ASSESSMENT AND MODELLING OF RESERVOIR PVT PROPERTIES

By

SAMUEL. P. AKOSA

51448593

A dissertation submitted in partial fulfilment of the requirements of the award of Master of

Science in Oil & Gas Engineering at the University of Aberdeen

(August, 2015)
 ABSTRACT
Designing the reservoir simulator usually requires formulating mathematical and numerical
models. The mathematical models, describe the behavior of the reservoir fluids and rocks
with mathematical equations. While the numerical models solve the mathematical equations
in discrete cells and then extend their formulations to the whole extent of the reservoir.
Nevertheless, in coupling each cell formulation, changes occur in fluid component phases
with movement between neighboring cells. These changes tend to impact on computational
time during simulation.
Currently, the practice of modelling thermodynamic state variables i.e. the relating pressure,
volume and temperature (PVT) has become increasingly important in catering for the cell to
cell fluid phase changes and complex volumetric behavior of reservoir fluids. These
thermodynamic mathematical models usually follow either a black oil or a compositional
approach. The black oil handles the hydrocarbon components as two components phases: a
pseudo oil phase and a pseudo gas phase. Whereas compositional models honor the pure
components of the fluid and make use of an equation of state to describe the phase
equilibrium between these pure components. Compositional models tend to account for this
phase changes more than the black oil models. However in considering computational time,
most engineers prefer the black oil approach
This report aims to develop a fluid phase PVT model which will enable the engineer to
perform analysis on a reservoir sample in a short time. The proposed tool also aimed at
describing the reservoir fluid with a pseudo split approach as opposed to a black oil modelling
approach.
The outputs from the formulation of the phase model showed that computational time could
be reduced by using a reverse black oil modelling approach. The results also showed that the
pseudo split approach could considerably function similar to the black oil models and in turn
act like a compositional model in accommodating phase changes.

i
 DEDICATION
This thesis is dedicated to the Almighty God who has made it possible for me to
successfully complete this phase of life.

ii
 ACKNOWLEDGEMENTS
I will like to express my gratitude to my supervisor Dr. Jefferson Gomes, for his patience,
guidance, advice, and scrutiny during the thesis period. Moreover, special thanks goes to
Petroleum Technology Development Fund (PTDF) for the help they rendered to me in
achieving my life goals.

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CONTENTS
ABSTRACT ............................................................................................................................ i
DEDICATION ....................................................................................................................... ii
ACKNOWLEDGEMENTS .................................................................................................. iii
LIST OF TABLES ............................................................... Error! Bookmark not defined.
NOMENCLETURE ............................................................................................................. vii
CHAPTER 1 ........................................................................................................................... 1
1.1 INTRODUCTION ............................................................................................................ 1
1.2 FLUID PVT MODELLING ............................................................................................. 2
1.3 OBJECTIVE: .................................................................................................................... 4
1.4 CHAPTER BY CHAPTER SUMMARY ..................................................................... 5
OBTAINING THE FLUID PVT PROPERTIES AND ANALYSIS METHODS................. 6
2.1 RESERVOIR FLUID PROPERTIES ...................................................................... 6
2.2 PHASE BEHAVIOR OF RESERVOIR FLUIDS .................................................. 6
2.3 PHASE EQUILIBRIA AND FLASH CALCULATIONS ................................... 10
2.4 PVT LABORATORY EXPERIMENTS .............................................................. 12
2.5 FLUID DATA PROPERTIES ............................................................................... 14
2.6 CHAPTER SUMMARY........................................................................................ 16
CHAPTER THREE .............................................................................................................. 17
OVERVIEW OF RESERVOIR FLUID PVT MODELING APPROACHES ..................... 17
3.1 RESERVOIR FLUID PVT MODELS ....................................................................... 17
3.2 BLACK OIL PVT MODELS ..................................................................................... 17
3.2.1 CLASSICAL BLACK OIL PVT MODEL (CBO): ............................................. 18
3.2.2 MODIFIED BLACK OIL MODELS ............................................................. 20
3.3 METHODS IN BLACK OIL PVT MODELING ....................................................... 22
3.4 COMPOSITIONAL PVT MODELS .......................................................................... 23
3.5 BRIEF OVERVIEW OF SOME THERMODYNAMIC MODELS THAT ARE
SUITED FOR SPECIFIC PURPOSES IN COMPOSITIONAL RESERVOIR
SIMULATION.................................................................................................................. 24
3.5.1 ACTIVITY COEFFICIENT MODELS ............................................................... 25
3.5.2 EQUATION OF STATE ............................................................................... 27

iv
 3.6 OTHER MODELS: THERMAL MODELS ............................................................... 36
3.7 REGRESSION-TUNING AND CHARACTERIZATION ........................................ 36
3.8 CHOOSING A FLUID PVT MODEL ....................................................................... 37
3.9 CHAPTER SUMMARY............................................................................................. 38
4.1 FLUID PVT MODEL ................................................................................................. 39
4.2 MODEL DESCRIPTION ........................................................................................... 39
4.3 MODEL ARRANGEMENT....................................................................................... 39
4.3.1 RECOMBINATION MODULE (RC) ................................................................. 39
4.3.2 FOR FLASH MODULE ...................................................................................... 40
4.3.3 FOR BLACK OIL PVT MODULE: ............................................................. 40
4.4 FLUID MODEL VALIDATION.......................................................................... 41
4.5 MODEL RESULTS ............................................................................................. 41
4.5.2 FLASH MODULE (F-M): ................................................................................... 43
4.5.3 BLACK OIL PVT CALCULATOR MODULE (BC): ........................................ 44
4.6: ANALYSIS AND DISCUSSION ............................................................................. 46
4.7 SOURCES OF POSSIBLE ERRORS ............................................................................ 49
4.8 CHAPTER SUMMARY............................................................................................. 49
5.1 CONCLUSION ........................................................................................................... 50
APPENDIX A ...................................................................................................................... 62
A ALGORITHM FOR THE THREE MODULES ............................................................. 62
(A.1) RECOMBINATION MODULE ............................................................................. 62
(A.2) PSEUDOIZATION MODULE ............................................................................... 64
(A.2) FLASH MODULE .................................................................................................. 65
(A.3) BUBBLE AND DEW POINT PRESSURE CALCULATIONS ............................ 68
APPENDIX B ................................................................................................................... 72
B: PLOTS AND DIAGRAMS ......................................................................................... 72

v
 LIST OF FIGURES
Figure 1. The Sequence of fluid modelling in reservoir simulation………………….…….…2
Fig 1.2 Assessment of reservoir fluid PVT models………………………………………………5
Fig 2.1 Phase diagram of a binary mixture to illustrate the reservoir fluid phase
behavior..9
Figure 2..2 : Principle of pressure temperature flash process for a hydrocarbon reservoir
fluid mixture. Diagram extracted from [8] ........................................................................... 10
Fig 3..1 Schematic diagram of a Classical Black oil PVT model. Taken from [22] ............ 18
Figure 4.1 phase envelop of fluid mixture frrom F-M module……………………………..….44
Fig 4.2: Black oil model for reservoir wellstream:…………………..………………..….……45

Fig 4.3: Hypothetical black oil model with Gaussian quadrature……………………………46

Fig: B1: Snapshot of Recombination Module from Matlab…………………………………...70
Fig B2 Phase diagram of reservoir mixture from laboratory (Diagram from
Multiflash)……………………………………………………………………………………………71

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 LIST OF TABLES

Table 2.1 Equations of PVT properties. Adapted from [13]…………………………………...15

Table 3.1: Cubic equation of state with their formula. Table adapted from [55]…………..35

Table 4.2 Range between values From RC Module and Multiflash ..................................... 42
Table 4.3 Comparison from RC module recombination with Multiflash results.................. 42
Table 4.4: Absolute average error from measured lab recombination ................................ 43
Table 4.5: Black oil PVT parameters from PVTP and BC module………………………..45

Table B.3 : Comparative showing the flash of the combined reservoir stream by Multiflash
and the F-M module……………………………………………………………………………………………………………..73

vii
 NOMENCLETURE
LIST OF SYMBOLS Meaning and Unit
Bo, Oil formation volume factor, rbbl/stb
Bg, Gas formation volume factor rbbl/scf
Bw, Water formation volume factor rbbl/stb
Rs, Solution Gas oil ratio, scf/stb
Rp, Producing gas oil ratio, scf/stb
rs Condensate or Vaporized oil gas ratio stb/scf
γ Gas specific gravity
ρ Density, lbm/ft3
v molar volume, ft3/mole
V Volume, ft3
P Pressure, psia
T Temperature, oF
G Gibbs free energy,
f Fugacity ,psia
R Universal gas constant, =10.73 lbmft/oR
μ Viscosity, cp
μ Chemical potential
U Internal energy
M Molecular weight, lb/lbmole
x Liquid mole fraction, (%)
y Vapor mole fraction (%)
z Feed mole fraction (%)
Z Compressibility factor
𝛿𝛿𝑖𝑖𝑖𝑖 Binary interaction parameter
𝜔𝜔 Acentric factor
co Isothermal compressibility factor, 1/psi
a Hermolthz energy
OB Objective function
CC Calculated observation

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OBj Objective function
Rj Residual observation
nPR Number of regression parameters.
nOBS Number of experimental observations
Ω𝑎𝑎 , Ω𝑏𝑏 EOS critical parameters
a, and b Attractive and repulsive terms

SUBSCRIPTS
o Oil phase
g Gas phase
w Water
v Vapor phase
l Liquid phase
API American petroleum Institute
c critical
air air

ABBREVIATION
SCN Single Carbon Number
wj weight Factor
EOS Equation of state
PVT Pressure, volume and temperature
SCN Single Carbon Number
CVD Constant volume depletion
CCE Constant composition Expansion
DLE Differential liberation experiments
BC Black oil calculator module
RC Recombination Module
FM Flash Module

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CHAPTER 1

1.1 INTRODUCTION
Nowadays, the reservoir simulator has been used to tackle lots of problems in reservoir
engineering. Due to its sophisticated nature, it has been is relied upon to describe the behavior
of the reservoir to any given length of time and also to optimize hydrocarbon production
using different operating conditions [1].
Moreover, in designing the simulator, formulating mathematical and numerical models are
usually required. The mathematical models describe the behavior of the reservoir fluids and
rocks with mathematical equations. While the numerical models divide the whole reservoir
into small cells (also called grids) in order to accommodate any minute reservoir description
such as wells positioning. Also, these numerical models solve the mathematical equations in
these cells and then extend their formulations to the whole extent of the reservoir.
Nevertheless, in coupling each cell formulation, changes in fluid component phases and
movement do occur between neighboring cells. [2]. Since these cell to cell relationship do
experience changes resulting from the fluid composition and state, it is important to
adequately account for the fluid properties that lead to such changes. [3]. Thus a sound
understanding these fluid properties is fundamental to the reservoir simulator design [4].
Presently, the practice of modelling thermodynamic state variables i.e. the relating pressure,
volume and temperature (henceforth called PVT) has become successful in catering for the
cell to cell fluid phase changes and complex volumetric behavior of reservoir fluids. This
modelling approach has gained wide acceptance because it is capable of yielding lots of fluid
properties of interest (e.g. Pressure, volume and temperature can be used to derive the
isobaric heat capacity: a property that determines how hot a substance gets) the that are
useful in determining the nature of the fluid at the reservoir as well as the surface when it is
produced [5].
Conversely, to accommodate computing time and to reduce the enormous mathematical
relations (used to account for the complex behavior of reservoir fluid) in the cells, huge
challenges of improper predictions have been encountered. Thus, retarding the accuracy of

1
the simulators overall results and its robustness over time. Therefore, there is the need for a
PVT model that will accommodate computing time and also predict fluid behavior to a large
extent and for different cases.

1.2 FLUID PVT MODELLING

In reservoir simulation, fluid modelling involves describing the physical properties of the
reservoir fluids, which depend on the reservoir rock, pressure, temperature as well as the fluid
composition. Basically, the sequence followed in fluid modeling begins with collecting the
samples from the reservoir, analyzing the samples and then developing the mathematical
models that describe the thermodynamic behavior of the fluid. After describing the fluids
behavior, the next stage is to describe its flow with regards to the reservoir rock as shown in
Fig 1 below

FLUID
PVT
RESERVOIR

SIMULATOR
FLUID
FLOW

Figure 1.1 The Sequence of fluid modelling in reservoir simulation

Diagram adapted from [2].

The volumetric properties of the fluid will first be defined and modelled before the fluid
flow properties are handled since fluid flow properties depend on the inherent
thermodynamic behavior of the fluid.
However, this thesis concentrates on the thermodynamic aspect of the fluid model and thus
further discussions on the flow stage will be omitted.
Moreover, the mathematical models used in describing the thermodynamic behavior of the
fluids are classified into two which include: the Black oil PVT models and the Compositional
models.

2
The black oil PVT model presumes that properties of phases depend only on pressure at a
constant temperature. The black oil model divides the hydrocarbon components into two
components: a pseudo oil phase and a pseudo gas phase (the pseudo gas phase is analogous
to the separator gas and whereas the pseudo oil is to the stock tank oil). Thus the Separator
gas is considered a pseudo-component consisting of hydrocarbons in the reservoir that remain
in the gas phase at standard conditions. On the other hand, the stock tank oil is the other
pseudo-component consisting of hydrocarbons in the reservoir that remains in the oil phase
at standard conditions [6].
However, the PVT properties suited for this modelling approach involves those properties
that describe the volumetric relationship between the amount of oil and gas phases at
reservoir and at surface. These properties include the gas oil ratio 𝑅𝑅𝑠𝑠, the vaporized oil gas
ratio 𝑟𝑟𝑠𝑠 , the oil formation volume factor,𝐵𝐵𝑜𝑜 as well as the gas formation volume factor,
𝐵𝐵𝑔𝑔 [7]. Equations 1.1 to 1.4 shows the relationship of these properties to volume.

𝑉𝑉𝑜𝑜
𝐵𝐵𝑜𝑜 =
𝑉𝑉𝑜𝑜�𝑜𝑜 (1.1)

𝑉𝑉𝑔𝑔
𝐵𝐵𝑔𝑔 =
𝑉𝑉𝑔𝑔�𝑔𝑔 (1.2)

𝑉𝑉𝑔𝑔�𝑜𝑜
𝑅𝑅𝑠𝑠 =
𝑉𝑉𝑜𝑜�𝑜𝑜 (1.3)

𝑉𝑉𝑜𝑜�𝑔𝑔
𝑟𝑟𝑠𝑠 =
𝑉𝑉𝑔𝑔�𝑔𝑔 (1.4)

Where, 𝑉𝑉𝑜𝑜 is the volume of reservoir oil, 𝑉𝑉𝑜𝑜�𝑜𝑜 is the volume of stock tank oil from the reservoir
oil, 𝑉𝑉𝑔𝑔 is the volume of reservoir gas, 𝑉𝑉𝑔𝑔�𝑔𝑔 is the volume of surface gas from reservoir oil, 𝑉𝑉𝑜𝑜�𝑜𝑜

3
is the volume of surface oil from reservoir oil, 𝑉𝑉𝑔𝑔�𝑜𝑜 is the volume of surface gas in reservoir
oil (it is usually the same as 𝑉𝑉𝑔𝑔�𝑔𝑔 ) .
However, if the oil and gas composition starts varying strongly such as in the case of volatile
oil reservoir, retrograde gas condensate reservoir, gas injection, solution-gas, and gas-cap
reservoirs drive studies. The large number of components will need an equation of state
which can provide consistent densities, compositions, and molar volumes, hence the need for
a full compositional model. The Compositional model therefore refers to models that make
use of an equation of state to describe the phase equilibrium behavior based on its pure
components. Equilibrium phase splits and phase properties are determined by blending the
properties of the stream constituents. The equation of state (henceforth called EOS) is used
to predict the vapor liquid equilibrium (VLE), and associated thermodynamic properties such
as gas and liquid enthalpies, gas and liquid densities, gas and liquid viscosities, surface
tension and thermal properties.
Furthermore, it is impractical to model every component of a reservoir fluid due to the large
numbers of components that are present [8]. Generally, for acceptable phase behavior
prediction, it is sufficient to specify the mole fractions of the main light end hydrocarbons
(typically from methane to decane for black oils). Heavier components are lumped together
and handled as pseudo or hypothetical components [9].
Nevertheless, computational considerations and cost can favor companies to choose the black
oil model for their simulation studies. On the other hand, it is highly advisable to derive the
properties of black oil using the equation of state for interpretation of the results of the
analysis to ensure proper understanding and identification of the quality of PVT data
obtained. [10] Most modern reservoir flow simulators are usually written with a general
compositional formulation whereas the black oil PVT properties are converted internally to
a two component compositional model.

1.3 OBJECTIVE:
The aim of this report is to describe the reservoir fluid PVT properties and how they are
formulated in the simulator design. This description will include the methods used in
analyzing fluid properties and their modeling approaches. Furthermore, at the end of the

4
project, a fluid phase model will be designed to predict the phase behavior of a gas condensate
fluid by combining the black oil and compositional modeling approach.

1.4 CHAPTER BY CHAPTER SUMMARY:

This report provides an assessment of the whole process involved in developing a fluid PVT
model to be used in the reservoir simulator. The flow of ideas is broadly classified into two
sections which include Assessment of PVT properties and their Modeling approaches
(Chapters two and three), and then coding of a fluid PVT property model (Chapter four). The
introductory chapter gives a brief description of the fluid PVT modeling process as related
to reservoir simulation while also stating the aims of the report. Chapter two discusses the
methods of analyzing these fluid properties which serves as inputs to the fluid models.
Moreover, chapter three discusses the description of the fluid PVT models. The next chapter
shows the coding of a black oil PVT model to predict phase behavior and fluid properties.
Then Chapter five summarizes the report. A schematic of the whole report process is shown
in Fig 1.2. The chapters are arranged in such a way to show the sequence in modeling the
fluid properties are developed
ASSESSMENT AND
MODELING OF
RESERVOIR FLUIDS

Chapter Chapter two Chapter three Chapter Chapter five

one four
Nature of Fluid Pvt Conclusion
Introducti reservoir fluid Model’s types Overview and
on of Phase Recommend
Overview of Black oil Pvt behavior ation
Review of Phase equilibria Model pvt model
fluid and Pvt Analysis
models Compositional Model
Fluid Properties validation
Project
objectives Critical
analysis of
Fig 1.2 Assessment of reservoir fluid PVT models

5
CHAPTER TWO

OBTAINING THE FLUID PVT PROPERTIES AND ANALYSIS METHODS

2.1 RESERVOIR FLUID PROPERTIES

Gaining proper insight of the reservoirs fluid nature and its behavior usually requires
obtaining and analyzing representative samples of the reservoir. In order to ensure reliability
of results from the fluid models, it is important to understand the results from the analyses
that was carried out on the reservoir samples. This chapter will describe the methods used to
analyze the fluid samples and how they affect the fluid modelling process. Moreover as a
background overview, it will also discuss the phase behavior of the reservoir fluid which
affects the analyses performed on the fluid.

2.2 PHASE BEHAVIOR OF RESERVOIR FLUIDS

In thermodynamic studies, a phase refers to a continuous homogenous portion of a system
which is physically distinct from other parts by definite boundaries. Thus, a reservoir consists
of liquid phases i.e. both oil and water phases as well as a vapor or gaseous phase. In some
reservoirs the gaseous phase tends to be dissolve in the oil but later presents itself during
depletion [11].
Moreover, the state of equilibrium that is where no state changes occur with time is important
to the concept of phase behavior at a particular temperature and pressure. This equilibrium is
usually attained at minimum Gibbs [12] energy and when the chemical potentials of each
component in the phases are equal [13]. Equations 2.1 to 2.8 describe how this energy is
related to phase behavior

𝜕𝜕𝜕𝜕
𝜇𝜇𝑖𝑖 = (2.1)
𝜕𝜕𝑛𝑛𝑖𝑖

Where μi is the chemical potential of component-i, G is the Gibbs free energy and ni is the
number of moles of component-i. Thus for a system with two phases the condition for
equilibrium is
𝜇𝜇𝑖𝑖(𝑥𝑥) = 𝜇𝜇𝑖𝑖(𝑦𝑦) (2.2)

6
 𝑃𝑃𝑖𝑖(𝑥𝑥) = 𝑃𝑃𝑖𝑖(𝑦𝑦) (2.3)

𝑇𝑇𝑖𝑖(𝑥𝑥) = 𝑇𝑇𝑖𝑖(𝑦𝑦) (2.4)

Where, P is the pressure, T is the temperature, x and y represents the phases. Chemical
potentials are usually expressed in terms of fugacity, fi,

𝑑𝑑𝑑𝑑𝑖𝑖 = 𝑅𝑅𝑅𝑅 ln 𝑓𝑓𝑖𝑖 (2.5)

It is readily shown that equation (2.2) is readily satisfied by the equal-fugacity constraint,

𝑓𝑓𝑖𝑖𝑣𝑣 = 𝑓𝑓𝑖𝑖𝐿𝐿
(2.6)

Where, 𝑓𝑓𝑖𝑖𝐿𝐿 is the fugacity of component-i in the liquid phase and 𝑓𝑓𝑖𝑖𝑣𝑣 is the fugacity of
component-i in the vapor phase.
Fugacity is a property of a real substance that is a measure of the tendency of the substance
to prefer one phase at a particular temperature and pressure. It has same dimensions as
pressure but is related to the partial pressure of a component in a mixture. The ratio of the
fugacity to the pressure is referred to as the fugacity coefficient, φ and is given by

𝑓𝑓𝑖𝑖
= 𝜑𝜑𝑖𝑖
𝑥𝑥𝑖𝑖 𝑝𝑝 (2.7)

Where, xip =partial pressure of the component in the mixture,

fi, p, x and φi are the fugacity, pressure, phase component molar composition and partial
fugacity coefficient of component-i respectively.
The fugacity coefficient of a component in a mixture is also related to temperature and
volume by the expression

7
 ∞
fi 1 ∂P RT
ln φi = ln = �� - � dV- ln Z (2.8)
xi p RT ∂ni V
V

Where R,T,V ,ni, and Z are the universal gas constant, temperature, volume , number of
moles of each component and the compressibility factor of component- i
Nevertheless, the phase with the lowest fugacity coefficient will thermodynamically be the
most favorable i.e. the phase with minimum Gibbs energy. Gibbs free energy can be related
to fugacity as shown in equations (2.9) and (2.10)
𝑛𝑛

𝐺𝐺𝑦𝑦∗ = � 𝑦𝑦𝑖𝑖 ln 𝑓𝑓𝑖𝑖𝑣𝑣

𝑖𝑖=1
(2.9)

𝑛𝑛

𝐺𝐺𝑥𝑥∗ = � 𝑥𝑥𝑖𝑖 ln 𝑓𝑓𝑖𝑖𝑙𝑙 𝑖𝑖

𝑖𝑖=1
(2.10)

Where, 𝐺𝐺𝑦𝑦∗ 𝑎𝑎𝑎𝑎𝑎𝑎 𝐺𝐺𝑥𝑥∗ are the normalized Gibbs free energies in the vapor and liquid phases
respectively. Most compositional PVT models rely of the concept of equal fugacities of the
phase components and minimum Gibbs energy to determine phase equilibrium state of
multicomponent mixtures.
In order to describe the percentage of a component in a phase at a particular pressure and
temperature a Pressure-Temperature phase diagram could be used [14] .
Fig 2.1 shows a typical pressure temperature phase diagram with characteristic features used
in describing fluids. The phase diagram is bounded by the bubble point and dew point curves
with the two curves meeting at the critical point (C). The critical point is where all differences
between the two phases seize and the phases become indistinguishable.
Furthermore, since critical properties are just properties of individual components in a
mixture, for fluid modeling the pseudo critical values (e.g. pseudo critical pressure and
temperature) for the mixture are used. The pseudo critical value of a mixture is derived from
mixing the critical values of individual components by using a mixing rule. A widely used

8
mixing rule is the Kay’s [15] mixing rule which is based on molar averaging of the
components.
Mathematically the Kay’s rule is

𝑛𝑛

.𝑝𝑝 𝜃𝜃𝑐𝑐 = � 𝑧𝑧𝑖𝑖 𝜃𝜃𝑐𝑐𝑐𝑐

𝑖𝑖
(2.11)

Where zi is the mole fraction, .pθc is any pseudo critical property such as temperature, pressure
or volume and θci is the critical component of component i and n is the number of
components.

B
Pressure

C
Critica
l point
D

TWO PHASE

Temperature

Fig 2.1 Phase diagram of a binary mixture to illustrate the reservoir fluid phase behavior
Diagram taken from [14]. The maximum pressure (B) on the phase diagram is called the
Cricondenbar and refers to the pressure beyond which no gas can be formed regardless of the
temperature. While the maximum temperature (D) beyond which no liquid can be formed
regardless of the pressure is the Cricondentherm [14].

9
2.3 PHASE EQUILIBRIA AND FLASH CALCULATIONS
To determine the phase equilibrium, calculations that estimate the percentage or molar
amount of compositions of the mixtures that are vaporized or condensed is paramount. These
percentages can also help in determining the phase diagram by calculating the bubble point
and the dew point curves. Thus also yielding the temperatures and pressures at which the
mixture begins to vaporize of condense [16]. Mixtures molar amounts can be obtained by
flashing the mixture at a particular temperature and pressure in a flash separator. Figure 2.2
gives an illustration of a pressure-temperature flash process for a hydrocarbon mixture.
If the pressure , temperature and mole fractions in the feed (zi = z1,z2,z3…zn) are known, a
flash calculation can provide the number of phases; molar amounts of each phase e.g. FV ,FL
and also the individual component molar compositions for each phase i.e. for the vapor
phases (y1,y2,y3…..yn) and the liquid phase(x1,x2,x3….xn). Moreover , referring to equation
(2.6) and (2.7) at equilibrium

(y1,y2,….yn)

FV
Gas
Feed, 1mole
T, P
(z1, z2….zn)

(1-Fv)

Oil (x1, x2,…xn)

Figure 2.2 : Principle of pressure temperature flash process for a hydrocarbon reservoir
fluid mixture. Diagram extracted from [8]
A feed of 1 mole (with mole fractions z1, z2…. zn) entering a separator is flashed at the
temperature of the separator, T and pressure P. The flashing yields two phases at equilibrium
with the phases being a gaseous (vapor) phase with Fv moles ( containing y1, y2 ….yn mole
fractions) and liquid phase with (1-Fv) moles (containing x1, x2,…xn mole fractions),

10
 𝜑𝜑𝑖𝑖𝐿𝐿 𝑦𝑦𝑖𝑖
=
𝜑𝜑𝑖𝑖𝑉𝑉 𝑥𝑥𝑖𝑖 (2.12)

For i = 1,2,….n. where n is the total number of components

The above relation is equal to the equilibrium constant K for each component, hence

𝜑𝜑𝑖𝑖𝐿𝐿 𝑦𝑦𝑖𝑖
𝐾𝐾𝑖𝑖 = =
𝜑𝜑𝑖𝑖𝑉𝑉 𝑥𝑥𝑖𝑖 (2.13)

Also performing a mass balance on the diagram, Feed F=1

𝐹𝐹𝑣𝑣 + 𝐹𝐹𝐿𝐿 = 1
(2.14)

𝑧𝑧𝑖𝑖 = 𝐹𝐹𝑣𝑣 𝑦𝑦𝑖𝑖 + (1 − 𝐹𝐹𝑣𝑣 )𝑥𝑥𝑖𝑖 (2.15)

Thus, relating zi and Fv to K yields and rearranging

𝑧𝑧𝑖𝑖 𝐾𝐾𝑖𝑖
𝑦𝑦𝑖𝑖 =
1 + 𝐹𝐹𝑣𝑣 (𝐾𝐾𝑖𝑖 − 1) (2.16)

𝑧𝑧𝑖𝑖
𝑥𝑥𝑖𝑖 =
1 + 𝐹𝐹𝑣𝑣 (𝐾𝐾𝑖𝑖 − 1) (2.17)

For i =1, 2…n.

The sum of the mole fractions of the phases and the entire mixture must all be equal to one
or a hundred in percentage form. Thus

11
 𝑛𝑛 𝑛𝑛 𝑛𝑛

� 𝑧𝑧𝑖𝑖 = � 𝑦𝑦𝑖𝑖 = � 𝑥𝑥𝑖𝑖 = 1.0

𝑖𝑖=1 𝑖𝑖=1 𝑖𝑖=1
(2.18)

This implies that

𝑛𝑛 𝑛𝑛

� 𝑦𝑦𝑖𝑖 − � 𝑥𝑥𝑖𝑖 = 0
𝑖𝑖=1 𝑖𝑖=1
(2.19)

Thus substituting equations 2.16 and 2.17 for yi and xi into the above equation yields the
Rachford-Rice equation [13]

𝑛𝑛
𝑧𝑧𝑖𝑖 (𝐾𝐾𝑖𝑖 − 1)
ℎ(𝐹𝐹𝑣𝑣 ) = � =0 (2.20)
1 + 𝐹𝐹𝑉𝑉 (𝐾𝐾𝑖𝑖 − 1)
𝑖𝑖=1

This could be solved to obtain the vapor mole fraction Fv using an iteration scheme. However
a stability analysis is usually performed before commencing a flash calculation because it
determines the number of phases present. Michelsen (1982) [17] proposed a consistent phase
stability check that is based on the minimization of the Gibbs free energy by splitting off a
vapor phase [8]. Currently most compositional PVT models usually depend on stability
checks and Rachford equation to perform vapor liquid equilibrium calculations.
Nevertheless, thorough details of the stability analysis are beyond the scope of this report but
an overview of stability criteria is shown in Appendix A.2

2.4 PVT LABORATORY EXPERIMENTS

After collecting representative fluid samples (samples that maintain same quality with the
reservoir fluids) of the reservoir, the next step involves measuring the fluid properties by
analyzing the PVT properties of the sample [18].
Generally, the samples are usually transferred to a laboratory for its analysis but it can also
be analyzed On-site. However, to ensure accuracy and reliability, an integration of the both
methods is more acceptable as a suitable means [19]. Accurate sampling and analysis

12
techniques often provide critical input to reservoir simulation models and help to optimize
processing facility designs while boosting the profitability of an oil or gas field [20].
Laboratory experiments performed determine the phase behavior and physical properties of
the fluid. The lab experiments are broadly classified into the following groups [13] namely
(i) Constant Composition Expansion (CCE)
(ii) Constant Volume Depletion test (CVD)
(iii) Fluid composition
(iv) Separator test (multistage)
(v) Differential liberation test (DLE)
(vi) Viscosity measurements
(vii) Swelling test
The constant Volume depletion (CVD) experiment is generally used for retrograde
condensate fluid samples to measure the composition and specific gravity of the fluid. It
could provide useful data for the mathematical models depicting the changes in a condensate
reservoir. Also Fluid composition test involves measuring the vapor and liquid phase
compositions (mole percent and specific gravity [13]) of the components of the sample using
a gas chromatograph [21]. The compositions can also be used for phase calculations in the
mathematical thermodynamic models.[11]
Constant composition expansion or flash expansion test involves placing a known volume of
an equilibrated single phase fluid in a windowed PVT cell and monitoring the fluid change
with reduction in pressure isothermally which eventually leads to the production of two
phases under agitation. It usually consists of stages of equilibration, whereby the cell volume
is increased until the next predetermined pressure level is obtained with no gas or liquid
removed at any point. This test is used to determine the bubble point pressure [13, 21]
Another important laboratory test is the differential liberation or vaporization test. It usually
involves equilibration of the reservoir fluid sample in a PVT cell at the bubble point pressure
and at its reservoir temperature. The pressure inside the cell is usually reduced by increasing
the volume, thus enabling a gas phase to form. Agitation is also employed to equilibrate this
gas with the liquid. The gas is then displaced isobarically by reducing the volume of the cell
slowly. Parameters that could be measured from this test include the specific gravity, volume
of the expelled gas and volume of the liquid remaining in the cell.

13
Other properties like Gas and oil compressibility factors, density of the remaining oil,
solution gas-oil ratio, gas and oil formation volume factors could be obtained from this test
as calculated parameters. [13]
In the separator or flash vaporization test, a known volume of the fluid sample at bubble point
and reservoir temperature is charged into the PVT cell. It is displaced at bubble point pressure
via two or more stages of separation. Similar equilibration process to the differential
liberation test is used however the pressures and temperatures of the laboratory separators
are selected to be closed to expected field conditions. The gas oil ratio and formation volume
factor at separator could be measured by this test.[10, 13].
Other laboratory tests include swelling or extraction test and viscosity tests are also important
in proper characterizing of the fluids. The swell test is carried out to investigate the reaction
of the reservoir fluid to gas injection.[8] It is paramount in measuring phase behavior and it
is used to determine the reservoir fluid volume -compositions changes with regards to the
injected fluid (e.g. CO2) dissolution at reservoir temperature. While the Oil viscosity test are
performed by using a capillary viscometer or an electromagnetic viscometer. Measurements
are usually done at same pressure levels just as in differential liberation experiments with
samples deficient of gas at each pressure level. [13]
Alternatively, PVT analysis could be performed on Well-site rather than taking samples to
the laboratory as this could save time and ensure early warnings of problematic chemicals
like hydrogen sulphide and mercury. This test could also be used to: check levels of oil-based
mud contamination in liquids and to analyze of amounts of rare gases present in hydrocarbon
gas. A current example of this technique is the Schlumberger’s PVT Express which uses less
than 50cm3 volume of a sample to conduct full PVT study.[18]

2.5 FLUID DATA PROPERTIES

To handle fluid problems with reservoir simulation, the required PVT properties needed
include the following: Specific gravity, molecular weight, density, viscosity, formation
volume factors (FVF) for oil and gas, solution gas oil ratios, and compressibility. Table 2.2
shows some important PVT properties that are critical in defining a reservoir fluid. The
formulae presented in the tables are just the basis of how such properties are obtained.

14
Table 2.1 Equations of PVT properties. Adapted from [13]
PVT TYPE SYMBOL BASE EQUATION FOR
PROPERTY FORMULATION

Specific gravity Oil γo 𝜌𝜌𝑜𝑜�

𝛾𝛾𝑜𝑜 =
𝜌𝜌𝑤𝑤�

Gas γg 𝜌𝜌𝑔𝑔�
𝛾𝛾𝑔𝑔 =
𝜌𝜌𝑎𝑎𝑎𝑎𝑎𝑎
�����

Solution gas oil Condensate Rs 𝑉𝑉𝑔𝑔�

𝑅𝑅𝑠𝑠 =
ratio 𝑉𝑉𝑜𝑜�

Formation Water Bw 𝑉𝑉𝑤𝑤

𝐵𝐵𝑤𝑤 =
volume factor 𝑉𝑉𝑤𝑤�

(FVF) Oil Bo 𝑉𝑉𝑜𝑜

𝐵𝐵𝑜𝑜 =
𝑉𝑉𝑜𝑜�

Gas Bg 𝑉𝑉𝑔𝑔
𝐵𝐵𝑔𝑔 =
𝑉𝑉𝑔𝑔�

Density Oil ρo 𝑀𝑀𝑜𝑜

𝜌𝜌𝑜𝑜 =
𝑉𝑉𝑜𝑜

Gas ρg 𝑀𝑀𝑔𝑔
𝜌𝜌𝑔𝑔 =
𝑉𝑉𝑔𝑔

Isothermal Gas Cg 1 𝜕𝜕𝜌𝜌𝑔𝑔

𝐶𝐶𝑔𝑔 = � �
Compressibility 𝜌𝜌𝑔𝑔 𝜕𝜕𝜕𝜕 𝑇𝑇

Viscosity Oil μo 𝜇𝜇𝑜𝑜 = 𝑓𝑓(𝑇𝑇, 𝛾𝛾𝐴𝐴𝐴𝐴𝐴𝐴 )

Gas μg 𝜇𝜇𝑔𝑔 = 𝑓𝑓(𝑇𝑇, 𝑀𝑀𝑔𝑔)

Where subscripts o, g and w represent reservoir conditions while 𝑜𝑜̅ , 𝑔𝑔̅ , 𝑎𝑎𝑎𝑎𝑎𝑎
���� and 𝑤𝑤
� represent
surface conditions. Also subscript T is the isotherm temperature and 𝛾𝛾𝐴𝐴𝐴𝐴𝐴𝐴 is the API gravity
and is closely related to the specific gravity of oil.

15
2.6 CHAPTER SUMMARY
The following are the points what noting from this chapter
(i) Minimizing the Gibbs free energy determines the equilibrium of the phases. At this
equilibrium the fugacity's of the individual phases are equal
(ii) The phase of a mixture is determined by its composition, pressure and temperature
(iii) PVT laboratory analysis are important deducing the input parameters (fluid
properties) needed for the fluid mathematical modeling stage. Integration of on-site
analysis and laboratory analysis could yields good result.

16
 CHAPTER THREE

OVERVIEW OF RESERVOIR FLUID PVT MODELING APPROACHES

3.1 RESERVOIR FLUID PVT MODELS

After measuring the composition of the fluid in the laboratory, the next step is to model the
volumetric behavior of the hydrocarbons fluids in the reservoir. This step involves
representing the physical properties of the fluid by consistent mathematical formulations that
describes the samples behavior close to the reservoir condition. The approaches taken in fluid
PVT modeling can be broadly classified into two which include
(a) Black oil PVT models
(b) Compositional PVT models
Moreover, it is imperative to note that the chosen approach strongly affects the kind of model
that will be used in the fluid flow modeling stage of the simulator

3.2 BLACK OIL PVT MODELS

. Generally, black oil PVT models are models that describe the volumetric behavior of
reservoir fluids by using phase’s properties which depend only on pressure at a constant
temperature. These properties that depend on pressure include: solution gas oil ratio Rs,
reservoir oil and gas formation volume factors Bo and Bg and surface oil and gas gravities
𝛾𝛾𝑜𝑜 and 𝛾𝛾𝑔𝑔 respectively as shown in equation (3.1) They are used to calculate the densities and
relative amounts of oil and gas phases at reservoir conditions . [22]

�𝐵𝐵𝑜𝑜 , 𝐵𝐵𝑔𝑔 , 𝑅𝑅𝑠𝑠 , 𝛾𝛾𝑜𝑜 , 𝛾𝛾𝑔𝑔 � = 𝑓𝑓(𝑃𝑃)

(3.1)

Where, subscript o and g refers to oil and gas phase respectively.

Moreover, black oil models divides the reservoir hydrocarbons into binary components: a
pseudo oil phase and a pseudo gas phase (the pseudo gas is analogous to the separator gas
and whereas the pseudo oil is to the stock tank oil). Thus the Separator gas is considered a
pseudo-component consisting of hydrocarbons in the reservoir that remain in the gas phase

17
at standard conditions. While the stock tank oil is the other pseudo-component consisting of
hydrocarbons in the reservoir that remains in the oil phase at standard conditions [6].
Presently, two approaches have been used in black oil PVT modeling and they include the
following [7]
(a) Classical or standard black oil model(CBO)
(b) Modified black oil models (MBO)

3.2.1 CLASSICAL BLACK OIL PVT MODEL (CBO):

This approach assumes that there is no oil component in the gas phase, thus a reservoir gas
at surface will remain the same without any liquid (oil) condensing out. Fig 3.1 shows
diagrammatically how the reservoir gas remains similar to the gas at the surface. Since the
gas never contains any liquid, the model can be referred to as a dry gas black oil model [23].
The dry gas approach means that the solution oil-gas ratio rs is approximately zero, thus no
oil comes out of the gas phase.
Reservoir Surface condition
condition

2 G
3- Hydrocarbon
a
surface gas
s

2 Vapor

Liquid
1 2
2- Hydrocarbon surface
2 Gas
gas
1
Oil
1-Nonvolatile surface oil

Fig 3.1 Schematic diagram of a Classical Black oil PVT model. Taken from [22]

Initially at reservoir conditions there is equilibrium between the liquid and the vapor phases.
As they are produced to the surface (e.g. at the separator) there is a split into separate phases
whereby the gas coming out at surface components contains no oil, thus rs=0. However, the

18
lowermost box in the diagram is analogous to the stock tank where some hydrocarbon gas
still comes of the oil at surface contains some gas leaving at the bottom a non-volatile oil.
Thus only a non-volatile oil and a hydrocarbon gas is present at the surface in a classical
black oil model.
Moreover, to compare the changes in volumetric amounts of the phases at surface and at
reservoir conditions, three properties of the fluids are used to capture the changes. This
properties are the Solution gas oil ratio, Rs; the gas formation volume factor Bg and the oil
formation volume factor Bo and are described by equation (3.2) to (3.4)
𝑉𝑉𝑜𝑜
𝐵𝐵𝑜𝑜 =
𝑉𝑉𝑜𝑜�𝑜𝑜 (3.2)

𝑉𝑉𝑔𝑔
𝐵𝐵𝑔𝑔 =
𝑉𝑉𝑔𝑔�𝑔𝑔 (3.3)

𝑉𝑉𝑔𝑔�𝑜𝑜
𝑅𝑅𝑠𝑠 =
𝑉𝑉𝑜𝑜�𝑜𝑜 (3.4)

Where, 𝑉𝑉𝑜𝑜 is the volume of reservoir oil, 𝑉𝑉𝑜𝑜�𝑜𝑜 is the volume of stock tank oil from the reservoir
oil, 𝑉𝑉𝑔𝑔 is the volume of reservoir gas, 𝑉𝑉𝑔𝑔�𝑔𝑔 is the volume of surface gas from reservoir oil, 𝑉𝑉𝑜𝑜�𝑜𝑜
is the volume of surface oil from reservoir oil, 𝑉𝑉𝑔𝑔�𝑜𝑜 is the volume of surface gas in reservoir
oil (it is usually the same as𝑉𝑉𝑔𝑔�𝑔𝑔 , cause it contains similar elements as shown in the diagram).
Equation (3.2) and (3, 3) refers to the shrinkage of the oil and gas volume (from the reservoir)
at the surface respectively, while Equation (3.3) gives the volumetric ratio of the oil and gas
at the surface.
According to Whitson [7], the assumptions used in formulating the standard black oil model
include the following
(i) Reservoir oil consists of two surface “components,” stock-tank oil and surface (total
separator) gas.
(ii) Reservoir gas does not yield liquids when brought to the surface.
(iii) Surface gas released from the reservoir oil has the same properties as the reservoir gas.
(iv) Properties of stock-tank oil and surface gas do not change during depletion of a reservoir.

19
Furthermore, as stated earlier, these three parameters (Bo, Bg and Rs) are functions of pressure
and can be obtained from correlations mentioned in chapter two, whenever PVT laboratory
data is not sufficient.
Classical black oil formulations are suited for modelling:
(a) Reservoir oil with Rsi < 750 SCF/STB. , where Rsi is initial solution gas oil ratio
(b) Reservoir oil with productions higher than its bubble point pressure (e.g., strong water-
drive, gas-cap-drive, or water-flooded reservoirs). [7]

3.2.2 MODIFIED BLACK OIL MODELS:

These models are referred to as wet gas models, because they honor the vaporized oil that
condenses out of the gas phase. In this approach, new PVT properties are added to the
classical formulations in order to account for the vaporized oil or dropped out liquid [7] and
they include the solution oil gas ratio, rs and the dry gas formation volume factor Bgd. A
useful explanation of the modified black oil formulation is captured by Fig 3.2 [23]

Separator Gas 𝑉𝑉𝑔𝑔�𝑔𝑔, 𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀

in gas phase
Gas phase, Vg (STB)
Stock tank oil
vaporized 𝑉𝑉𝑜𝑜�𝑔𝑔 , 𝑆𝑆𝑆𝑆𝑆𝑆
into gas phase
Separator gas
dissolved in oil
phase 𝑉𝑉𝑔𝑔�𝑜𝑜 , 𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀
Oil phase, Vo (STB)

Stock tank oil in 𝑉𝑉𝑜𝑜�𝑜𝑜 , STB

oil phase

Fig 3.2 Diagram of Modified black oil PVT models. Taken from [23].

The “-“sign on the subscripts indicates surface conditions, while the subscripts g and o
represent gas and oil phases. For the subscripts with two alphabets, the first letter in the

20
subscript is the current state of the substance while the second letter shows the origin of the
substance.
From the diagram above, the volume of the reservoir gas (Vg) is split into a separator gas in
gaseous phase (Vgg) with a condensate or a vaporized oil dropping out of the gas phase (Vog).
Whereas the reservoir oil volume (Vo) is also separated into a separator gas (Vgo) and an oil
phase (Voo).
Moreover comparing Fig 3.2 to Fig 3.1, the new term added is the Vog term, while the terms
Vgo and Vgg are considered the same i.e. the hydrocarbon gas as in Fig 3.1.
Thus,

𝑉𝑉𝑔𝑔�𝑔𝑔 = 𝑉𝑉𝑔𝑔�𝑜𝑜 (21)

Moreover, introducing the volumetric properties of interest that indicate the ratio of the
reservoir to stock tank volumes, PVT parameters used here usually the Rs, Bo, rs, Bgd ,
where[24]
𝑉𝑉𝑔𝑔
𝐵𝐵𝑔𝑔𝑔𝑔 =
𝑉𝑉𝑔𝑔�𝑔𝑔 (226)

𝑉𝑉𝑜𝑜�𝑔𝑔
𝑟𝑟𝑠𝑠 =
𝑉𝑉𝑔𝑔�𝑔𝑔 (3.7)

𝑉𝑉𝑜𝑜�𝑔𝑔, is the stock tank oil produced from reservoir gas and 𝑉𝑉𝑔𝑔�𝑔𝑔 is the volume of surface
gas from reservoir gas. Moreover 𝐵𝐵𝑔𝑔𝑔𝑔 is related to 𝐵𝐵𝑔𝑔 (wet gas formation volume factor) by
the relation
𝐵𝐵𝑔𝑔𝑔𝑔 = 𝐵𝐵𝑔𝑔 × [1 + 𝐶𝐶𝑜𝑜�𝑜𝑜 𝑟𝑟𝑠𝑠 ]
(3.8)

Where, in equation (3.8)

𝛾𝛾𝑜𝑜�𝑔𝑔
𝐶𝐶𝑜𝑜�𝑜𝑜 = 133,000
𝑀𝑀𝑜𝑜�𝑔𝑔 (3.9)

Where, 𝑉𝑉𝑜𝑜�𝑜𝑜 is the stock tank oil from reservoir oil, 𝑀𝑀𝑜𝑜�𝑔𝑔 molecular weight and 𝛾𝛾𝑜𝑜�𝑔𝑔 is the
stock tank oil specific gravity. rs is the term that accounts for the condensate that drops out of

21
the separator gas. The Rs and the Bo terms still maintain same forms as in Equations (3.2)
and (3.4)
If the value of rs =0, then the value of Bgd = Bg which then becomes the classical black oil
formulation.
The modified approach is suitable for modeling all types of reservoirs especially volatile oils
and retrograde condensate reservoirs cause the solution oil gas ratio term helps to account for
liquid drop out [25]and retrograde liquid in the gas stream.[7]

3.3 METHODS IN BLACK OIL PVT MODELING

Presently, many methods have been proposed for modeling black oil properties but the
Walsh-Towler [26] (1995) method, Coats [27] (1985) method and the Whitson-Torps (1983)
[28]methods have gained wide importance over the years. Walsh-Towler suggested a
procedure using material balance to calculate the PVT properties. Their method did not use
equations of state to predict the fluid properties instead it made use of measured quantities
from CVD [26]. Also, Fekete [23] black oil model (2003) made modifications to the Walsh-
Tower method by honoring consistency checks from other experiments like the CCE test in
calculating the black oil properties.[23].
Conversely, Coats method and Whitson method made use of modified (pseudoized) forms of
equation of states to model the fluids. Further details of all the methods mentioned above
could be viewed from reference 26 to 28.
Considering Whitsons [22] method, a reservoir fluid e.g. a condensate with components
ranging from N2, CO2, C1 to C7+, is transformed into three components whereby C5, C6
and C7+ fractions are lumped together as a pseudo component analogous to the non-volatile
oils due to their high molecular weight. Then a second group consisting of C2, C3 and C4
are considered as a second pseudo component which would account for the vaporized oil in
the gas phase. While the last group will contain hydrocarbon gas consisting of + N2, CO2
and C1. (Note the divisions used here are not exactly how Whitson [22] did in his work, but
are illustrated to capture the overall concept. C1, C2 …C7+, refers to hydrocarbons with their
carbon number starting from methane).
Referring to section 2.3, assigning mole percent’s to the above pseudo components will give
values such as y1, y2, y3 and x1, x2 and x3 for the vapor and liquid phase of the three

22
components respectively. Thus for a black oil model, the component 1-2 are referred as the
oil pseudo phase while component 2-3 is the pseudo gas phase.
Moreover, comparing these mole fractions with respect to black oil PVT properties, the
following relationships are relevant:

𝑉𝑉𝑔𝑔�𝑜𝑜 𝑥𝑥3
𝑅𝑅𝑠𝑠 = = 2130 (23.10)
𝑉𝑉𝑜𝑜�𝑜𝑜 𝑥𝑥2 𝑣𝑣2 + 𝑥𝑥1 𝑣𝑣𝑖𝑖
𝑉𝑉𝑜𝑜�𝑔𝑔 𝑦𝑦2 𝑣𝑣2
𝑟𝑟𝑠𝑠 = = (3.1124)
𝑉𝑉𝑔𝑔�𝑔𝑔 2130(𝑦𝑦3 + 𝑦𝑦4 )

𝑉𝑉𝑔𝑔 𝑍𝑍𝑣𝑣 𝑇𝑇�𝑃𝑃 (3.1225)

𝐵𝐵𝑔𝑔𝑔𝑔 = = 0.02827
𝑉𝑉𝑔𝑔�𝑔𝑔 (𝑦𝑦3 + 𝑦𝑦4 )
𝑉𝑉𝑜𝑜 𝑣𝑣1
𝐵𝐵𝑜𝑜 = = (3.1326)
𝑉𝑉𝑜𝑜�𝑜𝑜 𝑥𝑥1 𝑣𝑣1 + 𝑥𝑥2 𝑣𝑣2

Where v is the molar volume, P T and 𝑍𝑍𝑣𝑣 are the pressure, the temperature and the gas
compressibility factor respectively. Therefore if the molar volume of a phase is known as
well as the gas compressibility, at a given temperature and pressure, the black oil PVT
properties could be estimated. Also, flash calculations might be needed to obtain individual
components (i.e. methane, ethane etc.) of vapor and liquid phase compositions. Then mixing
rules are applied to combine them into black oil pseudo forms. (All elements in the above
equation are in field units. Thus the constants 2130 and 0.0287 are conversion factors from
standard unis to field units). Appendix A contains details of a black oil model approach.

3.4 COMPOSITIONAL PVT MODELS

When oil consists of two or more hydrocarbons and those hydrocarbons exhibit distinctly
different phase and composition changes relative to temperature and pressure, a more
complex definition of the fluid behavior is required for reservoir simulation and predictions
of recovery. For example, retrograde gas condensate reservoirs as well as volatile oils and
other gas reservoir systems (e.g. gas cap, solution gas and gas injection) usually exhibit such
variations between their oil and gas compositions. Therefore, the large number of
components in these systems will need a strong formulation which can provide consistent
densities, compositions, and molar volumes. Typically, an equation of state is dully suited
for such a purpose because it is able to account for the fluids phases, the phase equilibria of

23
the phases and also the thermodynamic properties of the compositions of the phases. The
approach to formulating the fluids properties by totally relying on an equation of state to
model the components and thus mix them up to yield a single result for the total mixture is
what is referred to as compositional modeling [29]. Here properties of phases are a function
of not only pressure as in black oil models but also of their composition
This approach usually considers the critical properties of individual pure components present
in a fluid mixture and their overall effect on the system. These properties are entered for each
component, allowing the liquid and vapor phases to be broken down into their constituent
components.
𝑦𝑦𝑖𝑖
𝐾𝐾𝑖𝑖 =
𝑥𝑥𝑖𝑖
� 𝜌𝜌 � = 𝑓𝑓(𝑃𝑃, 𝑥𝑥𝑖𝑖 , 𝑦𝑦𝑖𝑖 )
(3.14)
𝜇𝜇

For instance, the percentage of butane present in the gas phase and liquid phase could be
determined. Equilibrium phase splits and phase properties are determined by blending the
properties of the stream constituents.
Moreover, it is impractical to model every component of a reservoir fluid due to the large
numbers of components that are present. Generally, for acceptable phase behavior prediction,
it is sufficient to specify the mole fractions of the main light end paraffin’s, (typically
methane to decane for black oils) [8]. Heavier components are handled as pseudo or
hypothetical components (a process referred to as pseudoization) [9].
Nevertheless, such a fluid model is more computationally expensive to solve but allows the
hydrocarbons of different compositions to mix during the simulation [2]

3.5 BRIEF OVERVIEW OF SOME THERMODYNAMIC MODELS THAT ARE

SUITED FOR SPECIFIC PURPOSES IN COMPOSITIONAL RESERVOIR
SIMULATION
Since the predictions from a compositional PVT model rely on the type of thermodynamic
model used will thus dictate the nature of the result from such formulations. Presently, there
are many types of thermodynamic models that could be used in reservoir simulators to predict

24
physical properties of the reservoir fluids. These models have been formulated created by
many authors and they can be classified broadly into the following
(a) Activity coefficient models
(b) Equations of state
3.5.1 ACTIVITY COEFFICIENT MODELS
An activity coefficient is a dimensionless factor used in thermodynamics to account for
deviations of ideal behavior in a mixture of chemical substances [30]. The activity coefficient
can be related to the chemical potential for a substance B in a liquid or solid mixture
containing mole fractions xB and xc of substances B, C by the relation below

RTln(𝑥𝑥𝐵𝐵 𝛾𝛾𝐵𝐵 ) = 𝜇𝜇𝐵𝐵 (𝑇𝑇, 𝑃𝑃, 𝑥𝑥) − 𝜇𝜇𝐵𝐵∗ (𝑇𝑇, 𝑝𝑝)

(3.15)

Where μB is the chemical potential of substance B, x denotes the set of mole fractions xB, xC
, … and T and P represents the temperature and pressure of the system at that point.[30]
As models, they are the simplest possible models for the composition dependence of the
phase i-component fugacity fi, representing a standard to which actual behavior may be
compared. Liquid activity methods are based on the following equation for the fugacity of
the ith- component in the mixture.
Mathematically,

𝑓𝑓𝑖𝑖𝑙𝑙
𝛾𝛾𝑖𝑖 =
𝑥𝑥𝑖𝑖 𝑓𝑓𝑖𝑖𝑜𝑜 (3.16)

Where, 𝛾𝛾𝑖𝑖 is the activity coefficient of component i. xi is the liquid phase mole fraction and
𝑓𝑓𝑖𝑖𝑜𝑜 is the fugacity of the pure component which is usually approximated to the vapor pressure
of the pure component, 𝑃𝑃𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠
Thus an activity coefficient of a component can be related to the equilibrium constant by the
relation
𝑃𝑃 𝑦𝑦𝑖𝑖 𝑃𝑃 𝑦𝑦𝑖𝑖 𝑃𝑃
𝛾𝛾𝑖𝑖 = 𝐾𝐾𝑖𝑖 𝑠𝑠𝑠𝑠𝑠𝑠 = 𝑠𝑠𝑠𝑠𝑠𝑠 =
𝑃𝑃𝑖𝑖 𝑥𝑥𝑖𝑖 𝑃𝑃𝑖𝑖 𝑥𝑥𝑖𝑖 𝑓𝑓𝑖𝑖𝑜𝑜 (3.17)

25
For i=1, 2….n, where n is the total number of components.
Ideal solutions i.e. solutions where liquid fugacity of each component is directly proportional
to the mole fraction of each component with activity coefficient equals to unity, assumes that
all molecules interact with the same intermolecular potential but this assumption is only
reasonable for molecules of similar size and type. Most real mixtures tend to deviate from
ideality, thus their activity coefficient is different from unity.
Such models are can handle vapor –liquid systems and also perform well in simulating
asphaltenes, waxes and other solid systems cause they can be used to handle the solubility.
These models also allow the use of binary interaction parameters to alter the predictions until
values are obtained similar to experimental data. A few examples of these models include
Andersen and Speight [31], Chung[32], Yarranton and Masliyah[33], Zhou et al [34]models,
predictive UNIQUAC [35][36], predictive Wilson [37], predictive UNIFAC [38] and regular
solution theory [39].
In general, the approaches taken in determining the parameters of the activity coefficient
model include:
(i) determining the parameters by fitting to experimental vapor liquid equilibrium data on
binary mixtures at a single temperature. E.g. the Predictive Wilsons model
(ii) Determining the parameters by treating the excess Gibbs free energy e.g. the predictive
UNIFAC model.
The former is unable to handle liquid-liquid equilibria or vapor liquid- liquid equilibria while
the latter is capable of performing such equilibria scenarios.
Nevertheless, Al Ghafri [40], showed that the limitations associated with these models are
evident around the critical regions. He proposed that the limitation comes from the fact that
the activity coefficients are defined based on the mixing of liquid components at conditions
of temperature equal to that of the mixture, and so the pure components must be liquid at
those conditions. Also, since these coefficients are not written as explicit functions of
temperature, pressure and composition they do not have the flexibility of equations of state
to calculate densities and other derivative properties.

26
3.5.2 EQUATION OF STATE
An equation of state refers to an analytical thermodynamic expression that describes the state
of matter by relating state variables i.e. pressure, volume and temperature. An example of an
equation of state is the ideal gas equation, which shows how volume and pressure are related
to temperature.
𝑃𝑃𝑃𝑃 = 𝑛𝑛𝑛𝑛𝑛𝑛
(3.18)

Where R is the universal gas constant and n is the number of moles.

However in reality most gases never obey this arrangement (for pressure and volume against
temperature), instead they experience lots of deviations from the ideal. Due to this, different
equations of state where developed to capture the real permutation of pressure and volume
against temperature. Originally, the equations formed where basically created for describing
phase behavior for single pure components, but they have been extended to handle mixtures
[41]. The extension of EOS to multicomponent systems required the use of mixing rules (as
stated in chapter two) to determine the mixture parameters [42]
Currently there are three basic formulations of equations of state used to determine
volumetric properties and vapor liquid equilibrium with respect to hydrocarbon system and
they include the following:
(a) Cubic Equations of state
(b) Higher order equations of state (not discussed in this report)
(c) Perturbed chain and statistical associating fluid theory equations of state
In this report, only the cubic equations of state and their statistical neighbors will be explained
here. Although higher order equations of state might be used in parts of the petroleum system
like pipelines, they will not be discussed because most current commercial reservoir
simulators hardly use them in PVT modeling.

3.5.2.1 CUBIC EQUATIONS OF STATE (CEOS):

These refer to equations of state that where originally developed to account for the non-
ideality of real gases. This non ideal behavior was denoted by a deviation factor, Z (also
referred to as the compressibility) and on solution of this factor, three (cubic) real roots are
usually obtained hence the name cubic EOS.

27
The first person to propose such a relation was Van der Waals (Vdw) [43]. He proposed the
fact that the total pressure of a substance is equal to the difference between the repulsive
pressure element and the attractive pressure element as shown below
𝑃𝑃𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 𝑃𝑃𝑟𝑟𝑟𝑟𝑟𝑟 − 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎
(3.19)

𝑅𝑅𝑅𝑅 𝑎𝑎
𝑃𝑃 = − 2
(𝑉𝑉 − 𝑏𝑏) 𝑉𝑉 (3.20)

Where b is the effective molar volume to correct for volume occupied by the molecules, ‘a’
is the attraction parameter to correct for pressures for attraction of molecules. Although his
relation proved superior to the ideal gas law and does predict the formation of a liquid phase,
the agreement with experimental data is limited for conditions where the liquid forms. Other
modern equations have been developed and have thus replaced the VdW EOS successfully.
Table 3.1 shows the basic formulas for some of these cubic equations of state.
In general, for a compositional simulation, two important equations are paramount which
include the compressibility and the fugacity equation.

𝑍𝑍 = 𝑍𝑍(𝑃𝑃, 𝑇𝑇, 𝑥𝑥)

(3.21)

𝑓𝑓 = 𝑓𝑓(𝑃𝑃, 𝑇𝑇, 𝑥𝑥)

(3.22)

Martin [44] proposed that all cubic equation could be written in the following generalized
way

𝑍𝑍 3 + [(𝑚𝑚1 + 𝑚𝑚2 − 1)𝐵𝐵 − 1]𝑍𝑍 2

+ [𝐴𝐴 + 𝑚𝑚1 𝑚𝑚2 𝐵𝐵 2 − (𝑚𝑚1 + 𝑚𝑚2 )𝐵𝐵(𝐵𝐵 + 1)]𝑍𝑍
(3.23)
−[𝐴𝐴𝐴𝐴 + 𝑚𝑚1 𝑚𝑚2 𝐵𝐵 2 (𝐵𝐵 + 1)] = 0

28
 𝑓𝑓𝑖𝑖
ln 𝜑𝜑𝑖𝑖 = ln � �
𝑃𝑃𝑃𝑃𝑖𝑖
= − ln(𝑍𝑍 − 𝐵𝐵)
𝐴𝐴 2 ∑𝑛𝑛𝑗𝑗=1 𝐴𝐴𝑖𝑖𝑖𝑖 𝑥𝑥𝑗𝑗 𝐵𝐵𝑖𝑖 𝑍𝑍 + 𝑚𝑚2 𝐵𝐵
+ � − � ln (3.24)
(𝑚𝑚1 − 𝑚𝑚2 )𝐵𝐵 𝐴𝐴 𝐵𝐵 𝑧𝑧 + 𝑚𝑚1 𝐵𝐵
𝐵𝐵𝑖𝑖
+
𝐵𝐵(𝑍𝑍 − 1)

Where,
𝑛𝑛 𝑛𝑛

𝐴𝐴 = � � 𝑥𝑥𝑗𝑗 𝑥𝑥𝑘𝑘 𝐴𝐴𝑗𝑗𝑗𝑗

𝑗𝑗=1 𝑘𝑘=1 (3.25)

𝑛𝑛

𝐵𝐵 = � 𝑥𝑥𝑗𝑗 𝐵𝐵𝑗𝑗
𝑗𝑗=1 (3.26)

0.5
𝐴𝐴𝑗𝑗𝑗𝑗 = �1 − 𝛿𝛿𝑗𝑗𝑗𝑗 ��𝐴𝐴𝑗𝑗 𝐴𝐴𝑘𝑘 �
(3.27)

𝑃𝑃𝑟𝑟𝑟𝑟
𝐵𝐵𝑗𝑗 = Ω𝑏𝑏𝑏𝑏
𝑇𝑇𝑟𝑟𝑟𝑟 (3.28)

𝑃𝑃𝑟𝑟𝑟𝑟
𝐴𝐴𝑗𝑗 = Ω𝑎𝑎𝑎𝑎 2
𝑇𝑇𝑟𝑟𝑟𝑟 (3.279)

In Equation (3.21), 𝛿𝛿𝑗𝑗𝑗𝑗 are the binary interaction coefficients (BICS), symmetric in j and k
with 𝛿𝛿𝑗𝑗𝑗𝑗 = 0. For two identical components e.g. N2-N2, the 𝛿𝛿𝑗𝑗𝑗𝑗 is zero. For two different
nonpolar compounds (e.g. CO2-N2) 𝛿𝛿𝑗𝑗𝑗𝑗 is equal to or close to zero. But for a binary pair of at
least one polar component e.g. (N2-CH4), non- zero 𝛿𝛿𝑗𝑗𝑗𝑗 is appropriate [8]. The subscripts j, k
indicate components in the mixture while r represent reduced values. For Redlich-Kwong
(RK) [45], and. Soave-Redlich- Kwong (SRK) [46]. For the PR EOS, 𝑚𝑚1 = 1 + √2 and

29
𝑚𝑚2 = 1 − √2. In describing all the parameters used in the above equation, the Peng
Robinson (PREOS) will be considered. The parameters Ω𝑎𝑎𝑎𝑎 𝑎𝑎𝑎𝑎𝑎𝑎 Ω𝑏𝑏𝑏𝑏 represent the
dimensionless constants (particular to an equation of state) and are universal constants
independent of component identity and temperature. However, in practice they are treated as
functions of temperature and component identity. For PR EOS they are defined by the
following relations,

Ω𝑏𝑏𝑏𝑏 = Ω0𝑏𝑏 (28)

2
Ω𝑎𝑎𝑎𝑎 = Ω0𝑎𝑎 �1 + (0.37464 + 1.5422𝜔𝜔𝑖𝑖 − 0.26992𝜔𝜔𝑖𝑖2 ) �1 − 𝑇𝑇𝑟𝑟𝑟𝑟0.5 �� (3.3129)

Where in equation 3.31 above

(30.32)
Ω0𝑎𝑎 = 0.457235529 and Ω0𝑏𝑏 = 0.077796074

30
Table 3.1: Cubic equation of state with their formula. Table adapted from [55]

Equation of state Model

Van der Waals(VDW EOS) 𝑅𝑅𝑅𝑅 𝑎𝑎

𝑃𝑃 = − 2
(𝑉𝑉 − 𝑏𝑏) 𝑉𝑉

Redlich Kwong[45] (RK EOS) 𝑅𝑅𝑅𝑅 𝑎𝑎

𝑃𝑃 = −
𝑉𝑉 − 𝑏𝑏 √𝑇𝑇𝑇𝑇(𝑉𝑉 + 𝑏𝑏)

Soave [46] RK(SRK EOS) 𝑅𝑅𝑅𝑅 𝑎𝑎𝑎𝑎

𝑃𝑃 = −
(𝑉𝑉 − 𝑏𝑏) [𝑉𝑉(𝑉𝑉 + 𝑏𝑏)]

Peng Robinson [47] (PR EOS) 𝑅𝑅𝑅𝑅 𝑎𝑎𝑎𝑎

𝑃𝑃 = −
(𝑉𝑉 − 𝑏𝑏) [𝑉𝑉(𝑉𝑉 + 𝑏𝑏) + 𝑏𝑏(𝑉𝑉 − 𝑏𝑏)]

Usdin and McAullife (UM EOS) 𝑅𝑅𝑅𝑅 𝑎𝑎𝑎𝑎

𝑃𝑃 = −
[48] (𝑉𝑉 − 𝑏𝑏) [𝑉𝑉(𝑉𝑉 + 𝑑𝑑)]

Stein-Redlich-Kwong [49] EOS 𝑅𝑅𝑅𝑅 𝑎𝑎

𝑃𝑃 = −
(𝑉𝑉 − 𝑏𝑏) [𝑉𝑉(𝑉𝑉 + 𝑏𝑏)𝑇𝑇 0.5 ]

Heyen EOS[50] 𝑅𝑅𝑅𝑅 𝑎𝑎

𝑃𝑃 = − 2
(𝑉𝑉 − 𝑏𝑏) (𝑉𝑉 + (𝑏𝑏 + 𝑐𝑐)𝑉𝑉 − 𝑏𝑏𝑏𝑏)

Kubic EOS [51] 𝑅𝑅𝑅𝑅 𝑎𝑎

𝑃𝑃 = −
(𝑉𝑉 − 𝑏𝑏) (𝑉𝑉 + 𝑐𝑐)2

Adachi and Lu (AL EOS) [52] 𝑅𝑅𝑅𝑅 𝑎𝑎

𝑃𝑃 = − 2
(𝑉𝑉 − 𝑏𝑏) 𝑉𝑉

Patel and Teja (PT EOS) [53] 𝑅𝑅𝑅𝑅 𝑎𝑎𝑎𝑎

𝑃𝑃 = −
(𝑉𝑉 − 𝑏𝑏) [𝑉𝑉(𝑉𝑉 + 𝑏𝑏) + 𝑐𝑐(𝑉𝑉 − 𝑏𝑏)]

Schmidt and Wenzel (SW 𝑅𝑅𝑅𝑅 𝑎𝑎𝑎𝑎

𝑃𝑃 = − 2
EOS)[54] (𝑉𝑉 − 𝑏𝑏) [𝑉𝑉 + (1 + 3𝜔𝜔)𝑏𝑏𝑏𝑏 − 3𝜔𝜔𝑏𝑏 2

. All the equations of state are arranged like the Van der Waals equation or similar to equation
(3.20). The term 𝜔𝜔 is the acentric factor. The acentric factor is a measure of the sphericity of
a molecule and has it values usually between zero and one (spherical molecules have acentric
factor of one) [56]. It is important to note that these equations of state where created for single

31
components but can be extended to multicomponent mixtures by using mixing rules as stated
in chapter two.

The SRK and PR equations have gained wide acceptance over the years in fluid modeling
but PR is more accurate than the former in regions around the critical point. Nevertheless
they both do not accurately account for the liquid density. To handle this problem (liquid
density prediction), Martins introduced the concept of volume translation to improve the
volumetric prediction. Peneloux et al [57] used the volume translation or shift to improve
the SRK EOS volumetric predictions while Jhaveri and Youngren [58] extended Peneloux
work to the PR EOS.

Presently in the reservoir simulation, PR and the SRK and their modifications have been
widely accepted for used in fluid PVT modeling because they yield good results over a wide
range of conditions. However, Ahmed [55] performed suitable comparisons on eight cubic
equations and he outlined their performance capabilities in his work. He concluded that
SWEOS exhibits suitable predictive capability for gas condensate systems, PT and SW
equations are found to predict reliable gas compressibility factors while the PR, PT and SW
equations yield good Vapor liquid equilibrium predictions.

3.5.2.2 PERTURBED CHAIN AND STATISTICAL ASSOCIATING FLUID

THEORY EQUATIONS OF STATE:
Simple molecules with prevalent intermolecular forces being those of attraction and
repulsion (e.g. the Van der Waals force and weak electrostatic forces) can be modelled
successfully by means of a cubic equation of state. Most hydrocarbons fall within this
category, thus making the wide use of cubic equations of state for their modelling. However,
mixtures containing strong intermolecular forces like hydrogen bonds, complex electrolytes,
polar solvents and polymers cannot be accurately described by both cubic equations of state
and even activity coefficient models. The non-ideality in such systems do require more
advanced associating fluid theories to handle them [40]. These theories usually account for
the chemical reactions that forms distinct associating chemical species.

32
Associating fluid theories are be broadly classified into two types which include: integral
equations models and perturbation models. The integral models considers molecular
associations as strong symmetrically spherical attractive forces. On the other hand, the
perturbation theories consider a reference fluid with known thermodynamic properties and
relates it to an unknown fluid by mean of a correction or perturbation term.(Moreover, this
report will be restricted to just the perturbation models and as such integral models will not
be discussed further) .
Statistical perturbation models are based on the principle that the potential energy of a
relative complex molecular fluid can be described as the sum of the potential energy of a
simple known reference fluid (e.g. a hard sphere term) and a correction term [59]. Once this
correction term exists as a function of pressure temperature or density and composition then
other thermodynamic relations could be derived for the physical and derivative properties
[59].
Previously, the hard sphere system usually was adopted as the reference term but it was later
considered not reliable because it was did not regard chain length (a key feature that affects
the fluid structure). Thus, it is inappropriate for modelling mixtures with highly non-spherical
associating terms. A more appropriate reference term that considers both chain length and
molecular attraction was then sorted after. Wertheim [60] and Chapman [61] proposed a
method whereby molecules are treated as different species with respect to the number of
associating sites that are bonded together. The latter also extended the principle to modelling
molecules as chains of spherical segments (divided monomers) that interact through evenly
dispersive and repulsive forces. This proved to be the basis of the statistic associating fluid
theories (SAFT).
SAFT models are commonly written as summations of the residual Helmholtz free energy
terms that occur due to differences in molecular interactions of pure components in the
system [59]. They usually employ the Helmholtz energy term because a differentiation of it
could yield properties of interest such as pressure, isothermal compressibility coefficient,
isobaric heat capacity and so on [62]. For a system consisting of associated chains, the SAFT
equations can be expressed as

33
 𝐴𝐴𝑟𝑟𝑟𝑟𝑟𝑟 𝑎𝑎𝑟𝑟𝑟𝑟𝑟𝑟 (𝑇𝑇, 𝜌𝜌) 𝐴𝐴𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝐴𝐴𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝐴𝐴𝑐𝑐ℎ𝑎𝑎𝑎𝑎𝑎𝑎 𝐴𝐴𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎
= = + + + (3.33)
𝑁𝑁𝑘𝑘𝐵𝐵 𝑇𝑇 𝑘𝑘𝐵𝐵 𝑇𝑇 𝑁𝑁𝑘𝑘𝐵𝐵 𝑇𝑇 𝑁𝑁𝑘𝑘𝐵𝐵 𝑇𝑇 𝑁𝑁𝑁𝑁𝐵𝐵 𝑇𝑇 𝑁𝑁𝑘𝑘𝐵𝐵 𝑇𝑇
Where,

N is the number of molecules and 𝑘𝑘𝐵𝐵 is the Boltzmann’s constant. “a” is the Helmholtz free
energy per mole and the superscripts res, ideal, mono, chain and assoc refer to residual, ideal,
monomer reference fluid (e.g. hard sphere), chain dispersion and association respectively,
𝐴𝐴𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 is the ideal free energy of the fluid to which three residual contribution are added: the
monomeric contribution (𝐴𝐴𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 ) due to the repulsion-dispersion segment-segment
interactions; the contribution due to the chain formation (𝐴𝐴𝑐𝑐ℎ𝑎𝑎𝑎𝑎𝑎𝑎 ) and the contribution that
takes into account the short range intermolecular association (𝐴𝐴𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 ).

Different possible choices for the reference fluid has given rise to lot of SAFT versions.
Examples of these versions include: the Statistical Associating Fluid theory (SAFT) model
developed by Wertheim [60, 63, 64] , Huang-Radosz (HR- SAFT also called CK-SAFT)
[65], SAFT-VR (Variable Range) [66] , simplified SAFT [67], SAFT-LJ (Lennard-Jones)
[61] and the Perturbed Chain statistical Associating fluid theory (PC-SAFT) model
developed by Gross and Sadowski [68, 69]. In the next lines details of PC-SAFT model
would be discussed since it is a modification of the SAFT model. PC-SAFT usually employs
a hard sphere reference system as opposed to a monomer reference fluid. The PC-SAFT
model can be expressed in terms of compressibility factor, Z as

𝑍𝑍 = 1 + 𝑍𝑍 ℎ𝑐𝑐 + 𝑍𝑍 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 + 𝑍𝑍 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 (3.34)

Where superscripts hc is the contribution hard chain part, assoc and disp give the respective
contribution from the association and dispersion terms. The contribution from the ideal term
is 1, thus 𝑍𝑍 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 = 1. Moreover for two pure components parameters with association sites
𝐴𝐴𝑖𝑖 and𝐵𝐵𝑗𝑗 , the characteristic energy ∈ , determining their association interactions is given by

1 𝐴𝐴 𝐵𝐵
∈𝐴𝐴𝑖𝑖 𝐵𝐵𝑗𝑗 = (∈ 𝑖𝑖 𝑖𝑖 +∈𝐴𝐴𝑗𝑗𝐵𝐵𝑗𝑗 ) (3.35)
2

34
While the association volume k is

9
�𝜎𝜎𝑖𝑖𝑖𝑖 𝜎𝜎𝑗𝑗𝑗𝑗
𝑘𝑘 𝐴𝐴𝑖𝑖 𝐵𝐵𝑗𝑗 = �𝑘𝑘 𝐴𝐴𝑖𝑖 𝐵𝐵𝑖𝑖 𝑘𝑘 𝐴𝐴𝑗𝑗𝐵𝐵𝑗𝑗 � � (3.36)
1� �𝜎𝜎 + 𝜎𝜎 �
2 𝑗𝑗𝑗𝑗 𝑖𝑖𝑖𝑖

𝐴𝐴𝑖𝑖 𝐵𝐵𝑖𝑖�
Where 𝜖𝜖 𝑘𝑘 and 𝑘𝑘 𝐴𝐴𝑖𝑖 𝐵𝐵𝑖𝑖 are the effective association energy and effective association
volume. 𝜎𝜎 is the monomeric segment. Equation (3.35) and (3.36) shows the relationship
between the characteristic energy, the monomeric segment, and the association volume.
According to Senol [62] , perturbation in PC-SAFT applies to connected chains for the hard
sphere segment rather between disconnected segments. This approach is similar to
considering attractive (dispersion) interactions between connected segments which could
really represent the behavior of hydrocarbons and polymers in solution. The PC-SAFT
equation of state model is capable of predicting thermo- physical properties and also vapor-
liquid equilibriums for virtually different types of mixtures ranging from associated to non-
associating components as well as others mentioned above. However, for a system to be
modeled with it, the segment number, diameter and energy of the pure component must be
estimated and validated for a certain range of pressure and temperature. [62]

Al Ghafri [40] outlined generalized requirements for SAFT models and they are
(1) SAFT models requires a minimum of two parameters, the characteristic energy, ∈ and the
monomeric segment 𝜎𝜎
(2) A third parameter for the number of segments per molecule, m is required to describe the
non-sphericity of the fluids.
(3) For associating fluids, two additional parameters must be assigned to characterize both
the association energy and the volume available for bonding.
(4) For each additional specie the associating sites and their bonding correspondence (site
which to bond with) must be defined.
(5) Parameters for new systems can be estimated from those of previously modelled systems.
(6) Mixing rules are needed in the dispersion term while combining rules are needed for the

35
segment energy and volume parameters where a correcting interacting parameter 𝑘𝑘𝑖𝑖𝑖𝑖 is often
used similar to binary interaction parameter in CEOS.

3.6 OTHER MODELS: THERMAL MODELS

A Thermal PVT model refers to a special kind of compositional model developed to
accommodate temperature variation [70]. It is suited for system involving non isothermal
temperature such as heavy oil recovery, water flooding, steam, air and other chemical
injection. Not only do they allow temperature variation, they also account for pressure and
phase changes effects during simulation [29].
The EOS used in this models are usually tuned with distillation or other separation data. This
is imperative because additional pressure volume temperature requirements like density,
viscosity and even K-values have dependence on the temperature.[71]. Further details of
thermal models can be viewed in reference (73).

3.7 REGRESSION-TUNING AND CHARACTERIZATION

It is important to note that all equations of state, activity coefficient models, black oil models
and even thermal models are not overly accurate formulas and thus work needs to be done in
aligning them to suit laboratory observed data.[70] To achieve this, regression is applied to
match the models parameters to closely represent the experimental data in such a way that
deviations between the measured and simulated data are eliminated [8] . Typically in a
reservoir simulation, a non- linear regression model with a Chi-squared distribution test
might be employed to ensure a good fit.
Parameters of compositional models that render themselves suitable for regression include
the critical parameters (i.e. Critical pressure, critical Temperature, Critical Volume), Acentric
Factors, omega A and B (in cubic equations of state) Binary interaction coefficient and
Volume shift factors. While for black oil models, their correlations are the ones suited for
regression [70]. . Conversely from experimental data parameters such as saturation points,
gas phase compressibility factors, liquid drop outcurves or liquid phase densities at reservoir
temperature as well as gas oil ratios are usually the data aimed at matching. Christensen [8]
proposed a procedure for regression capable of obtaining match to PVT data properties.
It is also necessary to note that the number of regression parameters must not exceed the

36
number of data points or observations. Thus, for a given number of n experimental
observations,
𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 2
𝑟𝑟𝑗𝑗
𝑂𝑂𝑂𝑂 = � � � (3.37)
𝑤𝑤𝑗𝑗
𝑗𝑗=1

𝑂𝑂𝑂𝑂𝑂𝑂𝑗𝑗 − 𝐶𝐶𝐶𝐶𝑗𝑗
𝑟𝑟𝑗𝑗 =
𝑂𝑂𝑂𝑂𝑂𝑂𝑗𝑗 (31)

𝑛𝑛𝑛𝑛𝑛𝑛 = 1 + ln(𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛) (3.39)

Where OB is the objective function to be minimized during regression calculation, OBS is

the experimental observations used in the regression, CC is the calculated observation, wj is
the weight factor for the j- observation, rj is the residual observation of the jth term and nPR
is the number of regression parameters [8].
Moreover, in laboratory analysis of reservoir fluids, heavy hydrocarbons are lumped together
+
and classified as a plus fraction, 𝐶𝐶𝑛𝑛+ e.g. (𝐶𝐶7+ 𝑜𝑜𝑜𝑜 𝐶𝐶10 ). Nevertheless, using this plus fraction
in analysis could lead to inaccuracies in predicting PVT properties because only few data
such as molecular weight and specific gravity of these pseudo fractions are usually reported.
A true boiling point analysis for single carbon number (SCN) groups by distillation usually
annihilates such problems but since it is rarely available in most PVT reports other techniques
had to be developed. Amongst others, two modern techniques have been widely used to
perform this split. The first, proposed by Whitson [72, 73] and the later by Behrens and Sadler
[74]. The former uses a probability density function to split up the plus fractions and regroup
them into multiple carbon number groups (MCN) with various averaging techniques. While
the latter employed semi-continous thermodynamic approach and has gained wide
acceptance in the petroleum industry. Continous thermodynamics theory is based on
representing a fluid mixture with identifiable, discrete components while also using a
continous distribution function to represent the remaining components in the mixture.[9]

3.8 CHOOSING A FLUID PVT MODEL

The decision of using a black oil PVT model over a compositional model or vice versa might
prove to be worthwhile or even turn out to be detrimental. However, Schlumberger’s PVTi
[70] had outlined some consideration that will aid the decision making process and full details

37
will be given in reference. Moreover, Fevang et al [75] proposed some guidelines in for
choosing black oils models or compositional models in volatile oils and retrograde
condensate systems. (Further details of these guidelines could be viewed from reference 66)

3.9 CHAPTER SUMMARY

There fluid modeling process in reservoir simulation might be approached by using either a
black oil formulation or a fully compositional model. Black oil models tend to approximate
the physical properties of the fluid as functions of only pressure, while the compositional
models honor the fluid compositions as well as the pressure in defining the fluids physical
properties. Regression-tuning and characterizing of the hydrocarbon heavy end is also
necessary in ensure quality results from the simulator.

38
CHAPTER FOUR

4.1 FLUID PVT MODEL

The major task here is to develop a phase behavior PVT model. The model was developed
by assembling all the ideas in the previous chapters to model PVT properties for reservoir
simulation. The design of the model is suited for gas condensate and volatile reservoirs with
sufficient data from a flash separation test.

4.2 MODEL DESCRIPTION

The proposed fluid PVT model has been developed using Matlab software. The workflow
begins with obtaining classical black-oil PVT properties (GOR, specific gravity and
molecular weight), which is based on standard PVT laboratory results such as chromatograph
separation analysis. Then combining the data from the separation and describing the fluid
behavior with an equation of state. After that, black oil PVT properties are then calculated
from the model and other test scenarios could be considered.
Moreover the designed routines for the model are classified into three modules which include
(1) A Recombination module (RC)
(2) A Flash Module (FM) and
(3) A Black oil PVT properties calculator (BC) module
In a nutshell, the recombination module accepts inputs such as composition from a separation
test (which are usually split into gas and liquid compositional streams) and gas oil ratio of
separator and stock tank, and then combines them to form an original reservoir stream. The
flash module then performs vapor- liquid equilibrium calculations on the recombined stream.
Then the black oil calculator calculates black oil properties

4.3 MODEL ARRANGEMENT

4.3.1 RECOMBINATION MODULE (RC)
(a) Input parameters: The input parameters for the recombination module include the
following: Separation gas and liquid compositions, Specific gravities of heavy fractions,
surface Gas gravity (separator and stock tank) , API gravity of tock tank oil, GOR of separator
and stock tank oil, Molecular weight of heavy fractions, reservoir and surface(both separator
and stock tank) pressures and temperature.

39
(b) Output parameters: Specific gravity of oil, average molecular weight gas molecular
weight, total molecular weight of reservoir stream, total reservoir specific gas gravity, vapor
and liquid phases of reservoir well stream. Elmabrouk’s [76] bubble pressure, Standings [77]
bubble pressure, and vapor mole fraction of reservoir fluid and well stream or recombined
composition of the reservoir fluid (i.e. zi as used in chapter two). Also the recombination
module is responsible for splitting the heavy fractions of the fluid mixture to three to five
pseudo fractions. It uses Whitson method stated in chapter three to perform this operation.
Outputs from here include the critical properties (acentric factor, critical temperature,
pressure and volume) of the pseudo fractions, the molecular weights and the mole fractions
of each fraction.

4.3.2 FOR FLASH MODULE:

(a) Input parameters: Input data here consists of vapor mole fraction (same as Fv in chapter
2) from recombination modules, Elmabrouk’s bubble pressure, Nemeth’s dew point pressure,
reference pressure, temperature, recombined composition, critical properties, binary
interaction coefficients (estimated from Chueh-Prausnitz [78] correlation for hydrocarbon
interactions and from Whitson’s [7] Monograph for non-hydrocarbon systems) and. Peng-
Robinson[47] Equation-of-State (PR EOS, 1976) is used to calculate Pressure-Volume-
Temperature (PVT) relationship of the reservoir fluid
(b) Output parameters: The output from flash subroutine consists of number of phases,
bubble point pressure, dew point pressure, molar fraction, composition, molecular weight,
compressibility factor, density, fugacity, density and viscosity of each fluid phase.

4.3.3 FOR BLACK OIL PVT MODULE:

(a) Input parameters: Data to be inputted here involve pressure values to compute the black
oil values, output and input values from the recombination module, temperature range.
(b) Output parameters include: Elmabrouk bubble pressure, Standings bubble pressure,
Glaso bubble pressure, Petrosky and Farshad [79] formation volume factors for oil,
Beggs[80] viscosity for oil and gas, Glaso [81] GOR. (For proper details of each models
algorithm see Appendix A.4).

40
4.4 FLUID MODEL VALIDATION
To validate the model, a gas condensate sample from Gulf of Mexico, USA M-4/M-4A
reservoir taken from reference 9 [9] was used. Results gotten from the recombination module
(RM) and flash modules (FM) where compared with Multiflash Infochem results. Multiflash
infochem (2013) is a recent commercial PVT modelling software created by Infochem
Computer services ltd. Multiflash is a fully integrated toolkit with multiple equations of state
(ranging from cubic, higher order to statistical equations of state). This feature enabled it to
be adopted by lots of oil companies adopted it for PVT modeling. However, it does not pay
much attention to black oil modelling therefore another thermodynamic package was chosen
for comparing the output from the black oil model. PVTP (2013) fluid thermodynamics
package (created by Petroleum Experts) was chosen for this purpose, since it honors black
oil as well as compositional modelling approaches. It is imperative to note that PVTP has
only two equations of state (SRK and PR equation of state without their variations) and does
not show vapor liquid equilibrium splits, thus is not considered suitable for comparing the
flash module.

4.5 MODEL RESULTS

This section shows the results from each module tabulated alongside the results from
commercial software and also the laboratory results
4.5.1 RECOMBINATION MODULE (RC)
(a) Results from a Heptane fraction split

Table 4.1 Heptane plus Characterization (pseudo Fraction split)

PSEUDO FRACTION Pc (pa) Tc (K) MW ω Tb (K)

RECOMBINATION MODULE (RC) PSEUDO FRACTION
PS-1 2982327.26 573.44 106.47 0.30 386.58
PS-2 2005615.95 688.33 171.85 0.48 500.25
PS-3 1227059.95 863.00 310.92 0.83 688.39
-------------------------- MULTIFLASH FLASH PSEUDO FRACTION ---------------
PS-1 3010000.00 593.73 114.44 0.38 408.18
PS-2 2540000.00 656.04 149.00 0.46 465.25
PS-3 2380000.00 677.02 163.00 0.50 486.32

41
The table above shows a list of the critical values for the pseudo fractions pseudo fractions
PS-1, PS-2, and PS-3 pseudo fractions for a heptane characterization with Gaussian
quadrature (Whitsons [7] method). Where Pc- critical pressure in psi, Tc is the critical
temperature in (K), MW is the molecular weight, ω is the acentric factor while Tb is the true
boiling temperature (K).
Table 4.1 Range between values From RC Module and Multiflash

Range (Pc) Range (Tc) Range(MW) Range(Ac) Range(Tb)

PS-1 27672.739 20.2855097 7.97 0.08284 21.6026088
PS-2 534384.055 32.2933884 22.85 0.01296 35.00004
PS-3 1152940.047 185.979137 147.92 0.32477 202.068944
PS-1 27672.739 20.2855097 7.97 0.08284 21.6026088
Mean 571665.6137 79.51934503 59.58 0.14019 86.22386427
range
Table shows the deviation of values of RC model to Multiflash critical values in table 4.1
Range refers to the absolute range between the values of the critical parameters in Multiflash
to the RC model. Mean range is reported as a single value for easy analysis

(b)
Table 4.2 Comparison from RC module recombination with Multiflash results

LAB MULTIFLASH RC MODULE

RECOMBINATION RECOMBINATION RECOMBINATION
component Mole Component Mole percent component Mole
percent percent
N2 0.19 N2 0.19274309 N2 0.19553
CO2 0.93 CO2 1.1159177 CO2 0.93023
CH4 88.01 CH4 87.158423 CH4 88.701
C2 5.3 C2 6.2681336 C2 5.297
C3 1.82 C3 2.2325292 C3 1.7849
i-C4 0.42 i-C4 0.5028291 i-C4 0.39909
n-C4 0.5 n-C4 0.57266648 n-C4 0.47533
i-C5 0.23 0.15866919 i-C5 0.21249
n-C5 0.19 C5 n-C5 0.16802
C6 0.24 C6 0.14580306 C6 0.2136
C7+ 2.17 C7+ 1.6522855 C7+ 1.6226
The table indicates comparative result between the laboratory , Multiflash and the RC
Module recombination

42
Table 3.4: Absolute average error from measured lab recombination

Component Multiflash (AARE)i RC MODULE (AARE)i

NITROGEN 1.443731579 2.910526316

CO2 19.99115054 0.024731183
METHANE 0.967591183 0.785138052
ETHANE 18.2666717 0.056603774
PROPANE 22.66643956 1.928571429
ISOBUTANE 19.72121429 4.978571429
N-BUTANE 14.533296 4.934
C5 62.22162143 19.18146453
C6 39.248725 11
C7+ 23.85781106 25.22580645

TOTAL 222.9182523 71.02541316

AARE (%) 20.26529567 6.456855742

Calculating the Absolute Average Error (AARE) for both Multiflash and RC module.
The numbers in each row represent the individual average error for each row while the
absolute average error is calculated based on equation
𝑛𝑛
1 |𝐶𝐶𝐶𝐶 − 𝑀𝑀𝑀𝑀|
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 = � × 100
𝑛𝑛 𝑀𝑀𝑀𝑀 (4.1)
𝑖𝑖=1

Where ,
n is the number of items, CC is the calculated property and MP is the measured property. The
AARE helps to check the magnitude of errors in a set of results

4.5.2 FLASH MODULE (F-M): The recombined sample from the laboratory was flashed
at standard conditions and the Vapor–liquid equilibrium phase envelop (Pressure
Temperature diagram) plotted on Multiflash (see diagram in Appendix B.3). Whereas the RC
modules recombined sample was flashed with the F-M module and also the phase envelop
plotted on Matlab. The result of the phase envelop is shown below. (for results of the flashing
splits see Appendix B.2)

43
 PHASE DIGRAM OF RC MODULE SAMPLE FROM F-M MODULE FOR

CP GAS

2500

2000
Pressure, psia

1500

1000

X: 246.5
Y: 588.8

500

-100 -50 0 50 100 150 200 250

CT
Temperature, F

Figure 4.1 phase envelop of fluid mixture frrom F-M module

Diagram for gas mole equals to 1. The Cricondentherm and Cricondenbar values
predicted here where 246.5oF and 2830psia respectively.

4.5.3 BLACK OIL PVT CALCULATOR MODULE (BC): Results from this module are
tables with black oil properties. However further work was done to devise their critical values
and combine these surface terms to relate to reservoir terms to be used in the flash module.
Table showing black oil PVT properties developed with regard to correlations (see
appendices for list of correlations)

44
Table 4.5: Black oil PVT parameters from PVTP and BC module

Tempe Press Gas FVF Gas Gas OIL Oil Oil

rature (psia) (ft3/scf) Visco Density, FVF, Visco, Density,
(F) (cp) (lb/ft3) (rb/stb) (cp) (lb/ft3)
PVTP BLACK OIL OUTPUT
267 1155 0.0166737 0.015771 0.001041 1.2527 0.3264 4.3E+10
267 2000 0.0094481 0.017425 0.000589 1.4190 0.2678 2.83E+03
267 6000 0.0037528 0.028207 0.000234 2.6160 0.1506 14.4E+05
267 8000 0.0032118 0.034301 0.000201 3.4525 0.1218 6.9E+09
267 9912 0.0029365 0.040875 0.000183 1.2089 1.0214 5.1E+12
267 12688 0.0026804 0.047135 0.000167 1.2089 1.0215 3.7E+15

BC MODULE RESULTS
267 1155 0.02396 0.0049 0.001983 1.2639 0.6039 171.50
267 2000 0.009871 0.0052 0.004814 1.3401 0.5602 198.08
267 6000 0.003886 0.0058 0.012229 1.8936 0.4505 217.21
267 8000 0.003326 0.0059 0.014288 2.3433 0.4193 198.19
267 9912 0.002996 0.0061 0.015862 2.945 0.3959 172.98
267 12688 0.002726 0.0062 0.017433 4.3136 0.3693 131.71
The table shows a comparison between the black oil PVT results from PVTP with those from
BC module.
black oil model for the reservoir wellstream fluid
700

600

500

400
pressure, psia

300

200

100

0
0 100 200 300 400 500 600 700

temp, F

Fig 4.2: Black oil model for reservoir wellstream: Cricondentherm: 602.31F,
Cricondentherm: 683.633psia: here recombined wellstream was modelled with a modified

45
black oil approach (see appendix A.4 for full algorithm) fluid was modelled with a
conventional black oil

Hypothetical pseudo black oil model envelop with gaussian distribution for two pseudo components
1000

900

800

700

600
pressure, psia

500

400

300

200

100

0
0 100 200 300 400 500 600 700

temperature, F

Fig 4.3: Hypothetical black oil model with Gaussian quadrature

Cricondentherm: 607.71F, Cricondenbar 996.848 psia: A hypothetical black oil model was
develop by means of a Gaussian quadrature. Here the reservoir recombined stream is split
into two with the same technique Whitson proposed for in splitting heavy fractions (Note no
regression was performed).

4.6: ANALYSIS AND DISCUSSION

The three modules formed were all created to ensure that the mathematical model (equations)
that describes the fluid is consistent and reliable. The first module (Recombination module)
aimed at recombining the different phase of a fluid back to its original reservoir composition
with a consistent formulation. The underlying principle for recombination (see full algorithm
in appendix a) was a reverse black oil modelling approach. This reverse black oil modelling
approach makes use of the solution gas oil ratio at separator and stock tank, the specific
gravities of the gas and oil phases at the surface and the molecular weight to recreate the
reservoir stream. The major drive in using this means is to develop the initial vapour mole
fraction (FV), and the saturation pressure (both bubble and dew point pressures) from

46
correlations that would be plugged into the next module the F-M module. The presumption
here is that the initial Fv value is supposed to be closed to the Fv value that would be returned
from the Rachford- Rice solution in the F-M module (The Rachford rice solution usually
requires an initial guess for the start of the iterative process as mentioned in chapter two with
initial guesses sometimes far from the actual value). Thus this method aims at reducing the
amount of iterations to be performed at this stage, (considering a cell in the reservoir
simulator). From the R-C module, recombination yielded an initial Fv value of 0.977 which
was plugged into the Flash module and the final Fv value returned was 0.98 after performing
just two iteration (using Newton Raphson’s process). Therefore this method is able to achieve
convergence for Fv in short time.
Moreover, considering other aspects of the recombination module which include solving for
saturation pressures by updating saturation pressures gotten from correlations(for bubble
point pressure: Elmabrouk or Standing pressure is used, whereas for dew point pressure
Nemeth and Kennedy dew point pressure is used). The recombination module yields the
saturation pressure (by using correlations) which is then passed on to the Flash module (FM)
for updating. The Flash module uses this inserted pressure value as the guess pressure for the
bubble point or dew point pressure calculation. Such calculation of saturation pressure where
employed in phase envelop plotting. The phase envelop plots took a calculation time of was
less than a second to complete plot. Thus method is consider to be employed in
thermodynamics modelling of reservoir fluids in reservoir simulators.
An important feature to also consider is the nature of the result from the first two modules.
In comparing the results to Multiflash prediction, for pseudo splitting of heavy fractions the
linear deviations (as shown in table 4.2) of the RC model values was not considerably far
since the only the critical pressures where the only parameter with wide deviation. This
deviation is possibly due to the method used in split. (The RC-module uses a Guassian
quadrature or Whitsons method for splitting as shown in appendix A.2).
Moreover, the values of the calculated wellstream (from RC module) where compared to
Multiflash result and the original recombination from the PVT laboratory. The RC-modules
had an absolute average error value of about 6% from the original laboratory data while the
Multiflash module had an AARE value of 20.2% (see Table 4.4 above). Thus, the RC-module
predicts the reservoir wellstream composition with more accuracy than Multiflash.

47
Multiflash has this deviation from the laboratory sample because it uses few data points (i.e.
CO2, H2S N2, and C1 to C4) in developing its recombined fluid, (a feature properly accounted
for in the R-M module).
For the flash module, the value of the Cricondentherm and Cricondenbar are 246.5oF and
2830 psia respectively on the phase envelop (Pressure –Temperature diagram) for the
mixture. The value is comparative to the original reservoir mixture from the laboratory which
had 195.931oF and 2388.1 psia respectively. The little deviations comes from the
recombination average absolute error. Thus signifying that the models where suitable for
representing the fluid behavior.
Furthermore, output results from the black oil module are based on internal correlations and
the values it predicted for the PVT properties were close in some cases to the values from
PVTP. Wherever the values where similar to those from PVTP, it is assumed that the
correlation used is similar or the same. Also, it found that some correlations underestimate
values and thus they require regression. For instance the Nemeth correlation for dew point
yielded a value of approximately 6000psia which was far less than the dew point of the
system (9912 psia).
Moreover, the BC module was used to test a hypothetical formulated fluid to a modified
black oil model fluid. The hypothetical fluid was formed based on Whitson [7] heavy fraction
split which utilizes a Gaussian distribution (pseudo split) to break a component into
subsequent fractions. Here the hydrocarbon from the wellstream is considered as a single
mixture and is then broken down into two pseudo fractions (a hypothetical oil and gas
stream). Then critical properties are calculated for each stream so that they can be modelled
with an equation of state.(see Appendix A.2 for full algorithm)
To test the resemblance of this hypothesis with a modified black oil model. The phase
envelop was considered so as to see the volumetric behavior of the two fluids. The results of
the test showed for the hypothetical fluid a Cricondentherm and Cricondenbar of about
607.71oF, Cricondenbar 996.848 psia (see fig 4.3) whereas the modified black oil fluid had
a value of 602.31oF, 683.633psia (see Fig 4.2) respectively. Thus, indicating that the
deviation between the two models (hypothetical and modified approach) are not quite far.
Further adjustments to the pressure might be needed in the hypothetical model

48
4.7 SOURCES OF POSSIBLE ERRORS
The possible errors considered were errors that regression analysis would solve such as
differences in the binary interaction coefficients (BICs) and other critical parameters.
Moreover, to avoid large deviations, the BICs values where not set at zero instead their values
were taken from a text while for hydrocarbon to hydrocarbon interactions they were
calculated using the Prausnitz [78] equation. Moreover since these models did not honor
regression on the overall, the values from the flash module cannot be used directly in
simulator cell.

4.8 CHAPTER SUMMARY

The following points could be derived from this chapter
(1) The Recombination modules were used to ensure a close to accurate representation of the
reservoir fluid as well as develop possible values for the Rachford Rice equation
(2) The Flash module helps to update saturation pressure values gotten from correlations
(3) Black oil calculator modules capability usually rely on the type of correlation used
(4) Guassian quadrature (using Whitsons Characterization method) could be hypothetically
used to replace the modified black oil approach
(5) Regression analysis is key to the success of any model in order to ensure that errors in
predictions are reduced.

49
 CHAPTER FIVE

5.1 CONCLUSION
A phase behavior model able to perform analyses and also to reduce computational time in a
simulation was developed. The model proved capable of predicting phase equilibrium on a
gas condensate sample.
The proposed model formulated with three routines modules on Matlab software had each
module created for a define purpose. The first routine yielded a recombination sample from
separation analysis that was close to the actual reservoir samples composition. Moreover it
furnished the initial value of the vapour mole fraction Fv that would be used for flashing the
reservoir mixture at any time. This proves to be vital in reducing the number of iterations
would performed by the simulator in obtaining the vapour mole fraction. Thus helping in
reducing computation time for compositional modelling.
The second module was created for flashing reservoir fluids mixtures to obtain their vapour
and liquid fractions. However this module coupled with results from the first module
provided a means of updating saturation pressures (both bubble and dew points) predicted
from correlations.
Moreover, the third module predicted the PVT properties of the gas condensate sample. This
module also showed that using Gaussian quadrature means as predicted by Whitson could be
a possible replacement for the black oil modelling approach. Since its output was similar to
the output from of the black oil model.
5.2 RECOMMENDATION
The following are the recommendations proposed for future works with this model
(i) A recombination module formulated by the means above will be helpful in reducing
iteration time in cells during simulation. Also, obtaining proper predictions of saturation
pressures by updating a correlated bubble point or dew point (using such techniques as in the
flash module) when using a black oil modelling approach...
(ii) The proposed method of splitting hydrocarbon phases by means of a pseudo split (i.e
same method Whitson proposed for characterizing heptane’s C7+) should be further tested
for its accuracy. If found consistent (i.e. to resemble the modified back oil method closely)
could replace the Modified black oil model approach and could provide other dimensions for
applications of black oil models.

50
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61
APPENDIX A

A ALGORITHM FOR THE THREE MODULES

(A.1) RECOMBINATION MODULE

(A) STEP 1: START
STEP 2: Input the following
(i)Compositions of separator gas (ysp) and oil (xsp) taken from a chromatograph sampling
in the order N2,CO2,C1,C2,C3,i-C4,n-C4,i-C5,n-C5,C6,C7+
(ii) separator and reservoir conditions i.e. Pressure and temperatures (pressures in psia and
temperatures in Fahrenheit)
(iii ) Separator and Stock tank values i.e. Separator and stock tank :GOR(Rsp and Rst), Gas
gravity(SGsp and SGst) and API or condensate gravity (API_grav)
STEP 3 : Solve the following;𝐺𝐺𝑝𝑝𝑝𝑝 = 𝑅𝑅𝑠𝑠𝑠𝑠 × 𝑆𝑆𝑆𝑆𝑠𝑠𝑠𝑠
141.5
(i)Specific gravity of oil or stock tank liquid : 𝑆𝑆𝑆𝑆𝑜𝑜𝑜𝑜𝑜𝑜 = (𝐴𝐴𝐴𝐴𝐼𝐼
𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔 +131.5)

(ii) Average molecular weight of oil Mol_Oil =0.95*((42.42.*SGoil)./(1.008-SGoil))

42.42 × 𝑆𝑆𝑆𝑆𝑜𝑜𝑜𝑜𝑜𝑜
𝑀𝑀_𝑜𝑜𝑜𝑜𝑜𝑜 = ( )
1.008 − 𝑆𝑆𝑆𝑆𝑜𝑜𝑜𝑜𝑜𝑜
(iii) Condensate molecular weight of oil from gas, Mog from Cragoes Correlation
6084
𝑀𝑀𝑜𝑜𝑜𝑜 =
(𝐴𝐴𝐴𝐴𝐼𝐼𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔 − 5.9)
(iv);
𝑆𝑆𝑆𝑆
𝐶𝐶𝑜𝑜 = 133316 × 𝑀𝑀_𝑜𝑜𝑜𝑜𝑜𝑜
𝑜𝑜𝑜𝑜𝑜𝑜

𝑆𝑆𝑆𝑆𝑜𝑜𝑜𝑜𝑜𝑜
, 𝐶𝐶𝑜𝑜𝑜𝑜 = 133316 × ,
𝑀𝑀𝑜𝑜𝑜𝑜

𝐺𝐺𝑝𝑝𝑝𝑝 = 𝑅𝑅𝑠𝑠𝑠𝑠 × 𝑆𝑆𝑆𝑆𝑔𝑔𝑔𝑔𝑔𝑔 ,

𝑉𝑉𝑒𝑒𝑒𝑒 = 𝑅𝑅𝑠𝑠𝑠𝑠 + 𝐶𝐶𝑜𝑜
, 𝑉𝑉𝑒𝑒𝑒𝑒𝑒𝑒 = 𝑉𝑉𝑒𝑒𝑒𝑒 + 𝑅𝑅𝑠𝑠𝑠𝑠

�𝑅𝑅𝑠𝑠𝑠𝑠 ×𝑆𝑆𝑆𝑆𝑠𝑠𝑠𝑠 �+(4620×𝑆𝑆𝑆𝑆𝑜𝑜𝑜𝑜𝑜𝑜 )+𝐺𝐺𝑝𝑝𝑝𝑝

(v) Total reservoir specific gas gravity 𝑆𝑆𝑆𝑆𝑡𝑡𝑡𝑡 = 𝑉𝑉𝑒𝑒𝑒𝑒𝑒𝑒

(𝐺𝐺𝑝𝑝𝑝𝑝 +𝐺𝐺𝑝𝑝𝑝𝑝 )
(vi)Average specific gas gravity of surface stream, 𝑆𝑆𝑆𝑆𝑠𝑠𝑠𝑠 =
(𝑅𝑅𝑠𝑠𝑠𝑠 +𝑅𝑅𝑠𝑠𝑠𝑠 )

62
(vii)Elmabrouk’s bubble pressure, (Epb)
𝐸𝐸𝑝𝑝𝑝𝑝 = �𝑅𝑅𝑠𝑠𝑠𝑠 0.683 � × �𝑃𝑃𝑠𝑠𝑠𝑠 0.18 � × �𝑆𝑆𝑆𝑆𝑜𝑜𝑜𝑜𝑜𝑜 4.98 � × �𝑇𝑇𝑟𝑟 0.658 �
�𝑆𝑆𝑆𝑆𝑡𝑡𝑡𝑡 −𝑆𝑆𝑆𝑆𝑠𝑠𝑠𝑠 �
(viii) Calculate vaporized gas ratio from 𝑟𝑟𝑠𝑠 =
4600×𝑆𝑆𝑆𝑆𝑜𝑜𝑜𝑜𝑜𝑜 −𝐶𝐶𝑜𝑜 𝑆𝑆𝑆𝑆𝑠𝑠𝑠𝑠

STEP 4: Assume undersaturated conditions, let Rp= Rsp, where Rp is the producing gas oil
ratio. Solve for mole fraction of wellstream that comes from reservoir gas and oil (i.e Fg and
Fo respectively) using the relations below
Rp = Rsp; Km = 1 − Rsp.× rs;
Rsp
jm = ;
Rp
qm = rs × Rp;
1 − 𝑗𝑗𝑚𝑚 1 − qm
Fgg = , Foo = ;
𝐾𝐾𝑚𝑚 Km
gm = 1 − Foo;
gk = Co + Rsp;
gt = Cog + rs.−1 ;
jk = gm × gt;
jg = Foo.× gk;
1
Fk = �1 + �jg. ��
jk

Fg = Fk −1 ;
Fo = 1 − Fg
STEP 5:Calculate the approximate wellstream vapor (yr) and liquid (xr) compositions by the
following relations : 𝑙𝑙𝑙𝑙 == Cog × rs ;
𝑙𝑙𝑙𝑙 = 𝑙𝑙𝑙𝑙𝑥𝑥𝑥𝑥𝑥𝑥 ,
𝑔𝑔𝑔𝑔 = 𝑦𝑦𝑦𝑦𝑦𝑦 + 𝑙𝑙𝑙𝑙 ,
𝑗𝑗𝑗𝑗 = 1 + 𝑙𝑙𝑙𝑙 ,
Co
lb = Rsp ,

lc = lb × xsp ,

gb = ysp + lc ,

63
 𝑗𝑗𝑗𝑗 = 1 + 𝑙𝑙𝑙𝑙
xr = gb/jb

STEP 6: Calculate the approximate reservoir well stream composition (zi) by the relations
zg = Fg × yr
zo = Fo.×xr
zi = zg + zo
Calculate zi with the relations:
Co
FyG = 1/(1 + � �)
Rsp
Where, FyG is the mole fraction of wellstream that becomes separator gas. Then
zi = FyG × ysp + (1 − FyG)xsp
STEP 7: Calculate Nemeth-Kennedy’s dew point pressure using the relations in reference
[13]
STEP 7: disp all calculated values
STEP 8: END

(A.2) PSEUDOIZATION MODULE (using Whitson’s method)

STEP 1:START
STEP 2: Input the following:
Laboratory C7+ molecular weight in stock tank oil (M_cn), laboratory C7+ mole fraction in
mixture (z_cn), laboratory C7+ specific gravity in mixture (SG_cn)
STEP 3 Determine the number of Cn + split fractions, n. obtain the Guassian quadrature
values: function variables (Xi) and the weight factors (Wi).
STEP 4: Input the following
Lowest molecular weight in plus fraction𝜂𝜂 = 92. Also input shape of distribution as 𝛼𝛼 = 1
STEP 5: Estimate the heaviest molecular weight of fraction n as Mn by the formula
𝑀𝑀𝑀𝑀 = 2.5 × 𝑀𝑀_𝑐𝑐𝑐𝑐
Step6: calculate the parameters 𝛿𝛿 𝑎𝑎𝑎𝑎𝑎𝑎 𝛽𝛽 by the equations

64
 𝛼𝛼𝛼𝛼
� −1�
𝛿𝛿 = 𝑒𝑒 𝑀𝑀_𝑐𝑐𝑐𝑐 −𝜂𝜂
and
(𝑀𝑀𝑀𝑀 − 𝜂𝜂)
𝛽𝛽 =
𝑋𝑋𝑋𝑋
Step 7: Calculate the Cn+ mole fraction (zik) and molecular weight (Mi) for each fraction
(𝑋𝑋)𝛼𝛼−1 (1+ln 𝛿𝛿)𝛼𝛼
by the formula 𝑧𝑧𝑧𝑧𝑧𝑧 = 𝑧𝑧_𝑐𝑐𝑐𝑐 × [𝑊𝑊𝑊𝑊𝑊𝑊(𝑋𝑋𝑋𝑋)] , 𝑀𝑀𝑖𝑖 = 𝜂𝜂 + 𝛽𝛽𝛽𝛽𝛽𝛽 and 𝑓𝑓(𝑋𝑋) =
Γ(𝛼𝛼) ×𝛿𝛿 𝑥𝑥

Step8: Check the condition ∑𝑛𝑛𝑖𝑖=1 𝑧𝑧𝑧𝑧𝑘𝑘 𝑀𝑀𝑖𝑖 = 𝑀𝑀𝑐𝑐𝑐𝑐 is satisfied. Else modify the value of 𝛿𝛿 and
repeat steps % and 6 until a reasonable match is achieved.
Step 9: calculate Watson characterization factor 𝐾𝐾𝑤𝑤 and the specific gravities of each split
SGi by the relations
0.15178 −0.84573
𝐾𝐾𝑤𝑤 = 4.5579 × 𝑀𝑀_𝑐𝑐𝑐𝑐 × 𝑆𝑆𝑆𝑆_𝑐𝑐𝑐𝑐
𝑆𝑆𝑆𝑆𝑆𝑆 = 6.0108 × 𝑀𝑀𝑖𝑖0.17947 × 𝐾𝐾𝑤𝑤−1.18241
Step 10: calculate the boiling points (Tb) and the critical pressure (Pc), temperature (Tc) and
volume (Vc) from Riazi Daubert correlations. Also estimate the acentric factors (𝜔𝜔) from
Edminster’s correlation
𝑇𝑇𝑏𝑏𝑏𝑏 = (𝐾𝐾𝑤𝑤 𝑆𝑆𝑆𝑆𝑖𝑖 )3
−2.3125
𝑃𝑃𝑐𝑐𝑐𝑐 = (3.12281 × 109 ) × 𝑇𝑇𝑏𝑏𝑏𝑏 × 𝑆𝑆𝑆𝑆𝑖𝑖2.3201
0.58848
𝑇𝑇𝑐𝑐𝑐𝑐 = 24.27871 × 𝑇𝑇𝑏𝑏𝑏𝑏 × 𝑆𝑆𝑆𝑆𝑖𝑖0.3596
𝑃𝑃𝑐𝑐
3 log � �14.7�
𝜔𝜔 = � × − 1�
7 𝑇𝑇𝑐𝑐
�� �𝑇𝑇 � − 1�
𝑏𝑏
2.3829
𝑉𝑉𝑐𝑐 = (7.0434 × 10−7 )𝑇𝑇𝑏𝑏𝑏𝑏 × 𝑆𝑆𝑆𝑆𝑖𝑖−1.683

Volume is in ft3/lb mole, pressure in psia and temperatures (boiling and critical) are in
degrees Rankine.
Step 11: END

(A.2) FLASH MODULE

Step 1: Start
Step 2: input value of vapor mole fraction gotten from recombination module
Step 3: Enter pressure and temperature to flash

65
Step 4: Input values of critical pressure, temperature, acentric factors, critical volumes and
molecular weight for the mixture in the order N2, CO2, C1, C2….Ps-1, Ps-2, Ps-3…
Step 5: Input value for the binary interaction coefficient 𝑘𝑘𝑖𝑖𝑖𝑖 from Whitsons Monograph and
for hydrocarbon element interactions (C1 to C7+ pairs) use Chueh-Prausnitz correlation
given below
1� 1� 𝐵𝐵
6 6
2𝑉𝑉𝑐𝑐𝑐𝑐 𝑉𝑉𝑐𝑐𝑐𝑐
𝑘𝑘𝑖𝑖𝑖𝑖 = 𝐴𝐴 �1 − � 1 1� � �
�3
𝑉𝑉𝑐𝑐𝑐𝑐 + 𝑉𝑉𝑐𝑐𝑐𝑐 3

With A=0.18 and B=6

Step 6: Estimate K values by using the Wilson equation or use K values gotten from
recombination. Wilsons equation is given as
−1
𝑒𝑒 [5.37(1+𝜔𝜔𝑖𝑖 �1−𝑇𝑇𝑟𝑟𝑟𝑟 )�]
𝐾𝐾𝑖𝑖 =
𝑃𝑃𝑟𝑟𝑟𝑟
Where Tr and Pr are the reduced temperatures and pressures. (see chapter two)

Step 7: calculate the minimum and maximum values ok K i.e Kmin and Kmax respectively and
set Fv to be limited by 𝐹𝐹𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 < 0 𝑎𝑎𝑎𝑎𝑎𝑎 𝐹𝐹𝑣𝑣𝑣𝑣𝑣𝑣 > 1. Thus 𝐹𝐹𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 < 𝐹𝐹𝑣𝑣 < 𝐹𝐹𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 and the values
are obtained by
1
𝐹𝐹𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉 =
1 − 𝐾𝐾𝑚𝑚𝑚𝑚𝑚𝑚

1
and 𝐹𝐹𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉 = 1−𝐾𝐾
𝑚𝑚𝑚𝑚𝑚𝑚

Step 8: Solve the Rachford-Rice phase split equation (2.20) at start value of Fv being the Fv
from recombination using Newton-Raphson’s method.
Step 9: Calculate the phase compositions x and y as given by equations (2.19 and 2.18)
Step 10: Calculate phase Z factors ZL , Zv and components fugacities fLi and fvi using Peng-
Robinson’s equation of state
Step 11: Calculate the phase Gibbs energy functions 𝐺𝐺𝑦𝑦∗ 𝑎𝑎𝑎𝑎𝑎𝑎 𝐺𝐺𝑥𝑥∗ as in equation (2.9).
Determine the correct Z-factor roots of each phase (if multiple roots exist) and calculate the
mixture Gibbs energy given by the relation

66
 ∗
𝐺𝐺𝑚𝑚𝑚𝑚𝑚𝑚 = 𝐺𝐺𝑥𝑥∗ (1 − 𝐹𝐹𝑣𝑣 ) + 𝐺𝐺𝑦𝑦∗ 𝐹𝐹𝑣𝑣
Step 12: Check the equal fugacities constraints from equation ()
Step 13: (a) if a convergence is reached, stop (b) if convergence is not reached update the K
values with the fugacity ratio using Newton Raphson methods for K update

Step 14: Check for convergence at a trivial solution (𝐾𝐾𝑖𝑖 → 1) with the condition
𝑛𝑛

�(ln 𝐾𝐾𝑖𝑖 )2 < 10−4

𝑖𝑖=1

Step 15: if a trivial solution is not detected return to step 6. Otherwise perform a stability
check.
Step 16: For stability check : calculate mixture fugacities fzi (use normalized zi), with the
multiple Z-factor roots, choose root with the lowest g
Step 17: use Wilson equation to estimate the K values
Step18: calculate the second phase mole fractions (yi), with the assumption that zi is equal
to the other phase. Then it follows that
(𝑦𝑦𝑖𝑖 )𝑣𝑣 = 𝑧𝑧𝑖𝑖 (𝐾𝐾)𝑣𝑣
Step 18: add up the mole numbers to get 𝑆𝑆𝑣𝑣
𝑛𝑛

𝑆𝑆𝑣𝑣 = �(𝑦𝑦𝑖𝑖 )𝑣𝑣

𝑗𝑗=1

Step 19: calculate the fugacities of the second phase (fyi)v from Peng-Robinson equation of
state with multiple Z-factor roots (for the given phase) , choose root with the minimum Gibbs
energy 𝐺𝐺 ∗
Step 20: Calculate the fugacity-ratio corrections (𝑅𝑅𝑅𝑅)𝑣𝑣 for subsequent substitution to update
the K values ,
𝑓𝑓𝑧𝑧 𝑖𝑖 1
(𝑅𝑅𝑖𝑖 )𝑣𝑣 =
�𝑓𝑓𝑦𝑦𝑦𝑦 �𝑣𝑣 𝑆𝑆𝑣𝑣

Step 21: Test for convergence with the criteria 𝑒𝑒 < 1 × 10−12 , thus

67
 𝑛𝑛

�(𝑅𝑅𝑖𝑖 − 1)2 < 𝑒𝑒

𝑖𝑖=1

If convergence is not obtained , update K values with the relation below

(𝑛𝑛+1) (𝑛𝑛) (𝑛𝑛)
𝐾𝐾𝑖𝑖 = 𝐾𝐾𝑖𝑖 𝑅𝑅𝑖𝑖
Step 22: Test for a trivial solution by using the criteria below
𝑛𝑛

�(ln 𝐾𝐾𝑖𝑖 )2 < 1 × 10−4

𝑖𝑖=1

If trivial solution is not indicated return to step 17

Step 23: when S< 1 stability has been achieved
Step 24: END

(A.3) BUBBLE AND DEW POINT PRESSURE CALCULATIONS

STEP 1 : Start:
Step 2: For bubble point pressure estimate use the Elmabrouk’s bubble point pressure
reported by recombination module. (For dew point use the dew point pressure estimated
Nemeth and Kennedy correlation given by the recombination module). The next lines
describe the bubble point pressure scenario.
Step 3: Estimate K-values using Wilson’s equation
𝑗𝑗
Step 4: Calculate the vapor phase compositions from 𝑦𝑦𝑖𝑖𝑖𝑖+1 = 𝑧𝑧𝑖𝑖 𝐾𝐾𝑖𝑖 , i=1, 2….N, where j is an
iteration counter.
Step 5: Calculate the vapor and liquid phase fugacity coefficients ((𝜑𝜑𝑖𝑖𝑣𝑣 , 𝑖𝑖 = 1,2 … . 𝑁𝑁) and
(𝜑𝜑𝑖𝑖𝑙𝑙 , 𝑖𝑖 = 1,2, … . 𝑁𝑁) using estimates for bubble point pressure and vapor composition. The
liquid composition equals the feed composition
Step 6: Calculate the new K factors from equation (2.13)
Step 7: Calculate h(FV) in the equation ℎ(𝐹𝐹𝑣𝑣 ) = ∑𝑛𝑛𝑖𝑖=1 𝑧𝑧𝑖𝑖 𝐾𝐾𝑖𝑖 − 1
𝑑𝑑(ℎ(𝐹𝐹𝐹𝐹)) 𝜕𝜕 ln 𝜑𝜑𝑖𝑖𝑙𝑙 𝜕𝜕 ln 𝜑𝜑𝑖𝑖𝑣𝑣
Step 8: Calculate the expression 𝑑𝑑𝑑𝑑
= ∑𝑛𝑛𝑖𝑖=1 𝑧𝑧𝑖𝑖 𝐾𝐾𝑖𝑖 � − �
𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕

(ℎ(𝐹𝐹𝑣𝑣 ))𝑖𝑖
Step 9: Calculate the (j+1)th estimate of bubble point pressure from 𝑃𝑃𝑗𝑗+1 = 𝑃𝑃𝑗𝑗 −
𝑑𝑑(ℎ(𝐹𝐹𝐹𝐹))𝑖𝑖
𝑑𝑑𝑑𝑑

Step 10: if solution did not converge return to step 4

68
Else
Step 11: END
Note: Phase envelope algorithm followed for this report was same as in Pedersen book
(reference )

(A.4) BLACK OIL PROPERTIES MODULE:

(i) CORRELATION CALCULATOR
STEP 1: START
STEP 2:calculate the following black oil properties by the correlations listed below: full
equations of these correlations can be found in their reference
(i) Bubble point pressure : Glaso
(ii) Dew point pressure by Nemeth and Kennedy correlation
(iii) Bubble point pressure using Standings correlation
(iv) solution gas oil ratio by Glaso correlation
(v) Viscosity by Ng and Egbogah correlation (for dead oil viscosity), Beggs and Robinson
correlation for saturated oil
(vi) Oil formation volume factor by Petrosky and Farshad correlation.
(vii) coefficient of isothermal Petrosky and Farshad correlation
STEP 3: END

(A.5) MODIFIED BLACK OIL PARAMETERS CORRELATION

STEP 1: START
STEP 2: Calculate the composition of the oil and gas phases at reservoir by the relation
For oil at surface
𝐶𝐶𝑜𝑜
𝑥𝑥𝑜𝑜 =
𝑅𝑅𝑠𝑠 + 𝐶𝐶𝑜𝑜
𝑥𝑥𝑔𝑔� = 1 − 𝑥𝑥𝑜𝑜
𝑀𝑀𝑔𝑔 = 𝑆𝑆𝑆𝑆𝑔𝑔𝑔𝑔𝑔𝑔 × 𝑀𝑀𝑎𝑎𝑎𝑎𝑎𝑎
For reservoir oil

69
 𝑀𝑀𝑜𝑜 = 𝑀𝑀𝑜𝑜 𝑥𝑥𝑜𝑜� + 𝑀𝑀𝑔𝑔 𝑥𝑥𝑔𝑔�

𝑀𝑀𝑜𝑜
𝑉𝑉𝑜𝑜 =
𝜌𝜌𝑜𝑜
62.48𝛾𝛾𝑜𝑜 + 0.0136𝛾𝛾𝑔𝑔 𝑅𝑅𝑠𝑠
𝜌𝜌𝑜𝑜 =
𝐵𝐵𝑜𝑜

STEP 3: calculate reservoir gas phase

Reservoir gas densities
𝜌𝜌𝑔𝑔𝑠𝑠𝑠𝑠 + 𝜌𝜌𝑜𝑜𝑜𝑜𝑜𝑜 𝑟𝑟𝑠𝑠
𝜌𝜌𝑔𝑔 =
𝐵𝐵𝑔𝑔𝑔𝑔
Mole fraction of surface oil in reservoir gas
𝐶𝐶𝑜𝑜
𝑦𝑦𝑜𝑜� =
1� + 𝐶𝐶
𝑟𝑟𝑠𝑠 𝑜𝑜

Mole fraction of surface gas in reservoir gas 𝑦𝑦𝑔𝑔� = 1 − 𝑦𝑦𝑜𝑜�

Molecular weight of reservoir gas 𝑀𝑀𝑔𝑔 = 𝑀𝑀𝑜𝑜� 𝑦𝑦𝑜𝑜� + 𝑀𝑀𝑔𝑔� 𝑦𝑦𝑔𝑔�
𝑀𝑀𝑔𝑔
Molar volume of reservoir gas 𝑣𝑣𝑔𝑔 = 𝜌𝜌𝑔𝑔

STEP 4: calculate EOS parameters using the Flash module

For oil critical properties use Matthews relation
𝑇𝑇𝑐𝑐 = 608 + 364 log(𝑀𝑀𝑜𝑜�− 71.2) + (2450 log 𝑀𝑀𝑜𝑜� − 3800) log 𝛾𝛾𝑜𝑜
𝑃𝑃𝑐𝑐 = 1188 − 431 log(𝑀𝑀𝑜𝑜� − 61.1) + [2319 − 852 log(𝑀𝑀𝑜𝑜� − 53.7)](𝛾𝛾𝑜𝑜 − 0.8)
2
𝛼𝛼 = �1 + 𝑚𝑚�1 − �𝑇𝑇𝑟𝑟 ��
𝜔𝜔 = 0.000003𝑀𝑀𝑜𝑜2� + 0.004𝑀𝑀𝑜𝑜� − 0.039
For gas critical properties use the Standings correlation
If 𝑦𝑦𝑔𝑔 < 0.75
𝑇𝑇𝑐𝑐 = 168 + 325𝛾𝛾𝑔𝑔 − 12.5𝛾𝛾𝑔𝑔2
𝑃𝑃𝑐𝑐 = 667 + 15.0𝛾𝛾𝑔𝑔 − 37.5𝛾𝛾𝑔𝑔2
If 𝑦𝑦𝑔𝑔 ≥ 0.75
𝑇𝑇𝑐𝑐 = 187 + 330𝛾𝛾𝑔𝑔 − 71. 5𝛾𝛾𝑔𝑔2

70
 𝑃𝑃𝑐𝑐 = 706 + 51.7𝛾𝛾𝑔𝑔 − 11.1𝛾𝛾𝑔𝑔2

𝑤𝑤 = 01637𝛾𝛾𝑔𝑔 − 0.0792

STEP 5:Calculate the EOS constants

0.5
𝑎𝑎 = 𝑎𝑎𝑜𝑜� 𝑥𝑥𝑜𝑜2� + 𝑎𝑎𝑔𝑔� 𝑥𝑥𝑔𝑔2� + 2�𝑎𝑎𝑜𝑜� 𝑎𝑎𝑔𝑔� � 𝑥𝑥𝑜𝑜� 𝑥𝑥𝑔𝑔�
𝑏𝑏 = 𝑏𝑏𝑜𝑜� 𝑥𝑥𝑜𝑜� + 𝑏𝑏𝑔𝑔�́ 𝑥𝑥𝑔𝑔�
EOS a and b still maintain the same forms as in Peng _Robinson (ref.)
STEP 8: Run the flash module
STEP: 7 END

Note: The algorithm for the hypothetical model using Gaussian distribution is the same as
the Pseudoization model in RM module. But the molecular weight used is the weight of the
total well stream, while the normalized mole fraction and specific gravity are 1 and the total
specific gravity of the well stream.

71
APPENDIX B

B: PLOTS AND DIAGRAMS

Fig: B1: Snapshot of Recombination Module from Matlab

B2

72
Fig B2: Phase diagram of reservoir mixture from laboratory (Diagram from Multiflash)

B3

Table B.3 : Comparative showing the flash of the combined reservoir stream by
Multiflash and the F-M module
Component feed Multiflash results F_M module
Vapour liquid vapor liquid
NITROGEN 0.0019 0.0019 0.0000 0.0019 0.0000
CO2 0.0095 0.0095 0.0002 0.0092 0.0003
METHANE 0.8996 0.9014 0.0042 0.8720 0.0054
ETHANE 0.0542 0.0543 0.0015 0.0525 0.0021
PROPANE 0.0186 0.0186 0.0018 0.0181 0.0028
ISOBUTANE 0.0043 0.0043 0.0010 0.0042 0.0017
N-BUTANE 0.0051 0.0051 0.0018 0.0050 0.0030
ISOPENTANE 0.0024 0.0024 0.0025 0.0023 0.0038
N-PENTANE 0.0019 0.0019 0.0028 0.0019 0.0042
C6 0.0004 0.0004 0.0112 0.0026 0.0197
C7+ 0.0021 0.0001 0.9730 0.0303 0.9569

73