell during the test, the composition of
the total hydrocarbon mixture in the cell remains fixed at the original composition.

The test is equivalent to determining the volume relations along an isotherm of a phase
diagram. The gas liberated from solution is the equilibrium vapour phase which forms in
the two-phase region.

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b) Differential vaporisation

The test measures the amount of gas in solution as a function of pressure and the
resultant shrinkage of the oil as this gas is released from solution. Also measured are the
properties of the evolved gas, including the specific gravity and compressibility factor.
The density of the oil phase is also measured as a function of pressure.

The sample is placed in a high-pressure cell with the pressure above the reservoir
bubble-point pressure and the temperature of the cell at reservoir temperature. The
pressure is lowered in increments, and the volume change in the cell noted. The
pressure is lowered until such time that free gas is liberated in the cell. Then for
predetermined pressure or volume increments, mercury is withdrawn from the cell, gas is
released from solution, and the cell is agitated until the liberated gas is in equilibrium
with the oil.
The total volume of the gas and oil is determined by the mercury-volume changes during
the test. All the free gas is ejected from the cell at a constant pressure by injecting
mercury. The volumes of the free gas displaced and the oil remaining in the cell are thus
measured at cell conditions. The free gas is also measured at standard conditions.
Depending upon future tests, either the free gas is analysed at each stage of liberation
or all the gas is collected in a sample bottle. This procedure is repeated for all the
pressure increments until only oil remains in the cell at reservoir temperature and
atmospheric pressure. The gas which is liberated by a differential process, from the
bubble-point pressure to atmospheric pressure at reservoir temperature, can be
calculated from these data.

The differential liberation process as conducted in the laboratory is a stepwise


equilibrium process (usually 10 to 15 flash liberations). At each pressure decrement
vapour and liquid phases are brought to equilibrium. The essential difference between
the equilibrium test and the differential test is the removal of a portion of the fluid from
the cell during the differential test. As a result the composition of the material remaining
in the cell is progressively changed during the test. The materials removed are
predominantly lighter hydrocarbons : methane, ethane, and propane.

In mercury free PVT benches, the routine of differential vaporisation is similar. Injection
and withdrawal of mercury are replaced by displacement of a piston.

The total volume of gas and oil is determined by piston position changes.

c) Viscosity

Viscosity, which is resistance to flow, is measured as a function of pressure at reservoir


temperature.

d) Separator tests

One or more separator tests should be carried out to determine the behaviour of the
reservoir fluids as it passes up the tubing, through the separator or separators, and

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finally into the stock-tank. The FVF (Bo) and gas in solution (Rs) are measured during
these tests.

It is usually recommended to use four of these tests to determine the optimum separator
pressure, which is usually considered the separator pressure that results in the minimum
FVF. At the same pressure, the stock-tank-oil specific gravity will be a maximum and the
total evolved gas (i.e. the separator gas and the stock-tank gas) will be at a minimum.

Several separators may be placed in the flow stream to achieve a near-optimum FVF.
The optimum separator pressure may be determined by the PVT laboratory either
experimentally or through equilibrium ratio calculations with the reservoir fluid
composition and computers.

Note : As reservoir pressure is lowered and gas is evolved from solution within the
reservoir, the FVF of the reservoir oil gradually becomes smaller. Ideally, the FVF
of the reservoir oil should be measured as a function of reservoir pressure by
placing a large sample of oil in the PVT cell and pressure depleting by
differential liberation at the reservoir temperature. At each of several pressure
levels during this differential depletion, samples are removed and passed through
a separator or separators at surface conditions, and the FVF and gas in solution
are measured. Sufficient pressure levels should be studied to obtain the data to
plot a curve of FVF and gas in solution as a function of reservoir pressure. This
method is an excellent way to study an ordinary oil and should be considered the
preferred method. Unfortunately, most reservoir fluid studies contain only the
separator data on the reservoir oil at its original bubble point.

e) Composition of the reservoir fluid

Most of the parameters measured in a reservoir fluid study can be calculated with some
degree of accuracy from the composition. It is the most complete description of reservoir
fluid that can be made.

In the past, reservoir fluid compositions were usually measured to include separation of
the components methane through hexane, with the heptane and heavier components
grouped as a single component reported with the average molecular weight and specific
gravity. With the development of more sophisticated equations of state to calculate fluid
properties, it was learned that a more complete description of the heavy components
was necessary. It is now recommended that compositional analyses of the reservoir fluid
include a separation of components through C10 as a minimum. The more sophisticated
research laboratories now use equations fo state that require compositions through C30
to higher.

Volatile oils (near-critical oils) must be studied differently in the laboratory and by the
reservoir engineer to arrive at an accurate prediction of reservoir performance.

Predicted liquid recovery with a compositional material balance calculation procedure


is in excellent agreement with cases of reservoir depletion measurement. Conventional

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volumetric material balance calculation procedure gives amount of liquid produced four
times lower than measured.

3.3.3. Retrograde gas reservoir fluid study

The reservoir fluid study should include a measurement of the retrograde dew point, the fluid
compressibility above the dew point, and the gas and liquid volumes below the dew point during a
constant-composition expansion.

Finally, the fluid study should consist of a simulated depletion. This depletion generally consists of
a series of expansions and constant-pressure displacements of the reservoir fluid such that the
volume of the cell remains constant at the termination of each displacement. This procedure is
referred to as a constant-volume depletion. The reservoir gas produced during each constant-
pressure displacement is charged to analytical equipment, and the composition and volume are
determined.

A reservoir fluid study on a condensate reservoir should include the composition of the separator
gas, separator liquid, and recombined reservoir fluid. In the past, these compositions were carried
only through hexanes, with heptanes plus lumped together as one fraction. It is recommended to
carried these compositions through decanes as a minimum, with the undecanes and heavier
lumped together as a single fraction, to facilitate compositional modeling of gas-condensate
reservoirs. As indicated earlier, some of the more sophisticate major producing companies now
request analyses to C30 and higher.

3.4. Remark about differential liberation of gas and flash liberation of gas

Reservoir depletion and production consist of two separate processes or a combination of them :
differential liberation of gas and flash liberation of gas. The differential liberation is defined as a
process whereby gas is removed from oil and it is released from solution. By contrast, in a flash
liberation of gas, all of the gas remains in contact with all of the oil until equilibrium between the
two phases is attained.

Reservoir process is a combination of differential and flash. Immediately below the bubble point,
while there is little or no permeability to a gas phase, the process is primarily a flash process. As
the reservoir gas saturation reaches the critical saturation, gas begins to flow and is removed from
the reservoir oil. This is a differential liberation of gas.

Much of the gas, however, remains in the reservoir with the oil as pressure in the reservoir falls.
This is a flash liberation of gas. So the reservoir process begins as a flash process and soon
becomes a combination flash and liberation process. As pressure continues to decline, more and
more gas flows, bringing the process closer to a differential process. Once oil and gas enter the
tubing, they flow together until they reach the separator. In the separator they are brought to
equilibrium, and the gas and oil are separated. This is a flash separation.

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USE OF EQUATIONS OF STATE TO DETERMINE THE BEHAVIOUR AND THE


CHARACTERISTICS OF PETROLEUM FLUIDS

1. INTEREST OF EQUATION OF STATE (EOS)

An equation of state describe the relationship between the volume of a fluid ands its pressure and
temperature. Accurate equations of state for predicting vapour pressure and pressure-volume-
temperature (PVT) properties of hydrocarbon mixtures are vital to the design and operation of
equipment in oil and gas field processing, as for reservoir engineering.

For modelling the volumetric behaviour and the phase equilibria of a fluid, none of the models
elaborated from statistical physics has ever been as successful as that of empirical EOS.

Cubic EOS have a significant success for representing the phase equilibria of reservoir fluids, the
main reason being the simplicity of subsequent expressions and calculations. Their main drawback
is a bad calculation of volumetric properties.

Cubic equations such as Soave-RedlichKwong (S.R.K.), Peng-Robinson (P.R.) are of particular


interest to determine liquid and gas characteristics at liquid-vapour equilibria (vapour fraction,
phase compositions, physical properties of the vapour and liquid phases).

The calculated determination of liquid-vapour equilibria for natural hydrocarbon mixtures, obtained
using a numerical model, may be applied to check the consistency of experimental results, as well
as to get extra data needed to predict performance of a reservoir or to define separator
characteristics. In this case, if the model is properly fitted with available experimental data, it will
give accurate determination for different operating conditions.

2. EQUATIONS OF STATE (EOS) FOR PETROLEUM MIXTURES

2.1. Equation of state for pure components

Any cubic EOS can be expressed in the generalised form as follows.

RT a
P= -
(V - b) (V - b 1 )(V - b 2 )

where :

P = absolute pressure of the fluid,


V = molal volume of the fluid,
T = absolute temperature of the fluid,
R = ideal gas constant, (value is unit depended),
b = volume occupied by the molecules,

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a = pressure correction parameter,


(Takes in account the forces of attraction between the molecule, because the
actual pressure exerted on the walls of the vessel by real gas is less than the
pressure exerted by an ideal gas).
b1, b2 = volume correction parameters,

Cubic form is related to the polynomial degree of V in the equation. Proposed in 1873, the Van
der Waals (VdW) EOS was the first relationship that could represent both vapour and liquid
phases. It is an improvement over the ideal gas equation. However, it has limited use since it is
accurate only at low pressures.

The Van der Waals equation illustrate the semi theoretical basis which most researchers have
used to develop equations of state from the basic form of the ideal gas equation.

Soon after the appearance of the VdW equation, other researchers began attempts to improve it.
These attempts have continued for over one hundred years. Usually a change of the molecular
attraction term "a", and a change of the molecular volum terms b, b1, b2 are proposed. APPENDIX
gives the modifications used in the (SRK) and (PR) equation of state.

All of these equations have some utility ; however, none is particularly accurate as pressure and
temperature approach the critical point. Also, those equations were formulated for pure substance.
Arbitrary mixing rules must be used to determine values of constants a, b, b1, b2 for mixtures.

To provide an accurate value of the vapour pressure and better vapour-liquid-equilibrium (VLE)
results of a given substance over the entire vapour/liquid temperature range from the triple point to
the critical point the parameter "a" in the (SRK) equation is determined in a generalised empirical
expression in terms of the Pitzer acentric factor w .

The Pitzer acentric factor is a characteristic parameter for each pure substance.

It is defined by relation :

w = - (log Pvr + 1)

Where :

Pvr = reduced vapour pressure, evaluated at Tr = 0.7

Pv T
Pvr = ; Tr =
Pc Tc

Pc = critical pressure of the pure substance,


Tc = critical temperature of the pure substance,
Pv = vapour pressure or the pure substance at temperature T = 0.7 Tc

In addition the Peng-Robinson (PR) EOS modifie the functional form for the "a" parameter, which
provides a slightly improved description of liquid densities. This model gained enormous
popularity in the petroleum industry.

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Cubic EOSs are usually forced to satisfy the inflection point of the critical isotherm at the critical
point, expressed by the equations as follows :

P 2P
= o and 2 = o
V TC V Tc

These equations provide the basis for determining the two component specific constants (a and b)
in terms of the measured critical properties (Tc and Pc). As a result, these models provide an exact
description of the critical pressure and the critical temperature, which is the end point of the vapour
pressure curve.

2.2. Equation of state for mixtures

The petroleum engineer is concerned mainly with the evaluation of mixture properties.

EOSs are extended to mixtures by making the parameters a, b, b1, b2 suitable functions of
composition. Many mixing rules have been proposed in the literature, but the best-known are the
Van der Waals mixing rules.
In the Van der Waals theory the thermodynamic properties of a given mixture are the same as
those calculated for an hypothetic elementary body whose parameters are obtained by an
adequate combination of parameters of the mixture components.

If the equation of state correctly represents the elementary compounds of a mixture, the problem of
behaviour modelling lies in the research of the correct combination of component parameters or
"mixing rule".

The mixing rules may be elaborated from excess quantities but an empirical formulation most often
prevails.

The following mixture rules are recommended for use with both the Soave-Redlich-Kwong and the
Peng-Robinson equations of state.

bm = z b i i and a m = z z i j (
a i a j 1 - d ij )
i i j

where :

zi = molal fraction of component i in the mixture,


bi = volume correction for component i,
bm = volume correction for the mixture,
ai = pressure correction parameter for component i,
am = pressure correction for the mixture,
d ij = binary interaction coefficient between component i and j (other writing : kij).

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Binary interaction coefficients are assumed to be independent of pressure and temperature.


Values of the binary interaction coefficients must be obtained by fitting the equation of state to gas-
liquid equilibria data for each binary mixture. The binary interaction coefficient have different values
for each binary pair and also take on different values for each equation of state.

2.3. Input data required for cubic EOS use

These relations demonstrate that fluid behaviour prediction with the use of cubic equation of state
requires the knowledge of :

the molar composition of the fluid,


the values of the critical parameters and characteristics parameters of each component :
pure component or "oil cut" defined as a pure component (usually called pseudo-
component or hypothetical).

Pure components are defined by the parameters as follows :

critical pressure,
critical temperature,
acentric factor,
molar mass,
normal boiling point,
specific gravity for the liquid phase.

For pure components mixtures, fluid behaviour requires :

composition and nature of each pure component,


binary interaction coefficient between components considered two by two.

If these values are well known for pure components they must be determined for "oil cuts" classed
as pure components.

Usual issues from the analysis report of PVT laboratories does not indicate all physical parameters
values indicated above.
Only two parameter values are given :

specific gravity,
molar mass (or molecular weight).

To produce the complete set of physical and critical properties for the "oil cuts" required by the
EOS use, with this minimum amount of information, particular correlations are necessary.

The most famous of these correlations are to determine :

the critical pressure and the critical temperature : Lee-Kesler, Cavett, Edmister, Riazi-
Daubert, Standing,
the liquid density : Lee-Kesler, Yarborough, Katz-Firoozabadi,

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the molecular weight : Lee-Kesler, Katz-Firoozabadi, Hariu-Sage, Robinson-Peng,


the acentric factor : Lee-Kesler, Pitzer, Robinson,

Some of those correlations are shown in appendix.

All thermodynamical simulation programs (PRO-II, HYSYS) contain these correlations in property
package to predict the remaining thermodynamic properties necessary for fluid modelling. Some
are default correlations, others are optional correlations. However, the most information the user
can supply about the fluid, the more accurate physical and critical properties will be, and the better
a thermodynamic simulation program will predict the fluid's actual behaviour.

The example as follows demonstrate the importance of the oil cut definition on its characteristics
and critical parameter values.

C6 cut

Normal boiling temperature (Teb) 36.5C < Teb < 69.2C

M TC PC
Constituent mol % w
kg/kmol K Bar a

Cyclopentane 0.089 70.14 511.6 44.5 0.1923


2.2. dimethyl butane 0.009 86.18 488.7 30.4 0.2310
2.3. dimethyl butane 0.030 86.18 499.9 30.9 0.2473
2. methyl pentane 0.263 86.18 497.5 29.7 0.2791
3. methyl pentane 0.158 86.18 504.5 30.8 0.2750
normal hexane 0.519 86.18 507.4 29.3 0.2957

C6 cut 1.068 84.85 503.1 30.47 0.2781

Number of carbon atoms in the molecule

M TC PC w
Constituent mol %
kg/kmol K Bar a

2.2. dimethyl butane 0.009 86.18 488.7 30.4 0.2310


2.3. dimethyl butane 0.030 86.18 499.9 30.9 0.2473
2. methyl pentane 0.263 86.18 497.5 29.7 0.2791
3. methyl pentane 0.158 86.18 504.5 30.8 0.2750
normal hexane 0.519 86.18 507.4 29.3 0.2957
methylcyclopentane 0.263 84.16 532.7 37.4 0.2395
benzene 0.297 78.11 562.1 48.3 0.2100
cyclohexane 0.455 84.16 553.4 40.2 0.2144

C6 cut 1.993 84.25 523.3 34.69 0.2781

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2.4. Thermodynamic model tuning

2.4.1. General tuning procedure

Whatever the procedure used to obtain a model of the fluid in "n" components, the critical
properties of the component that describe the heavy fraction are mere approximate values.

Therefore, it is justifiable to select these values as parameters for a regression over the available
experimental data. This regression can be performed by means of an optimisation software under
stress, or "manual" work.

Another approach is to select some well characterised heavy constituents for the modelling of the
heavy fraction of the fluid and the calculation of the optimum proportions of these components.

The objective is to reduce the deviation between the PVT measurements and the values
reproduced by the model according to the same process.

As analytical methods are essential for the evaluation of the cut properties, PVT experimental
procedures must be perfectly defined, and particularly the conditions under which the different
volumes are expressed.

A good knowledge of laboratory methods also allows the measurements to be weighted by


favouring the most reliable ones.

The knowledge of reservoir fluids today makes the fitting procedure almost always necessary and
its implementation always difficult.

2.4.2. Sensitivity to fluid description

The parameters used first are the critical properties of the heavy fraction and interaction
coefficients of light components and this heavy fraction.

The determination mode of the fluid molar composition may be also determinant, particularly the
presence of very heavy component traces in the selected composition.

On the other hand, the effluent recombination G.O.R. recorded at test separator has no significant
influence.

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APPENDIX

1. EXPRESSION OF SPECIFIC CONSTANTS IN VAN DER WAALS, SRK AND PR EQUATIONS


OF STATE

Generalised form of cubic equations of state :

RT a
P= -
(V - b ) (V - b1 )(V - b 2 )

a = a c [a (Tr , w)]
2
with :

EOS b b1 b2 ac a (Tr , w) zc

0.125RTc 0.42188R 2 TC2 3


VdW 0 0 1
Pc Pc 8

0.08664RTc 0.42748R 2 TC2 1


SRK -b 0 f SRK (w, Tr )
Pc PC 3

PR 0.08664RTc
Pc
(
-b 1 + 2 ) (
-b 1 - 2 ) 0.45724R 2 TC2
PC
fPR (w, Tr ) 0.307

Where :

( )(
f SRK (w, Tr ) = 1 + 0.480 + 1.574w - 0.176w 2 1 - Tr ,)
fPR (w, Tr ) = 1 + (0.37464 + 1.54226w - 0.26992w )(1 -
2
Tr , )
Tc = critical temperature of the pure substance,
Pc = critical pressure of the pure substance,
Zc = critical compressibility factor obtained from each EOS, by forcing the cubic
EOSs to satisfy the inflection point of the critical isotherm at the critical
point,
R = ideal gas constant,
T
Tr = reduced temperature ; Tr = ,
Tc
T = actual absolute temperature,

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w = Pitzer acentric factor


P
w = - log v + 1
Pc
Pv = vapour pressure of the pure substance at absolute temperature T = 0.7 Tc

Fluid compressibility factor expression

Fluid compressibility factor Z is required to determine fluid density r .

MP
r=
ZRT

where :

P = actual absolute pressure,


T = actual absolute temperature,
R = ideal gas constant,
M = mixture molar mass
M = z IMi
zi = molar fraction of component i in the mixture,
Mi = molar mass of component i in the mixture,

Z = fluid compressibility factor


Expression with the generalised form of any cubic EOS
PV V aV
Z= = -
RT (V - b ) RT(V - b1 )(V - b 2 )

Rearranging previous equation into compressibility factor forms gives for SRK and PR equation of
state equations as follows.

EOS Z equation A B

SRK ( )
Z 3 - Z 2 + A - B - B 2 Z - AB = 0
aP
(RT ) 2
bP
RT

PR ( ) ( )
Z 3 - (1 - B ) Z 2 + A - 2B - 3B 2 Z - AB - B 2 - B 3 = 0
aP
(RT ) 2
bP
RT

Note : the two-constant equation of state proposed by Peng and Robinson gives better
predictions than the Soave-Redlich-Kwong equations of vapour pressure, liquid
densities and phase equilibria, particularly near the critical point. However
computation of the density of simple hydrocarbons and reservoir-fluid systems,
despite the important advances achieved by the Peng-Robinson equation, still
remains the weak point of this type of cubic equation. The prediction of liquid
densities is an area that needed improvement in all the cubic equations.

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2. EXAMPLE OF CORRELATIONS USED TO DETERMINE PHYSICAL AND CRITICAL


PROPERTIES

2.1. Relation between molecular weight, specific gravity, normal boiling


temperature

Correlation of Lee-Kesler

MW = -12 272.6 + 9486 .4 SG + (4.6523 - 3.3287 SG) TB


( )
+ 1 - 0.77084 SG - 0.02058 SG 2 (1.3437 - 720.79 / TB )10 7 TB
+ (1 - 0.80882 SG + 0.02226 SG ) (1.8828 - 181.98 T
2
B ) 1012 TB3

where :

MW = molecular weight
TB = normal boiling temperature, R
SG = specific gravity
The specific gravity of a liquid is defined as the ratio of the density of the
liquid to that of water at 60F and one atmospheric pressure.

Correlation of Riazi (included in the API Technical Data Book)

MW = 204.38TB0.118 SG1.88 exp (0.00218TB ) exp (- 3.07 SG)

These equations based on the normal boiling point and specific gravity, give similar results for pure
compounds or "oil cuts" with a normal boiling point less than 425C.

2.2. Critical properties correlations

Correlations of Lee-Kesler

TC = 341.7 + 811.0 SG + (0.4244 + 0.1174 SG)TB


+ (0.4669 - 3.2623 SG) 10 5 TB

(
ln(PC ) = 8.3634 - 0.0566 SG - 0.24244 + 2.2898 SG + 0.11857 SG2 10 -3 TB )
(
+ 1.4685 + 3.648 SG + 0.47227 SG 10 2
) -7
TB2
- (0.42019 + 1.6977 SG )10 2 -10
TB3

where :

TC = critical temperature, R,
TB = normal boiling temperature, R,

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DGEP/SCR/ED/ECP TO OIL AND GAS PROCESSING"

SG = specific gravity,
PC = critical pressure, psia

2.3. Acentric factor correlation of Lee-Kesler (for fluids having Tbr > 0.8)

w = -7.904 + 0.1352K - 0.007465K 2 + 8.359Tbr + (1.408 - 0.01063K ) Tbr

where :

K = Watson characterisation,

1
K = (TB ) 3
SG

Tbr = reduced temperature at normal boiling temperature TB,

Tbr = TB TC

2.4. Binary interaction coefficient ( d ij )

The binary interaction coefficient ( d ij ) used in SRK and PR equation of state are not necessarily
the same.

The values of the binary interaction coefficients are usually obtained from experimental vapour-
liquid equilibrium data on binary mixtures by using, for example, a least square curve-fitting
method. The binary interaction coefficients may also be obtained from other sources of
experimental data.

The order of magnitude of interaction coefficient value is :

0.12 for nitrogen-hydrocarbons,


0.15 for CO2-hydrocarbons,
0 for methane, ethane, propane, butanes and n-pentane,
0.02 for methane-nC4, and methane-nC5,
0.025 for methane-nC6, and methane-nC7,
0.035 for methane-nC8, methane-nC9, methane-nC10,
0.054 for methane-nC20,
0.06 for methane-benzene,
0.03 for methane-cyclohexane.

Interaction coefficient between methane and heavy fractions has been correlated with the specific
gravity of the fraction by :

d ij = 0.12903 (SG) - 0.05871

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