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by

A THESIS

IN

PETROLEUM ENGINEERING

of Texas Tech University in

Partial Fulfillment of

the Requirements for

the Degree of

MASTER OF SCIENCE

IN

PETROLEUM ENGINEERING

^ Approved

May, 1998

i^^^o ACKNOWLEDGEMENTS

at the Department of Petroleum Engineering, for his guidance throughout the

duration of the research, as well as for helping me in formulating a research

topic. Equally important to me is all the moral support and timely help he has

provided me during my graduate work at Texas Tech University.

I would like to express my deep gratitude to Dr. John J. Day, Professor

and Chairperson of the Department of Petroleum Engineering, for the financial

assistance in the form of a Teaching/Research Assistantship which made this

research work possible.

A very special thanks is extended to the Computer Modelling Group

(CMG), Calgary, Canada, for providing their phase-property program WinProp

free of cost for this study. In particular, I would like to thank Mr. Jim Erdle and

Mr. Mohamed Hassam for helping me in understanding the software.

I would like to thank Dr. Lloyd R. Heinze and Dr. M. Arnold for their

encouragement and for making valuable suggestions. I thank Johnita, Donna,

and Melissa who provided me with friendship and moral support for all these

years, and helped me out with the paperwork in the university.

I would like to thank all my friends in the department, who mc.de my stay

at Texas Tech so cheerful and fruitful. I would like to thank all my other friends

for their friendship, support and all the help they provided.

My sincere and deepest gratitude goes to my parents whose love and

caring support throughout my life encourage me to pursue my dreams and to

whom this work is dedicated.

11

TABLE OF CONTENTS

ACKNOWLEDGEMENTS ii

ABSTRACT v

LIST OF TABLES vii

LIST OF FIGURES viii

NOMENCLATURE xi

CHAPTER

1. INTRODUCTION 1

2. LITERATURE REVIEW 5

2.1 Basic Concepts of Phase Behavior 5

2.1.1 One-Component System 6

2.1.2 Two-Component System 8

2.1.3 Effect of Composition 9

2.1.4 Multi-Component System 10

2.2 Vapor-Liquid Phase Equilibria 12

2.2.1 Equilibrium Ratios 12

2.2.2 Flash Calculations 14

2.2.3 Separator Processes 16

2.3 Equation of State 18

2.3.1 Cubic Equations of State 20

2.3.2 Redlich-Kwong EOS and its Modifications 22

2.3.3 Peng-Robinson EOS and its Modifications 28

2.3.4 Schmidt and Wenzel EOS 31

2.3.5 Patel and Teja EOS 34

2.4 Applications of Equations of State 37

2.4.1 Determination of Equilibrium Constants 38

111

2.4.2 Simulation of Constant Volume Depletion Test 39

2.4.3 Simulation of Constant Composition Expansion Test 42

2.4.4 Simulation of Differential Liberation Test 44

2.5 Comparison of Equation of State 46

2.6 Tuning of Equation of State 47

2.7 Characterization of Plus Fractions 49

3. METROLOGY 59

3.1 Setting-Up the Initial Data and Characterization of Plus

Fractions 60

3.2 Selection of Equation of State Model 61

3.3 Characterization of Vaporization/Condensation Process 63

3.4 Assumptions 66

4. DISCUSSION OF RESULTS 73

4.1 Plus Fraction Characterization Results 73

4.2 Selection of Equation of State model 74

4.3 Results from Characterization of Vaporization/condensation

Process 75

5. CONCLUSIONS 149

6. RECOMMENDATIONS 150

REFERENCES 151

IV

ABSTRACT

study the effect of the process on the gas enrichment and overall recovery of a

low density crude oil.

The simulation begins with the identification of the most suitable equation

of state model to characterize vaporization/condensation process. This was

accomplished by simulating the constant volume depletion test and constant

composition expansion test using three equation of state models and comparing

the simulation results with the available experimental data. The equation of

model, which predicted the constant volume depletion data most accurately, was

selected to be used further in the study. The Peng-Robinson equation of state

was found to be most accurate in predicting the experimental data.

The vaporization/condensation process was characterized by employing

a combination of constant volume depletion test simulation and flash

calculations using the selected equation of state. The entire characterization of

vaporization/condensation process was performed on WinProp, a phase

property program.

The vaporization/condensation process was found to be feasible as it was

resulting in gas enrichment and increase in liquid saturation. These results were

much more pronounced when conducted the vaporization/condensation at the

high pressure and high vaporization temperature. Therefore, it was concluded

that the vaporization/condensation may result in additional recovery if carried

out at high reservoir pressure and high vaporization temperature.

This study was conducted on two samples of retrograde condensate fluid

and only three equation of state model were tested. Future work needs to be

done on other types of reservoir fluids and other more recent equations of state

such as Patel-Teja and Schmidt-Wenzel EOS should be verified.

The effects of flow characteristics of the fluid and heating mechanism

(steam injection, in-situ combustion) in the reservoir should be incorporated in

the future studies.

VI

LIST OF TABLES

3.2 Properties of Plus Fractions 68

3.3 Experimental Data for Sample 1 69

3.4 Experimental Data for Sample 2 70

4.1 Composition and Properties of SCN Fractions (Sample 1) 81

4.2 Composition and Properties of SCN Fractions (Sample 2) 81

4.3 Comparison of Retrograde Liquid Volume Calculated By Different

EOS (Sample 1) 82

4.4 Comparison of Retrograde Liquid Volume Calculated By Different

EOS (Sample 2) 83

4.5 Comparison of Produced Gas Calculated By Different EOS (Sample 1) 84

4.6 Comparison of Produced Gas By Different EOS (Sample 2) 85

4.7 Comparison of Saturation Pressures Calculated By Different EOS 85

4.8 Comparison Between Experimentally Obtained Composition and

Composition Calculated By PREOS at Depleted Reservoir Pressure

(Sample 1) 86

4.9 Comparison Between Experimentally Obtained Composition and

Composition Calculated By PREOS at Depleted Reservoir Pressure

(Sample 2) 87

4.10 Calculated Compositions at Depleted Reservoir Pressures and

Original Reservoir Temperature (sample 1) 88

4.11 Calculated Compositions at Depleted Reservoir Pressures and

Original Reservoir Temperature (sample 1) 89

4.12 Moles of Fluid in Place After each Cycle 90

Vll

LIST OF FIGURES

2.2 Pressure-Temperature Diagram for a Single-Component System 52

2.3 Pressure-Volume Diagram for a Single-Component System 53

2.4 Typical Pressure-Temperature Diagram for a Binary System 54

2.5 Effect of Composition on Phase Envelope for a Binary System 55

2.6 Location of Critical Loci for Several Binary Systems 56

2.7 Typical Pressure-Temperature Diagram for a Multi-Component

System 57

2.8 The Exponential and Left-Skewed Distribution Functions 58

3.1 Flow Diagram of Procedure Used in the Study 71

3.2 Schematic Diagram of Vaporization/Condensation Process 72

4.1 Comparison of Relative Volume Data (Sample 1, PREOS) 91

4.2 Comparison of Relative Volume Data (Sample 1, SRKEOS) 92

4.3 Comparison of Relative Volume Data (Sample 1, SRKGDEOS) 93

4.4 Comparison of Relative Volume Data (Sample 2, PREOS) 94

4.5 Comparison of Relative Volume Data (Sample 2, SRKEOS) 95

4.6 Comparison of Relative Volume Data (Sample 2, SRKGDEOS) 96

4.7 Comparison of Z-Factor Data (Sample 1, PREOS) 97

4.8 Comparison of Z-Factor Data (Sample 1, SRKEOS) 98

4.9 Comparison of Z-Factor Data (Sample 1, SRKGDEOS) 99

4.10 Comparison of Z-Factor Data (Sample 2, PREOS) 100

4.11 Comparison of Z-Factor Data (Sample 2, SRKEOS) 101

4.12 Comparison of Z-Factor Data (Sample 2, SRKGDEOS) 102

4.13 Comparison of CVD Test Data (Sample 1, PREOS) 103

4.14 Comparison of CVD Test Data (Sample 1, SRKEOS) 104

Vlll

4.15 Comparison of CVD Test Data (Sample 1, SRKGDEOS) 105

4.16 Comparison of CVD Test Data (Sample 2, PREOS) 106

4.17 Comparison of CVD Test Data (Sample 2, SRKEOS) 107

4.18 Comparison of CVD Test Data (Sample 2, SRKGDEOS) 108

4.19 Variation in Mole % of Liquid and Vapor (Sample 1, 750 psia, 700 F 109

4.20 Variation in Mole % of Liquid and Vapor (Sample 1, 750 psia, 500 F 110

4.21 Variation in Mole % of Liquid and Vapor (Sample 1, 250 psia, 700 F 111

4.22 Variation in Mole % of Liquid and Vapor (Sample 1, 250 psia, 500 F 112

4.23 Variation in Mole % of Liquid and Vapor (Sample 2, 750 psia, 500 F 113

4.24 Variation in Mole % of Liquid and Vapor (Sample 2, 750 psia, 350 F 114

4.25 Variation in Mole % of Liquid and Vapor (Sample 2, 250 psia, 500 F 115

4.26 Variation in Mole % of Liquid and Vapor (Sample 2, 250 psia, 350 F 116

4.27 Variation in Volume % of Liquid and Vapor

(Sample 1, 750 psia, 700 F) 117

4.28 Variation in Volume % of Liquid and Vapor

(Sample 1, 750psia, 500 F) 118

4.29 Variation in Volume % of Liquid and Vapor

(Sample 1, 250psia, 700 F) 119

4.30 Variation in Volume % of Liquid and Vapor

(Sample 1, 250psia, 500 F) 120

4.31 Variation in Volume % of Liquid and Vapor

(Sample 2, 750psia, 500 F) 121

4.32 Variation in Volume % of Liquid and Vapor

(Sample 2, 750psia, 350 F) 122

4.33 Variation in Volume % of Liquid and Vapor

(Sample 2, 250psia, 500 F) 123

4.34 Variation in Volume % of Liquid and Vapor

(Sample2, 250psia, 350 F) 124

4.35 Variation in Overall Composition (Sample 1, 750 psia, 700 F) 125

4.36 Variation in Overall Composition (Sample 1, 750 psia, 500 F) 126

IX

4.37 Variation in Overall Composition (Sample 1, 250 psia, 700 F) 127

4.38 Variation in Overall Composition (Sample 1, 250 psia, 500 F) 128

4.39 Variation in Overall Composition (Sample 2, 750 psia, 500 F) 129

4.40 Variation in Overall Composition (Sample 2, 750 psia, 350 F) 130

4.41 Variation in Overall Composition (Sample 2, 250 psia, 500 F) 131

4.42 Variation in Overall Composition (Sample 2, 250 psia, 350 F) 132

4.43 Variation in Liquid Composition (Sample 1, 750 psia, 700 F) 133

4.44 Variation in Liquid Composition (Sample 1, 750 psia, 500 F) 134

4.45 Variation in Liquid Composition (Sample 1, 250 psia, 700 F) 135

4.46 Variation in Liquid Composition (Sample 1, 250 psia, 500 136

4.47 Variation in Liquid Composition (Sample 2, 750 psia, 500 'F 137

4.48 Variation in Liquid Composition (Sample 2, 750 psia, 350 138

NOMENCLATURE

ai Parameter 'a' for component 'i'

aj Parameter 'a' for component 'j'

am Parameter 'a' for a mixture

ai-as Constants defined in equations 2.59 and 2.60

A Constant defined in equation 2.16

b Equation of state parameter

bi Parameter 'b' for component 'i

bm Parameter 'b' for a mixture

B Constant defined in equation 2.17

Bod Relative oil volume

c Parameter for Patel and Teja equation of state

Ci Volume correction parameter

Cm Parameter 'c' for a mixture

C Constant defined in equation 2.94

Ci-Ce Alkane series hydrocarbons with 1-6 carbon atoms

C7+ Hydrocarbons with 7 or more carbon atoms

CO2 Carbon dioxide

CVD Constant volume depletion

CCE Constant composition expansion

d Parameter defined in equation 2.98

EOS Equation of State

EXP(x) Equivalent to e"

f Fugacity

f(nv) Function defined in equation 2.4

XI

f(nv) Function defined in equation 2.6

Gp Gas produced, scf

(Gp)t Total cumulative gas produced, scf

Ki Equilibrium constant for component 'i'

KiA Assumed equilibrium constant of component 'i'

Kij Binary interaction coefficient between components 'i' and ']

Kij Parameter defined in equation 2.44

In Natural logarithm

m Parameter defined in equation 2.29

rrio Constant defined in equation 2.56

mi Constant defined in equation 2.71

m2 Constant defined in equation 2.72

MWc7+ Molecular weight of C7+ fractions

n Number of components in the mixture

ni Initial moles in place

nL Number of moles in the liquid phase

nv Number of moles in the vapor phase

np Number of moles produced

(nL)actual Actual number of moles in the liquid phase

(nL)in-place Moles of liquid in place

(nv)actual Actual number of moles in the vapor phase

^nv}produceci Moles of produced gas

(nv)n New value of nv

(nv)r Remaining moles of gas

N2 Nitrogen

Pb Bubble point pressure, psia

Xll

pc Critical pressure, psia

pen Critical pressure of the component 'i', psia

pd Dew point pressure, psia

psat Saturation pressure, psia

PR Peng-Robinson

PT Patel-Teja

Q Parameter defined in equation 2.97

R Universal gas constant, 10.73 psia-ftV (lb-mole)(R)

Rsd Solution gas-oil ratio, scf/STB

Si Dimensionless shift parameter

SRK Soave-Redlich-Kwong

SRKGDEOS Soave-Redlich-Kwong equation of state with the constant 'a'

proposed by Graboski and Daubert

SW Schmidt-Wenzel

T System temperature, R

Tb Boiling point of the plus fraction, R

Tc Critical temperature, R

Tci Critical temperature of the component 'i', R

^ Coefficient for SW EOS defined in equation 2.74

^ Volume, ft^/mole

^i Initial volume, ft^/mole

^^1 Relative phase volume

^sat Volume at saturation pressure, ft^/mole

^L Volume of the liquid phase

^g Volume of the vapor phase

^t Total volume of the fluid, ft^

XIU

W Coefficient for SW EOS defined in equation 2.75

Xi Mole fraction of the c o m p o n e n t ' i ' in the liquid phase

(xi)in-piace Molc fraction of the c o m p o n e n t 'i' in the liquid in place

yi Mole fraction of the c o m p o n e n t 'i' in the v a p o r p h a s e

(yi)produced Molc fraction of the c o m p o n e n t 'i' in the p r o d u c e d gas

Zi Mole fraction of c o m p o n e n t 'i' in the h y d r o c a r b o n mixture

Zj Mole fraction of c o m p o n e n t 'j' in the h y d r o c a r b o n mixture

Z Compressibility factor

Z^ Compressibility factor of the liquid phase

Z^ Compressibility factor of the vapor phase

ZRA Rackett compressibility factor

Zc Critical compressibility factor

a T e m p e r a t u r e d e p e n d e n t coefficient in SRK a n d PR EOS

tti Coefficient a for c o m p o n e n t ' i '

ttj Coefficient a for component']

pc Smallest positive root of equation 2.64

Y Specific gravity

yc7+ Specific gravity of h e p t a n e - p l u s fraction

e Error tolerance

i P a r a m e t e r defined in equation 2.45

^c Parameter defined in equation 2.65

(J). Fugacity coefficient of c o m p o n e n t ' i ' in a mixture

<j,.L Fugacity coefficient of t h e c o m p o n e n t 'i' in the liquid p h a s e

(j).v Fugacity coefficient of the c o m p o n e n t ' i ' in the v a p o r p h a s e

yi, Coefficient defined in equation 2.39

^. Coefficient defined in equation 2.38

CO

Acentric factor

XIV

coi Acentric factor for component 'i'

com Acentric factor for a mixture

Qa Constant in equation of state

Qb Constant in equation of state

Qc Constant in PT equation of state

XV

CHAPTER 1

INTRODUCTION

hydrocarbon systems are important in several different aspects of the petroleum

industry. These include the development of reservoirs containing black oil,

volatile oil, gas condensate, and natural gas, as well as the design of gas injection

processes, enhanced oil recovery schemes, and hydrocarbon processing units.

Traditionally, chemical and petroleum engineers engaged in the production of

oil and natural gases from reservoirs have not devoted much interest to details

regarding the properties and compositions of the hydrocarbon fluids produced.

Design of production schemes and equipment was mainly based on experience.

This was, however, insufficient considering the enormous investment required

for oil and gas exploration and production. Today, production systems and

equipment undergo detailed engineering analysis and careful design to optimize

the amount of hydrocarbons produced and minimize the operating costs and

investments.

Analysis and design of oil and gas production facilities and schemes

require thorough knowledge of the thermodynamic and physical properties of

the hydrocarbon fluids. To determine the volume of oil and gas a separator

produces under given conditions, it is necessary to know the vapor-liquid

relationships and the densities of the mixture. Understanding the flow process

in the reservoir requires the knowledge of viscosity and capillary pressure. Heat

exchanger design requires the knowledge of the thermal conductivity of these

fluids.

It would be best if knowledge of the above mentioned properties were

available from experimental observations. Accurate laboratory studies of PVT

properties and phase-equilibria behavior of reservoir fluids are, therefore,

necessary for characterizing these fluids and evaluating their volumetric

performance at various pressure and temperature conditions. There are many

laboratory analyses that can be made on a reservoir fluid sample. The amount of

data desired determines the number of tests performed in the laboratory. In

general, there are three types of laboratory tests used to measure hydrocarbon

reservoir samples.

1. Primary Tests: These routine tests involve the measurement of the

specific gravity and the gas-oil ratio of the produced hydrocarbon

fluids.

2. Detailed Laboratory Tests: These typical tests are performed to

characterize the hydrocarbon fluids. They involve the measurement of

the fluid composition, molecular weight, viscosity, compressibility,

saturation pressure, formation volume factor, solubility, differential

liberation, constant volume depletion, and constant composition

expansion characteristics.

3. Swelling Tests: In addition to primary and detailed laboratory tests,

which are fairly standard, another type of test may be performed for

very specific applications. If a reservoir is planned to be depleted

under a gas injection or dry gas cycling scheme, a swelling test should

be performed.

If reservoir fluid samples are available, the fluid properties of interest can

be measured with the above mentioned laboratory analysis procedures.

However, these analyses are usually conducted at reservoir temperatures only

and the variation of the properties with temperature is not available for

production system calculations. Also, in many cases a PVT analysis may not be

available early in the life of the reservoir or may never be available because of the

relatively high cost of performing these experimental PVT tests and the

uncertainties in the accuracy of such laboratory measurements. To overcome

these obstacles, empirical correlation methods have been developed for

predicting various fluid properties and describing phase behavior characteristics

of reservoir fluids from limited data. In recent years, these empirical correlation

methods found wide acceptability among petroleum engineers for numerical

simulation of experimental PVT tests. One such very popular method is to

employ equations of state to simulate laboratory tests.

An equation of state (EOS) is an analytical expression relating the pressure

(p) to the temperature (T) and the volume (V). Numerous equations of state have

been proposed and applied for phase behavior modelling and compositional

reservoir simulators. The most commonly used equations have been compared

by a number of investigators,^-^ resulting in a general conclusion that none of the

equations can be singled out as the most superior one to predict all the properties

at all conditions. It is, however, widely accepted that equations of state, when

properly tuned, are capable of adequately simulating the PVT properties of

reservoir fluids and can consequently save significant time and expense by

eliminating the need to perform a complete set of experimental PVT tests on each

and every new reservoir fluid. In addition, equations of state can also be used to

check the quality of the fluid sample collected and relative accuracy of many

laboratory tests.

The primary objective of this study was to prove or disprove the concept

of a vaporization/condensation process of increasing the temperature of a low

pressure hydrocarbon reservoir that contains low oil saturation. It was

conceptualized^o that when the immobile residual oil is subjected to increase in

temperature, a part of this oil converts into vapor and moves ahead in the

reservoir because of the fact that vapors have a much higher mobility compared

to liquids. These vapors moves ahead to the position of the reservoir which is

not affected by the increase in the temperature and become partly or fully

condensed due to a decrease in temperature (original reservoir temperature). As

the heated zone moves toward this area of newly condensed fluids, this zone is

again subjected to increase in temperature. This vapor again moves ahead to the

zone which is at the reservoir temperature and becomes condensed partially or

completely due to reduced temperature. This process was repeated until either

the oil was completely vaporized or the increase in the vapor content after each

stage (one vaporization/condensation cycle) was insignificant.

The scope of this study begins with the tuning of an equation of state to

match available experimental data. The tuned equation of state was then used to

model various increases and decreases in temperature of the immobile reservoir

fluid to predict the volumetric and phase behavior properties of the fluid.

Additionally, to achieve and further complement the primary objective,

the following secondary objectives were set:

to identify the most appropriate equation of state model that simulates

the available experimental PVT data.

to show that the vaporization/condensation process, if proved, results

in additional recovery by either enrichment of the produced gases or

mobilization of the oil due to increased saturation.

to observe the variation in the mole percent and volume percent of the

vapor and liquid phases with every cycle.

to study the variation in the composition of the liquid and vapor

phases with every cycle.

CHAPTER 2

LITERATURE REVIEW

predominantly of naturally occurring hydrocarbons that may exist in the solid,

liquid, or gaseous states, depending upon the conditions of pressure and

temperature to which it is subjected. These hydrocarbons exist at elevated

temperature and pressure in the reservoir, and upon production of these

hydrocarbon mixtures at the surface, the temperature and pressure of the

mixture are reduced. The phase state of the mixture at the surface conditions

depends on the composition of the fluid as produced from the well and on the

temperature and pressure at which it is captured. The fluid remaining in the

reservoir at any stage of depletion also undergoes physical changes as the

reservoir pressure is reduced by production of oil and gas from the reservoir.

Under natural production, the reservoir temperature is assumed constant

through the life of the reservoir. It is necessary to study the physical properties

of these naturally existing hydrocarbons, and in particular, their variation with

changes in pressure and temperature of the system, to estimate the performance

of the reservoir.

The intent of this chapter is to review the concepts of phase behavior and

vapor-liquid phase equilibria. Additionally, various widely used equations of

state were reviewed and compared for their applicability and accuracy.

A ''phase" is defined as that part of the system that is uniform in physical

and chemical properties, homogeneous in composition, and separated from other

coexisting phases by definite boundary surfaces. For example, ice, water, and

steam constitute three separate phases of the pure substance H2O because each is

homogeneous and physically distinct from the others and each is clearly defined

by the boundaries existing between them.

There are three different familiar phases: solid, liquid, and gas (vapor). A

solid possesses a definite shape and is hard to the touch. It is composed of

molecules with very low energy that stay in one place even though they vibrate.

A liquid has a definite volume but no definite shape. It will assume the shape of

the container in which it is placed but will not necessarily fill the container. The

molecules of which the liquid is composed possess more energy than a solid. A

vapor has no definite volume or shape and will fill a container in which it is

placed. The molecules have more energy than in the liquid form.

Whether a substance exists in a solid, liquid, or vapor phase is determined

by the temperature and pressure acting on the substance. It is known that solid

phase (ice) can be changed to liquid phase (water) by increasing its temperature

and this liquid phase can be changed to vapor phase (steam) by increasing the

temperature further. This change in phases is termed as Phase Behavior.

The objective of this section is to review the basic principles of

hydrocarbon phase behavior and describe the use of phase diagrams in

characterizing the volumetric behavior of pure substances (single-component

system) and mixtures (multi-component system). A phase diagram is a record of

the effects of pressure, temperature, and the composition on the type and

number of phases that can coexist in equilibrium with each other.

The simplest type of hydrocarbon mixture is one that contains only one

component. A single component system is composed entirely of one kind of

atom or molecule. The word ''pure" is generally used to describe a single

component system. The qualitative understanding of the relationship between

temperature (T), pressure (p), and volume (V) of pure components can provide

an excellent basis for understanding the phase behavior of complex petroleum

mixtures. Figure 2.1 is a typical phase diagram for a pure substance. It has three

axes p, V, and T and is composed of a series of plane surfaces, each of which

represents a given phase or mixture of phases. For example, plane BDHG

represents solid plus liquid phase, plane FGIJ represents solid plus vapor, and

plane HCI for the liquid plus vapor. All these planes are perpendicular to the

temperature axis.

A three-dimensional phase diagram like Figure 2.1 is difficult to use and

generally not required to describe phase behavior in hydrocarbon systems where

the vapor-liquid region (plane HCI) of the phase diagram is of primary concern.

Therefore, a projection of the three dimensional diagram, like P-T and P-V

diagram, is sufficient to describe the phase behavior of the hydrocarbon systems.

Figure 2.2 is a Typical P-T diagram for single component system. Since all of the

two-phase planes in figure 2.1 are perpendicular to the T axis, they appear as

single line in a P-T diagram. The resulting curve (line HC), which terminates at

the critical point (point C), is the dividing line between the area where liquid and

vapor exists. The curve is commonly called the "vapor pressure curve" or the

"boiling point curve." The corresponding pressure at any point on the curve is

called the vapor pressure.

Figure 2.3 is a typical pressure-volume diagram for a single component

system and is obtained experimentally by placing a fixed quantity of pure

component in a cylinder fitted with a frictionless piston and subjecting the

component to changes in pressure and temperature. The initial condition is

represented by point E on this diagram. The pure component which was in the

vapor state in the initial conditions (point E, temperature Ti) was subjected to a

isothermal pressure increase by forcing the piston into the cylinder. This results

in a decrease in the gas volume until it reaches the point F in the diagram, where

the liquid begins to condense. The corresponding pressure is known as the dew

point pressure pd, and is defined as the pressure at which the first drop of liquid

is formed. Further increase in pressure results in additional condensation. This

condensation process is characterized by a constant pressure and represented by

horizontal line FG. At point G, only traces of gas remain and the corresponding

pressure is called the bubble point pressure pb, and is defined as the pressure at

which the first sign of gas formation is detected. The slight forcing of the piston

into the cylinder at point G results in a sharp increase in pressure (point H)

without an appreciable decrease in the liquid volume. This is because the

compressibility of the liquid phase is much less compared to the vapor phase.

By repeating the above procedure at progressively increasing

temperatures, a family of curves of equal temperatures (isotherms) is

constructed. The dashed curve connecting the dew points is called the dew point

curve (line FC) and the dashed curve connecting the bubble points is called the

bubble point curve (line GC). A characteristic of a single component system is

that at a given temperature, the dew point and the bubble point pressure are

equal. These two curves meet at point C which is known as critical point. The

corresponding pressure and volume are called the critical pressure pc and critical

volume Vc respectively. For a single component system, the critical point is

defined as the highest value of pressure and temperature at which two phases

can coexist. The area enclosed by the phase envelope AFCGB is called the two

phase region. Within this region, vapor and liquid can coexist in equilibrium.

Outside the phase envelope, only one phase can exist.

2.1.2 Two-Component system

A distinguished feature of a single-component system is that, at a given

temperature, two phases (liquid and vapor) can exist in equilibrium at only one

pressure. But for a two-component or binary system, two phases can exist in

equilibrium at various pressures at the same temperature. The phase behavior

description of a binary system is more complex compared to a one-component

system because of the addition of another variable, composition, to the system.

The thermodynamic and physical properties of a binary system vary with a

change in composition. The effect of this variable is seen by comparing the

pressure-temperature diagram for a single component system (Figure 2.2) with

that of binary system (Figure 2.4). Figure 2.4 indicates that the pressure-

temperature relationship can no longer be represented by a simple vapor

pressure curve as in the case of single-component system but takes on the form

of a phase envelope ACB. This phase envelope is formed by an intersection of

the dew point curve (line BC) and the bubble point curve (line AC) at the critical

point C. The dashed line within the phase envelope are called "quality lines"

and they represent the pressure and temperature conditions of equal volumes of

liquid. For each possible composition, a distinct phase diagram exists. The

critical point for a binary system is defined as the point at which all intensive

properties of the vapor and liquid phases are equal. An intensive property is one

that has the same value for any part of a homogeneous system as it does for the

whole system, i.e., a property which is independent of the quantity of the system.

Critical pressure, critical temperature, density, composition, and viscosity are

examples of intensive properties.

2.1.3 Effect of Composition

Figure 2.5 demonstrates the effect of changing the composition of the

binary system on the shape and location of the phase envelope. Two lines

that form the phase envelope are the vapor pressure curves for methane and

propane. Three phase envelopes are shown for three different compositions of a

methane and propane mixture. These envelopes pass continuously from the

vapor pressure of the one pure component to that of the other as the composition

is varied. The dashed line is the line drawn tangent to all possible phase

envelopes at the critical point on each curve. It illustrates the locus of critical

points for the binary system. It can be seen from Figure 2.5 that when one of the

constituents becomes more dominant, the binary system tends to exhibit a

relatively narrow phase envelope and displays critical properties close to the

dominant component. The size of the phase envelope enlarges as the

composition of the mixture becomes evenly distributed between the two

components.

Figure 2.6 shows the critical loci for a number of common binary systems.

It can be seen that the critical pressure of the mixtures is considerably higher

than the critical pressure of the components in the mixtures. The greater the

difference in the boiling point of the two components, the higher the critical

pressure of the mixture will be.

The phase behavior of a multi-component system in the liquid-vapor

region is very similar to that of a binary system. However, as the system

becomes more complex with a greater number of components, the pressure and

temperature ranges in which two phases can coexist increases significantly.

10

Figure 2.7 shows a typical pressure-temperature phase diagram of a multi-

component system with a specific overall composition. Although a different

hydrocarbon system would have a different phase diagram, the general

configuration is similar.

These multi-component pressure-temperature phase diagrams are

commonly used to:

classify reservoirs

classify the naturally occurring hydrocarbon systems

describe the phase behavior of the reservoir fluids.

To completely understand the significance of the p-T diagram (Figure 2.7),

it is necessary to identify and define following key points on the p-T diagram:

Cricondentherm Tct (point E) - The cricondentherm is defined as the

maximum temperature above which liquid can not be formed

regardless of pressure. The corresponding pressure is known as

cricondentherm pressure pct.

Cricondenbar pcb, (point D) - The cricondenbar is the maximum

pressure above which no gas can be formed regardless of temperature.

The corresponding temperature is called the cricondenbar temperature

Tcb.

system is referred to as the state of pressure and temperature at which

all intensive properties of the vapor and liquid phases are equal. At

the critical point, the corresponding pressure and temperature are

called the critical pressure pc and critical temperature Tc of the system.

Phase Envelope (line BCA) - The region enclosed by bubble point

curve (line BC) and dew point curve (line AC) is called the phase

11

envelope of the system. Two phases (liquid and vapor) can coexist in

equilibrium only inside the phase envelope.

Quality Lines - The dashed lines within the phase diagram are called

quality lines. They describe pressure and temperature conditions for

equal volume of liquids. All quality lines converge at the critical point.

A complex mixture of hydrocarbon compounds or components can

exist as a single phase liquid, a single-phase gas or as a two-phase mixture

depending on the pressure, temperature and composition of the mixture. The

conditions under which these different phases can exist is a matter of

considerable practical importance in designing surface separation facilities and

developing compositional reservoir simulator models. The quantitative analysis

of a two-phase system involves the determination of the mole fractions of vapor

and liquid present at a given condition and computation of the number of

coexisting phases. These type of calculations are based on the concept of

equilibrium ratios.

The distribution of a component of a system between vapor and liquid is

expressed by the equilibrium ratio, also referred to as a equilibrium constant.

The equilibrium ratio, Ki, of a given component is defined as the ratio of the mole

fraction of the component in the vapor phase, yi, to the mole fraction of the

component in the liquid phase, Xi. Mathematically, the relationship is expressed

as:

K^ = (2.1)

12

The K-values of each component in a system is a function of the pressure,

temperature, and composition of the system. The composition of the system

considerably affects the K-values above 1000 psi; below 1000 psi the effect is

relatively small. The K-values can be physically measured for each reservoir

fluid, calculated from empirical correlations, or selected from a large number of

K-value measurements available in the literature. Numerous methods have been

proposed for predicting the equilibrium ratios of the hydrocarbon mixtures.

These correlations range from simple mathematical expressions to complicated

expressions containing several compositional dependent variables. Among these

methods, the most widely used method is Wilson's correlation.^^

Wilson^^ proposed the following expression for estimating K-values at

low pressures:

n 5.37(l+a>,.)fl-y

K^=^EXP^ ^ '^^ (2.2)

P

Where, pd and Td are the critical pressure and the critical temperature of

the component i. T and p are the system temperature and system pressure, and

coi is the acentric factor of the component i. The acentric factor is a correlating

parameter used to characterize the acentricity or non-sphericity of a molecule.

For detailed procedure of other methods of calculating equilibrium ratios,

the reader may consult the following textbooks.

Hydrocarbon Phase Behavior by Tarek Ahmed.^^

Gas Conditioning and Processing by John M. Campbell.^2

The main disadvantage of Wilson's correlation and other methods is their

limited range of pressure and temperature within which they can provide

accurate results, and their inability to incorporate the effect of the other

components present in the mixture on the prediction of K-values. These

disadvantages can be overcome by using equation of state methods for

13

predicting equilibrium ratios. This method provides accurate prediction of K-

values over a larger range of pressure and temperature for complex hydrocarbon

mixtures. The main disadvantage of this method is that it is very complex and

normally requires use of computers. A detailed description of using an equation

of state to predict equilibrium ratios is presented in next chapter.

The vast amount of work that has been done on equilibrium ratio studies

indicates their importance in solving phase behavior problems in reservoir and

process engineering. Equilibrium ratios are commonly used in the petroleum

industry to perform flash and separator calculations and to determine dew-point

and bubble-point pressures.

Flash calculations are an integral part of all reservoir and process

engineering calculations. They are required whenever it is desirable to know the

amount (in moles) of hydrocarbon liquid and vapor coexisting in a reservoir or a

vessel at a given pressure and temperature. These calculations are also

performed to determine the composition of the existing hydrocarbon phases.

Flash calculations are used to determine:

the number of phases,

molar volume of each phase,

molar composition of each phase.

A step by step procedure of performing flash calculations on the basis of

one mole of the hydrocarbon mixture is as follows:

Stepl: Calculation of moles of vapor phase, nv

Assume a starting value of nv. A good starting value can be calculated

from the following expression:

14

ny = (2.3)

A-B

where

i *

-.(^,-lJ

'Z,(A:,-I)"

i

mixture.

Evaluate the function f(nv) as given by the following expression using

the assumed value of nv.

/K) = Z ny{K,-\) +\

=0 (2.4)

e.g., 10'^^ than the assumed value of nv is the desired solution.

If the absolute value of the function is greater than the preset tolerance,

then a new value of nv can be calculated from the following

expression:

( \ -^M (2.5)

(ny j =ny - (v-

where,

(nv)n = new value of nv

^,(^,-1)'

/(.)=-I (2.6)

the above procedure is repeated with the new values of nv, until

convergence is achieved.

Step 2: Calculation of moles in liquid phase nL from the following

15

expression:

,,=!-, (2.7)

Step 3: Calculation of composition of liquid phase Xi from the following

equation:

^L -^nyK,

equation:

^ - ^ . ^ ' ' ^

Produced reservoir fluids are complex mixtures of components having

different physical properties. As a crude oil mixture flows from a high pressure,

high temperature petroleum reservoir to the surface, it experiences a reduction in

pressure and temperature. Because of this reduction in pressure and

temperature, gases evolve from the liquid and the well stream changes in

character. The physical separation of these phases, and the manner in which

they are separated influences the stock tank oil recovery. The principal means of

surface separation of oil and gas is the conventional stage separation. The stage

separation is the process in which gaseous and liquid hydrocarbon are separated

into vapor and liquid phases by two or more separators. These separators are

usually operated in series of consecutive lower pressures. Each condition of

pressure and temperature at which hydrocarbon phases are flashed is called a

stage of separation. There are two types of gas-oil separation process:

differential separation,

flash separation.

16

The differential separation process is generally performed for a black oil to

simulate the conditions encountered in the reservoir. The sample of reservoir

fluid in the laboratory cell is brought to the bubble point pressure, and the

temperature is set to the reservoir temperature. Pressure is reduced by

increasing the cell volume. All the gas is expelled from the cell while the

pressure is held constant by reducing the cell volume. The process is repeated in

steps until atmospheric pressure is reached. The solution gas that is liberated

from an oil sample during a decline in pressure is removed continuously from

contact with the oil before establishing equilibrium with the liquid phase. This

type of separation is characterized by the varying composition of the total

hydrocarbon system. The similar process used to simulate the reservoir

conditions for gas condensate is called as constant volume depletion. The only

difference is that in the constant volume depletion process, the sample of the

reservoir fluid is brought to the dew point pressure and the reservoir

temperature, and then the pressure is reduced in steps.

In the flash liberation process, the gas which is liberated from the oil

during the pressure decline remains in contact with the oil from which it was

liberated. The overall system composition remains constant during this type of

liberation because no gas is removed from the PVT cell during pressure

reductions. This procedure is sometimes referred in the literature as flash

vaporization, constant composition expansion, or flash expansion.

The differential liberation test is considered to better describe the

separation process taking place in the reservoir and is also considered to better

simulate the flowing behavior of hydrocarbon systems at conditions above the

critical gas saturation. As the saturation of the liberated gas reaches the critical

gas saturation, the liberated gas begins to flow, leaving behind the oil that

originally contained it. This is attributed to the fact that gases have, in general,

17

higher mobility than oils. The fluids produced from the reservoir to the surface

are considered to undergo flash liberation process.

These processes can also provide considerable insight in describing PVT

relationship for complex hydrocarbons. The experimental data obtained from a

flash liberation test include:

bubble point pressure

isothermal compressibility coefficient of the liquid phase above the

bubble point pressure

the two phase volume as a function of pressure, below the bubble

point.

The experimental data obtained from the differential liberation test

include:

amount of gas in solution as a function of pressure

the shrinkage in the oil volume as a function of pressure

properties of the evolved gas including the composition,

compressibility factor, and gas specific gravity

density of the remaining oil as a function of pressure.

The procedure for numerical simulation of differential and flash liberation

using equation of state is discussed in section 2.4.

An equation of state (EOS) for any substance is a mathematical expression

that provides the relationship between the pressure (p), volume (V), and the

temperature (T) of that substance. Equations of state are very sophisticated tools

for engineering applications and commonly used in the petroleum industry for

volumetric and phase behavior modelling of reservoir fluids.

18

The development of an EOS for the description of real systems started in

1893 with the publication of van der Waal's equation of state. Since then

hundreds of equations of state have been published in the literature and

promising new equations keep appearing. Leland^^ (1980) conducted a

comprehensive review of equations of state and classified them into the

following four families:

van der Waal family (vdW)

Benedict-Webb-Rubin family

reference-fluid equations

augmented-rigid-body equations.

The van der Waal family mainly encompasses simple, mostly cubic

equations of state. Their main characteristic is the separation between the

repulsive and attractive molecular forces. Leland reported that vdW EOS,

despite their simplicity, display quantitatively accurate performances in

describing the PVT relationship for complex hydrocarbon fluids.

The Benedict-Webb-Rubin (BWR) family includes complicated equations

of state that are empirical extension of the virial EOS. Besides the Benedict-

Webb-Rubin^^ EOS itself, the most significant members of this family for oil and

gas applications are the Sterling^^ EOS, and the Lee and Kesler^o EOS.

The reference-fluid equations are generally focused on accurate

representation of a large amount of PVT data for pure substances. An important

application of reference-fluid equations is their use as reference fluids in

corresponding state theories.

The augmented-rigid-body family combines the description of repulsive

forces between hard molecules of different shapes with the expression for the

molecular attractions. The sound theoretical basis of the repulsive form is the

most important and promising characteristic of these EOS.

19

Although all four families of EOS received considerable attention in the

past, recent literature mainly contains the developments in EOS of the vdW

family because of their simplicity and practicality. Tsonopoulos and Heidman^i

attribute the widespread use of cubic equations of state for describing PVT

relationships of oil/gas and phase equilibrium computations to the following

reasons:

Cubic EOS of van der Waals families yield relatively simple expression

for the thermodynamic properties and phase equilibrium relationships

of interest.

The EOS of the other three families, though more complicated in

nature, do not provide quantitatively better descriptions of phase

behavior than cubic EOS.

The intent of this section is to present a qualitative review of some widely

used cubic type equations of state, their applications, and tuning process of these

equations for different hydrocarbon systems.

Cubic equations of state are commonly used in the petroleum industry,

particularly in compositional reservoir simulators, to predict the phase behavior

of petroleum reservoir fluids. Since van der Waal proposed his EOS in 1873,

numerous modified versions with two or more parameters have been developed

to improve predictions of volumetric, thermal, physical and phase equilibrium

properties of the fluids. In this study, only the equations which are widely used

in the petroleum industry and a few promising EOS recently developed have

been reviewed.

The van der Waals or any other cubic equation of state can be expressed in

a following generalized form:

20

P "" p repulsive " p attractive (2.11))

RT a

RT/(V-b) and the attractive pressure term (pattractive) is described by a/V^. The

parameters a and b are constants characterizing the molecular properties of the

individual components. The parameter 'b' represents the real or hard-sphere

volume of the molecules, and 'a' represents the intermolecular attraction. These

parameters are normally determined by imposing critical conditions. Other

parameters in the above equation are defined as follows:

p = system pressure, psia

T = system temperature, R

R = gas constant, 10.73 psia-ftV (lb-mole)(oR)

V = molar volume, ft^/mole.

Equation 2.11 is usually referred as the van der Waal two parameter cubic

equation of state. The term "two parameter" refers to parameters a and b. For

vdW equations, these parameters can be computed from the following

expressions.

a = Q, '- (2.12)

Pc

RZ

b=Q , ^ (2.13)

Pc

Tc = critical temperature, R

Q = 0.421875

Q^ = 0.125.

21

The term cubic equation of state implies an equation which, if expanded,

would contain volume terms raised to first, second, and third power. Equation

2.11 can be expressed in the following cubic form in terms of volume.

RT_

V'- b+ F ' + -\V- =0 (2.14)

PJ \pj \pJ

compressibility factor Z by replacing the molar volume V in equation 2.14 with

ZRT/p.

hp

B=^ - (2.17)

Equation 2.15, when solved, yields one real root in the single phase region

and three real roots in the two phase region, where the largest root corresponds

to the compressibility factor of the vapor phase Z^, and the smallest positive root

corresponds to the compressibility factor of liquid phase Z^.

The van der Waals equation of state provides a good qualitative

description of the PVT behavior of substances in the liquid and vapor state. But

it is not considered accurate enough to be suitable for design purposes. Several

investigators developed new and more accurate equations of state that can be

used for facility design and reservoir simulation purposes. All equations of state

are generally developed for pure fluids, then extended to mixtures through the

use of mixing rules. These mixing rules are means of calculating mixture

parameters equivalent to those of pure components. Some of most popular EOS

are next discussed.

22

2.3.2 Redlich-Kwong EOS and its Modifications

Redlich and Kwong^^ demonstrated that by a simple adjustment, the

attractive pressure term (a/V^) in the van der Waal equation can considerably

improve the prediction of the volumetric and physical properties of the vapor

phase. These investigators replaced the attractive pressure term with a

generalized temperature dependent term. Their equation has the following

form:

RT a

where all the parameters are as defined for vdW EOS except parameters a

and b. These parameters can be calculated from the following expressions:

n2a-2.5

a = Q, ^ (2.19)

Pc

b=Q , ^ (2.20)

Pc

Where, Q^ =0.42747

Q^ =0.08664.

The Redlich-Kwong EOS can be expressed in the following cubic form:

Z'-Z'+{A-B-B')Z-AB =0 (2.21)

5 =-^. (2-23)

RT ^ '

These authors extended the application of their equation to hydrocarbon

liquid mixtures by employing the following mixing rules:

, = Sz,/0.5 (2.24)

.'=1

23

K=T^,b, (2.25)

/=1

where,

n = number of components in the mixture

ai = parameter a for the i* component as defined by equation 2.19

bi = parameter b for the i* component as defined by equation 2.20

am = parameter 'a' for a mixture

bm = parameter 'b' for a mixture

Zi = mole fraction of component i in the liquid or vapor phase.

To calculate am and bm for a hydrocarbon gas mixture with a composition

yi, replace Xi with yi in equations 2.24 and 2.25.

Several modification of Redlick-Kwong EOS are reported in the literature.

Zudkevitch and Joffe^^ and Joffe et al.^s modified the RK EOS by assuming that

the Qa and Qb parameters were temperature dependent. These authors obtained

Qa and Qb for each pure substance at any temperature from saturated liquid

density data, and equalization of the saturated liquid and vapor phase fugacity.

The term fugacity can be defines as the vapor pressure modified to represent

correctly the escaping tendency of the molecules from one phase into the other.

The fugacity of a component can be expressed in the following mathematical

form:

where,

/ = fugacity, psia

p = pressure, psia

Z = compressibility factor.

The ratio of the fugacity to the pressure, i.e., / / p , is called the fugacity

coefficient, O.

24

Soave26 kept the RK EOS volume function and introduced a temperature

dependent function to modify the attraction parameter. This suggestion by

Soave has prompted an enormous increase in activity on the part of scientists

and engineers who are interested in the use of EOS to predict fluid properties.

The Soave-Redlich-Kwong (SRK) equation of state has the following form:

RT aa

defined as:

c^ = [l + m(l-7;')]' (2.28)

Soave corrected the slope (m) against the acentric factor (co) by the

following generalized relationship:

m = 0.480 +1.5746; - 0.176^;' (2.29)

where, Tr = reduced temperature, T/Tc

CO = acentric factor of the substance.

For any pure component, the constants can be found from the following

expressions:

fl = Q, '- (2.30)

Pc

RT

b = n,^ (2.31)

and are independent of temperature, pressure, composition, or particular

component. For the SRK equation, these parameters have the following values:

Qa = 0.42747

Qb = 0.08664.

SRK equation can be expressed in the following cubic form:

25

Z' -Z^ +{A-B-B')Z-AB =0 (2.32)

^ =( ^ (2.33)

bp

B = -:- (2.34)

RT ^ ^

Soave suggested the following mixing rules for the vapor-liquid

equilibrium calculations:

i^^X, = Z Z ^,^/(////) [KJ -1) (2.35)

K, = T{^A) (2-36)

where Zi is the mole fraction of the component 'i' in the liquid or vapor

phase, and parameter kij is an empirically determined correction factor called the

binary interaction coefficient, characterizing the binary formed by component i

and component j in the hydrocarbon mixture. These binary interaction

coefficients are used to model the intermolecular interaction between the binary

components and are dependent on the difference in the molecular size of the

components. Slot-Petersen^^ described the following properties of binary

interaction coefficients:

a. The interaction between hydrocarbon components increases as the

relative difference between their molecular weight increases.

b. Hydrocarbon components with the same molecular weight have a

binary interaction coefficient of zero.

c. The binary interaction coefficient matrix is symmetric, i.e., ki,j = kj,i

The fugacity coefficient, OiS of a component 'i' in the liquid phase in a

mixture is represented by the following expression proposed by Soave^^:

26

\

A(2V, B\

ln{<^^)='-K^Mz'-B)-iB V V K)

In 1 +

Z'J

(2.37)

m

' ./

Z^ = compressibility factor of the liquid phase.

Equation 2.37 can also be used to determine the fugacity coefficient of

component 'i' in the vapor phase. Of, by using the composition of the vapor

phase, yi, in calculating A, B, Z \ and other composition dependent terms.

Graboski and Daubert^^ suggested that no binary interaction coefficients

are needed for hydrocarbon systems. However, when non-hydrocarbons are

present in the mixture, binary interaction coefficients can substantially enhance

the volumetric and phase behavior predictions of the mixture. Vidal and

Daubert29 and Elliot and Daubert^^ described the theoretical background of the

interaction coefficients and the quadratic mixing rules of the Soave equation.

Elliot, et al., proposed the following correlations for calculating binary

interaction coefficients:

For N2 system

k^j = 0.107089+ 2.9776A:; (2.40)

k,j =0.07654+ 0.01792 U ; (2.42)

27

k,. = 0.17985 + 2.6958^; +10.853(yt;)' (2.43)

(2.44)

" " 2e.e

' ./

The SRK equation of state is found to be capable of predicting vapor-

liquid equilibrium conditions (pressure, temperature, composition) for

hydrocarbon mixtures, but it does not provide very satisfactory results for liquid

compressibility predictions.

Peneloux, Rauzy, and Freze^^ introduced a volume correction parameter,

Ci, into the SRK EOS to minimize the errors in the saturated liquid volumes as

predicted by the SRK EOS. The third parameter does not change the vapor-

liquid equilibrium conditions determined by the SRK equation, but affects the

liquid and gas volumes by the following translation along the volume axis:

RT

c, = 0.40768(0.29441 - Z ^ ^ ) - (2.46)

r^ci

for each compound. The values of ZRA are in general not much different from

those of the critical compressibility factors Zc. If their values are not available,

Peneloux et al., proposed the following correlation for calculating Ci:

T

c, = 4.43797878(0.00261 + 0.0928^;,)^^ (2.47)

r^ci

28

2.3.3 Peng-Robinson EOS and its Modifications

Peng and Robinson^ proposed a modified Redlich-Kwong equation of

state capable of predicting the liquid density as well as vapor pressure in order

to further improve vapor-liquid equilibrium predictions. Their equation has the

following form:

RT aa

p = yz^-v(v+b)+b{v-b) ^^ ^

where parameters a and b are defined as:

(RTY

a = 0.457235^^-^^ (2.49)

Pc

RT

b = 0.011796-. (2.50)

Pc

(equation 2.27) with the following expression for calculating m:

m = 0.3796 +1.54226^; - 0.26992a;'. (2.51)

This expression was later modified to improve predictions for heavier

components by the investigators to give the following relationship:

w = 0.3796+ 1.485(y-0.1644fi;' +0.0\661co\ (2.52)

The Peng-Robinson equation can be arranged in the following cubic

compressibility form:

Z' +{B + \)Z^ +{A-3B' -2B)Z-{AB-B'-B'). (2.53)

calculated from the following equation:

H<t>,^)=-^^T^Mz'-B)- 2.828435

In

Z'-0.4145>

(2.54)

29

Mixture parameters in equations 2.53 and 2.54 (A, B, bm, vj/i, \|/) are defined

previously for the SRK equation.

Stryjek and Vera^*- 35 observed that large deviations between experimental

and calculated vapor pressures as a function of reduced temperature given by

the PR equation. They further stated that the observed deviations are large at all

temperatures for compounds with large acentric factors and that the errors

increase rapidly at low reduced temperatures for all compounds. These

investigators proposed that a major improvement can be obtained with the

following expression for m:

adjustable parameter characteristic of each pure component, and mo is defined

by the following expression:

For all components with a reduced temperature above 0.7, Stryjek and

Vera recommended setting mi = 0.

Jhaveri and Youngren^^ found in their application of the PR equation to

reservoir fluids that the error in the prediction of the gas phase compressibility

factors range from three to five percent and the error in the liquid density

predictions from six to twelve percent. Following the procedure proposed by

Peneloux et al.,^^ these authors introduced the volume correction parameter Ci to

the PR equation of state. This third parameter had the same units as the second

parameter bi of the unmodified PR equation and is defined by the following

relationship:

c,. = S,b, (2.57)

The authors then presented values of the shift parameter for the well defined

30

hydrocarbons. They also outlined the characterization procedure of the shift

parameter for the heptane plus fractions. These investigators concluded that a

significant improvement in the volumetric prediction can be obtained by the

modified PR equation.

The problem of characterizing the C7+ fractions in terms of their critical

properties and acentric factors has been long recognized in the petroleum

industry. Changing the characterization of C7+ fractions present in even small

amounts can have a profound effect on the PVT properties and the phase

equilibria of a hydrocarbon system as predicted by Peng and Robinson equation

of state. Recognizing this problem, Ahmed^^ devised an approach to determine

parameters a, b, and a from the readily measured physical properties of C7+

fractions (molecular weight and specific gravity). The author proposed the

following expression for calculating parameters a, b, and a of C7+ fractions:

'520' 0.5\

a = 1+ m 1- \ T ) (2.58)

f \

i^/rln. + a, MW^ + a, MW^.^^ + " '

m

a,+a,(MF/r)J MW^

(2.59)

2 ^^8

7ci+

a = a^ +^2 + a. + a. +

^ r ^ci. ^ r \:i. \ Y J n. ^n. (2.60)

2 ^8

+ 6rC7. +7rc:7. + -

/ C7+

MWc7+ = molecular weight of C7+

yc7+ = specific gravity of C7+

31

ai-as = coefficients as given by Ahmed.^^

The PR and SRK equations of state predict a critical compressibility factor,

Zc, of 0.307 and 0.333, respectively, for all substances, whereas Zc is in the range

of 0.2 to 0.3 for most real substances. Schmidt and Wenzel (SW)^^ introduced a

component dependent compressibility factor by incorporating the acentric factor

in the van der Waal equation. The three parameter SW equation of state has the

following form:

RT aa

P ^ V^ ~ V'+(\ + 3co)bV-3a)b' ^^-^^^

with

i^'^cf , RT,.

a = Q^--^ and b = Q,-

re Pc

a,=M.. (2.63)

The parameter Pc is given by the smallest positive root of the following

equation:

[6co + \)pl + 3/3^ + 3/?, - 1 = 0 (2.64)

and

4 = ,/, \ y (2.65)

3(1 + p^o))

Equation 2.64 can be solved for Pc by employing the Newton-Raphson

iterative method with a starting value of:

p^ = 0.25989 - 0.02176; + 0.00375^;'. (2.66)

The dimensionless factor a is a function of temperature and is defined by

following equations:

32

For Tr > 1, a = \- (0.4774 +1.328^;) ln(r,) (2.67)

The parameter m in the above expression is correlated with the acentric

factor and the reduced temperature. The authors propose the following

expression for slope m:

w = w, For CO < 0.4

m = m2 For co > 0.5

m = [(0.55 - co)m^ +(o)- 0.40)w2 ] /0.15 For 0.4 < co < 0.5

with

m,=m,^+{yjQ){5T^-3m,-\f (2.69)

^2 = mo+0.71(7,-0.779)' (2.70)

where,

w = 0.465 +1.3476; - 0.528^' For co < 0.3671 (2.71)

w = 0.5361 + 0.9593a; For co > 0.3671. (2.72)

factor terms to give the following form:

Z' +{UB-B-\)Z'' +(WB^ -UB^ UB + A)Z

~ (2 73)

-[WB' ^WB"- +AB) = 0

For hydrocarbon mixtures, the coefficients of equation 2.72 are defined by

the following equations:

A = ^->rr.j and B =

R^T^ RT

U = \ + 3cD, (2.74)

W = -3cu, (2.75)

33

Schmidt and Wenzel adopted the following mixing rules for calculating

the mixture parameters am, bm, and com:

. = Z Z ^/^/(,>) (l-^/y)

/=1 7=1 L

/=1

<",,,= (2.76)

lUft"'

The three parameter Schmidt-Wenzel equation has been reported to be as

capable as Peng-Robinson22 and Soave-Redlich-Kwong^^ equations in predicting

the vapor pressure while improving the predicted liquid density.

Patel and Teja (PT)^^ developed a cubic equation of state by introducing

two substance dependent parameters which are obtained from the liquid density

and vapor pressure data. These authors corrected the two parameters with the

acentric factor. Patel-Teja proposed the following form of EOS:

RT _ aa

P-y-b v'+(b + c)V-bc ^ ^

Where parameters a, b, c, and a are defined by the following expressions:

fl = Q. (2.78)

Pc

RT^

b = Q, (2.79)

Pc

RT

c = Q, (2.80)

Pc

a= l + m(l-r)f (2.81)

34

where,

f^c = 1 - 34 (2.83)

and Qb is the smallest positive root of the following cubic equation:

iterative technique with an initial value of Qb is given by following equation:

Q^ = 0.32429Z,, - 0.0022005. (2.85)

The P-T equation requires the knowledge of four characterization constant

Tc, pc 5c, and m for any fluid of interest. The authors points out that ^c is not

equal to the experimental compressibility factor, but is obtained from one or

more liquid density data and m is obtained from the vapor pressure of the pure

fluids. They proposed the following generalized expressions for the parameters:

m = 0.452413 + 1.30982fi; - 0.295937^;' (2.86)

4 = 0.329032 - 0.07679926; + 0.0211947^;'. (2.87)

The P-T equation (equation 2.77) can be used for the calculations of the

mixture properties, if the constants a, b, and c are replaced by the mixture

constants am, bm, and Cm, respectively. The mixture constants are defined as

follows:

6,=Ez,6, (2.89)

e, Y.z.c,. (2.90)

Equation 2.77 can also be rearranged to produce the following cubic form

in terms of compressibility factor:

35

Z'+(C-I)Z'+{A-2BC-B-C-B')Z+{BC+B'C-AB) =O

(2.91)

where, for mixtures

^n,P

A= (2.92)

(RTf

5 = ^ (2.93)

RT

C = EEE (2.94)

RT

For the Patel-Teja equation of state, the fugacity coefflcient is deflned by

the following expression:

b, ( y^A, (Q + d\ A( b,+c, )

In

Z-B\RTdJ \Q-d) + 2KQ'-d'J +

ln(o,) = - l n ( Z - 5 ) + ^

RT Q + r^

d] 2Qd

-{cX3B + C) + bX3C + B)}

In

8 Q-dJ Q'-d'

(2.95)

where.

Patel and Teja^^ concluded that the proposed EOS is capable of yielding

accurate vapor-liquid equilibrium predictions while reproducing liquid and

vapor phase densities with sufficient accuracy.

Willman and Teja^o proposed that for undefined components such as C7+

fractions, the parameters m and ^c in PT equation can be correlated in terms of

the boiling point Tb and specific gravity y. They proposed the following

relationships:

36

fl, 2 ^3

Valderrama and Cisternas^^ modified the PT equation by using the critical

compressibility factor instead of the parameter ^c to correlate parameters of PT

EOS. They proposed the following correlations:

4 (2.101)

+ 0.003752658Z

Q, = 0.577500514-1.898414283Z^. (2.103)

Valderrama^^ later introduced both the critical compressibility factor and

acentric factor as generalized parameters in the PT equation.

The equations of state are widely used in petroleum and chemical process

industries for process design and reservoir simulation purposes. Some of the

most common application of equations of state are:

Determination of equilibrium constants

Determination of dew point pressure

Determination of bubble point pressure

Determination of mixture critical properties

Two and three-phase equilibrium calculations.

Apart from above the applications, equations of state are also commonly

used in petroleum industry for simulating the PVT properties of the reservoir

fluids in place of costly experimental PVT tests. Some of experimental

procedures which can be adequately simulated using equations of state are:

37

Constant volume depletion test

Constant composition expansion test

Differential liberation test

Flash separation test

Composite liberation test

Swelling test.

Some of the applications of equations of state which are employed in this

study are next discussed in detail.

The system temperature (T), system pressure (p), and the overall

composition of the mixture must be known to determine the equilibrium

constant of a component in a mixture. The step-by-step procedure for

determining the equilibrium constants, as described by Ahmed,^^ is as follows:

Step 1: Assume an initial value of the equilibrium ratio for each

component in the mixture at the specified temperature and pressure. Wilson's.^^

equation can provide the starting values for equilibrium ratios.

5.37(1+^, )[l-^)

A Pa

K; = ^^ EXP (2.2)

p

where,

K,^ = assumed equilibrium ratio of component 'i'.

Step 2: Using the overall composition and assumed K-values, perform

flash calculations.

Step 3: Using the calculated composition of the liquid phase, Xi, determine

the fugacity coefficient, OiS for each component in the liquid phase from the

desired equation of state method.

38

Step 4: Repeat step three by using the calculated composition of the vapor

phase, yi, to determine the fugacity coefficient, Oi^, for each component in the

vapor phase.

Step 5: Calculate the new set of equilibrium ratios by employing the

following equation:

OL

K,=r- (2.105)

/

z

/=]

< G (2.106)

where,

e = preset error tolerance, e.g., 0.0001

n = number of components in the system.

If the above condition is satisfied, then the solution has been reached. If

not, steps one through six are repeated by using the calculated equilibrium ratios

as initial values.

The constant volume depletion (CVD) tests are performed on a gas -

condensate reservoir fluid sample in such a manner as to simulate pressure

depletion of an actual reservoir, assuming that retrograde liquid appearing

during production remains immobile in the reservoir. In the absence of the CVD

test data on a specific gas condensate system, the prediction of pressure

depletion behavior can be obtained by using any of the well established

equations of state to compute the phase behavior when the composition of the

total gas condensate system is known. The step by step procedure, as described

by Ahmed,^^ is summarized below:

39

Step 1: Assume that the original hydrocarbon system with a total

composition (zi) occupies an initial volume of one cubic feet at the dew point

pressure (pd) and system temperature (T):

Vi = l.

Step 2: Calculate the gas compressibility factor at dew point pressure (Zd)

from compressibility factor cubic equation for chosen equation of state, e.g.,

equation 2.53 for Peng-Robinson equation of state.

Step 3: Calculate the initial moles in place by applying the real gas law

level, the equilibrium ratios are calculated and used in performing flash

calculations. The calculated numerical results include:

equilibrium ratios

composition of the liquid phase (retrograde liquid), Xi

moles of the liquid phase, UL

composition of the vapor phase, yi

moles of the gas phase, nv

compressibility factor of the liquid phase, Z^

compressibility factor of the vapor phase, Zy.

Step 5: Because the flash calculations are usually performed assuming the

total moles are equal to one, calculate the actual moles of the liquid and vapor

phases from:

(nL)actuai = ninL (2.108)

(nv)actuai = ninv. (2.109)

Step 6: Calculate the volume of each hydrocarbon phase by applying the

following expressions:

40

(nA Z'RT

V, = ^-^'^ (2.110)

(ny) Z'RT

V, = ^-^'^ (2.111)

where,

F^ = volume of the liquid phase

V^ = volume of the vapor phase.

K = VL + V, (2.112)

where V, = total volume of the fluid, ft^.

Step 8: Since the volume of the cell is constant at one cubic feet, remove

the following excess gas volume from the cell:

^ = ^ F ^ . (2.114)

( " - )',original

Step 11: Calculate the two-phase gas deviation factor from the following

relationship:

41

i^twophase / \ . (2.116)

[n^-n^)RT

Step 12: Calculate the remaining moles of gas by subtracting the moles

produced from the actual number of moles of the vapor phase

M.-M.,^-".- (2.117)

Step 13: Calculate the new total moles and new composition remaining in

the cell by applying the molal and component balances

"={"X..A"A (2.118)

;?.

Step 14: Consider a new lower pressure and repeat steps four through

thirteen.

Constant composition expansion experiments, commonly called

pressure-volume tests, are performed on gas condensate or crude oil to simulate

the pressure-volume relations of these hydrocarbon systems. These tests are

conducted to determine:

saturation pressure (bubble point or dew point pressure)

compressibility factor of the gas phase

total hydrocarbon volume as a function of pressure.

The simulation procedure of constant composition expansion test, as

described by Ahmed,!^ is illustrated in the following steps:

Step 1: Given the total composition of the hydrocarbon system, Zi, and

saturation pressure (bubble point pressure, pb, for oil systems and dew point

42

pressure, pd, for gas systems), calculate the total volume occupied by one mole of

the system at saturation pressure by applying the following expression:

{\)ZRT

K. = - ^ (2.120)

where,

Kai ~ volume at saturation pressure, ft^/mole

p^.^, = saturation pressure, psia

Z = compressibility factor Z^ or Z^ depending on the type of system.

Step 2: The pressure is increased in steps above the saturation pressure.

At each pressure, the compressibility factor Z^ or Z^ is calculated from

compressibility factor cubic equation for the chosen equation of state, e.g.,

equation 2.53 for PR EOS, and used to determine the fluid volume

^. _ JDZRT

P

where,

V = compressed liquid or gas volume at the pressure p, ft^/mole

Z = compressibility factor of the compressed liquid or gas.

The corresponding relative phase volume (Vrei) is calculated from the

expression:

V

V =

' sal

pressure. The equilibrium ratios are calculated and flash calculations are

performed at each pressure level. The resulting data include Ki, Xi, yi, nL, nv, ZK

and Z^. Since no hydrocarbon material is removed during pressure depletion,

the original moles (ni=l) and composition remain constant. The volumes of

liquid and gas phases can then be calculated from the following expressions:

43

V, = - ^ (2.121)

V, = - ^ ^ (2.122)

and

Step 4: Calculate the relative total volume from the expression:

V

Relative total volume = ^.

'^ sal

The simulation procedure, as described by Ahmed,^^ jg summarized in the

following steps:

Step 1: Starting with saturation pressure (psat) and reservoir temperature

(T), calculate the volume occupied by one mole of the hydrocarbon system with a

overall composition of Zi by applying equation 2.120.

Step 2: Reduce the pressure to a predetermined value at which the

equilibrium ratios are calculated and used in performing flash calculations. The

actual number of moles of liquid phase with a composition of Xi, actual number

of moles of the vapor phase with a composition of yi, are then calculated from the

expressions:

(nL)actuai = ninL (2.108)

(nv)actuai = ninv. (2.109)

Step 3: Determine the volume of liquid and gas from following

expressions:

44

(nA Z'RT

y ^ ^ \ ^)aclual P^^Qj

(ny) Z'RT

y \Jacluai P^^^.

P

The volume of the produced gas is determined from the following

relationship:

G,=379.4(,)_, (2.123)

The total gas produced can also be calculated from the expression:

Step 4: Assume that all the equilibrium gas is removed from contact with

the oil. This can be mathematically achieved by setting the overall composition,

Zi, equal to the composition of the liquid phase, Xi, and setting the total moles

equal to the moles of the liquid phase.

Zi = X i

n i = (nL)actual

Step 5: Using the new overall composition and total moles, step two

through step four are repeated. When the depletion reaches the atmospheric

pressure, the temperature is changed to 60 ^F and the residual oil volume is

calculated.

Step 6: The calculated volumes of the oil and removed gas are then

divided by the residual oil volume to calculate the relative oil volume (Bod) and

the solution gas-oil ratio (Rsd) from the following expressions:

Bod = VL/Vsat (2.124)

Rsd = (5.615)(volume of gas in solution)/(Vsat). (2.125)

45

2.5 Comparison of Equations of State

Numerous equations of state have been proposed and applied for phase

behavior modelling and compositional reservoir simulations. The more

commonly used equations have been compared by a number of

investigators,!-^' ^^ resulting mainly in a general conclusion that none of the

available equations can be singled out as the most superior one to predict all the

properties at all conditions. A number of comparative studies^- ^ limited to

predictions of volumetric and vapor-liquid equilibrium properties of petroleum

reservoir fluids have shown that certain equations exhibit a higher overall

accuracy. But the reliability of these equations varies for different fluid systems

and conditions.

Danesh et al.^'^^ studied extensively the reliability of ten leading equations

of state for predicting the phase behavior and volumetric properties of

hydrocarbon fluids, with particular relevance to North Sea gas injection systems.

Based on the experimental and simulation results, the authors found the

following conclusions:

1. The Patel-Teja equation with modification by Valderrama and Redlich-

Kwong equation with modification by Zudkevitch and Joffe are

generally superior than other equations.

2. All the equations of state exhibit a similar convergence behavior. They

either could not easily converge or converged to the trivial solution of

equal partitioning of the components between the phases at conditions

close to the predicted critical point.

Ahmed^ conducted a study to evaluate eight commonly used equations of

state to compare their ability to predict the volumetric and phase equilibria of

gas condensate systems and offered the following conclusions:

46

1. The Schmidt-Wenzel equation of state exhibits a superior predictive

capability for volumetric properties of gas condensate systems.

2. The Patel-Teja and Schmidt-Wenzel equations are found to give

reliable gas compressibility predictions.

3. In terms of vapor-liquid equilibrium predictions, the Peng-Robinson,

the Patel-Teja, and Schmidt-Wenzel equations all perform equally well.

Cubic equations of state have found widespread acceptance as tools which

permit the convenient and flexible calculations of the phase behavior of the

reservoir fluids. They facilitate calculations of complex behavior associated with

rich condensates, volatile oils, and gas injection processes. Despite their

flexibility, the parameters of a cubic equation of state often need adjusting prior

to application to a particular reservoir fluid. For an EOS to reproduce

experimental data, it is necessary to adjust some of its parameters.^^' ^^ This

adjustment is necessary since the existing equations of state are only

approximations when applied to multi-component systems, besides the presence

of ill-defined mixtures of hydrocarbons, known as plus fractions, for which

information relevant to equations of state is usually not available. Adjusting the

parameters to overcome these limitations is called tuning or characterizing an

equation of state.

The parameters required for employing an equation of state are:

1. The critical temperatures, Tc, the critical pressures, pc, and the acentric

factor, CO, of each component of the mixtures.

2. The binary interaction coefficients, kij, between each pair of

components.

3. The molar composition.

47

For the well defined components of the mixture (N2, CO2, Ci-Ce), accurate

measured data are normally available for Tc, pc and acentric factor, and it is

usually not considered justified to use these as tuning parameters. However,

critical pressures and temperatures, and acentric factors for plus fractions are

usually determined from empirical correlation's which are prone to errors.

Therefore, it is considered justified to use Tc, pc, and co of the plus fractions as

tuning parameters.

There are two common approaches by which the equations of state are

tuned. One approach, proposed by Whitson,^^ consists of keeping the theoretical

parameters of the equation and performing the match on the critical properties

(Tc and pc) and the acentric factor of the plus fractions. The second approach,

proposed by Coats and Smart,^^ consists of calculating the critical properties and

acentric factor of plus fractions from available correlations and adjusting

theoretical equation of state parameters Qa and Qb for methane and plus fraction

and the binary interaction fractions between methane and plus fractions by using

non-linear regression to laboratory data. The laboratory data might include

saturation pressures, densities, equilibrium constants, constant volume

expansions, differential liberation, etc. Merril et al.^^ discussed in detail about

the sort of data that should be used in the tuning process. Pedersen et al.^i

recommended the use of molecular weight of plus fraction as tuning parameter.

These authors argued that the experimental uncertainty on the molecular weight

of the plus fraction is normally of the order of five to ten percent and, therefore,

justified to adjust the molecular weight of the plus fraction.

It is generally accepted that proper tuning of an equation of state can

substantially enhance the accuracy of volumetric and phase behavior predictions.

Pedersen et al.,^^ however, warned that the indiscriminate tuning can lead to

inconsistent predictions. The authors further stressed that the tuning procedure

48

will not correct the deficiencies of the equation of state used and that the EOS

predictive capabilities depend entirely on the type and the accuracy of the data

used for the tuning. The investigators emphasized that attempts should be made

to ensure that the tuned parameters are within reasonable physical limits.

The hydrocarbon plus fractions that comprise a significant portion of

naturally occurring hydrocarbon fluids create major problems when predicting

the thermodynamic properties and the volumetric behavior of these fluids by

equations of state. These problems arise due to the difficulty of properly

characterizing the plus fractions in terms of their critical properties and acentric

factors.

Whitson^^ have shown the effect of the heavy fractions characterization

procedure on PVT relationships prediction by equation of state. Usually, these

undefined plus fractions, commonly known as C7+ fractions, contain large

number of components with a carbon number greater than six. Molecular

weight and specific gravity of the C7+ fractions may be the only measured data

available. In the absence of detailed analytical data for the plus fraction in a

hydrocarbon mixture, erroneous predictions and conclusions can result if the

plus fraction is used directly as a single component in the mixture phase

behavior calculations. Hariu et al.^^ suggested that these errors can be

substantially reduced by splitting or breaking down the plus fraction into a

manageable number of fractions (pseudo-components) for equation of state

calculations.

Splitting or breaking down schemes refer to the procedures of dividing

the heptanes-plus fraction into hydrocarbon groups with a single carbon number

(C7, Cs, C9, etc.) and are described by the same physical properties used for pure

49

components. Several investigators^^' ^^-^^ proposed different schemes for

extending the molar distribution behavior of C7+, i.e., the molecular weight and

specific gravity. In general, the proposed schemes are based on the observation

that lighter systems such as condensates usually exhibit exponential molar

distribution, while heavier systems often show left-skewed behavior. This

behavior is shown schematically in Figure 2.8.

Three important requirement should be satisfied when applying any of

the proposed splitting models. These requirement are:

the sum of the mole fractions of the individual pseudo-components is

equal to the mole fraction of C7+.

the sum of the products of the mole fraction and the molecular weight

of the individual pseudo-components is equal to the product of mole

fraction and molecular weight of C7+.

the sum of the product of the mole fraction and molecular weight

divided by the specific gravity of each individual component is equal

to that of C7+.

50

LU

CC

(f)

LU

DC

QL

SPECIFIC VOLUME

Figure 2.1

P-V-T Diagram for a Single-Component System

(After Reference 12, Page 80)

51

P

r

e

s

s

u

r

e

Temperature

Figure 2.2

Pressure-Temperature Diagram for a Single-Component System

52

o

CO

</)

0)

Pd = Pt <

I

JL.

Vc

Volume

Figure 2.3

Pressure-Volume Diagram for a Single-Component System

(After Reference 14, Page 3)

53

LI qu \ii

a.

Gas

luKipcr <i l u r e

Figure 2.4

Typical Pressure-Temperature Diagram for a Binary System

(After Reference 14, Page 17)

54

Temperature

Figure 2.5

Effect of Composition on Phase Envelope for a Binary System

(After Reference 12, Page 85)

55

Temperature

Figure 2.6

Location of Critical Loci for Several Binary Systems

(After Reference 12, Page 85)

56

l i i K l e r s a t u r a t e d Oil Reservoir

H r 1

Ci n u ij 1 I'oiiiL

b Cricondenbar

Saturated

Reservoir

E Cricondentherm

Two-Phase /

Region

ijc ^ ct

Temperature

Figure 2.7

Typical Pressure-Temperature Diagram for a Multi-Component System

(After Reference 14, Page 22)

57

M

o

1 Left-Skewed Distribution

e (Heavy Hydrocarbon System)

F

r

a

c

t

I

o

n

Exponential Distribution

(Condensate System)

Molecular Weight

Figure 2.8

The Exponential and Left-Skewed Distribution Functions

58

CHAPTER 3

METHODOLOGY

The experimental data available from the PVT studies of two hydrocarbon

fluids were used to characterize the vaporization/condensation process of a low

density crude oil by elevating the temperature at constant pressure. The

experimental data included the composition of the hydrocarbon fluid at the

initial reservoir conditions and data from the constant composition expansion

test and constant volume depletion test.

Initially, an attempt was made to characterize the entire

vaporization/condensation process on HYSIM,^^ a process simulator provided

by Hypertech Limited. Although, this program provided good results for K-

value predictions and flash calculations, it was not capable of simulating the PVT

experimental procedures such as constant volume depletion test and constant

composition test which were required in this study.

Therefore, the entire characterization process was performed on WinProp,

a phase property program provided by Computer Modelling Group.^'^ This

program was capable of predicting K-values and performing flash calculations as

well as simulating required laboratory procedures.

This study was conducted in the following stages to achieve the study

objectives:

1. Compositional data was set for both fluids at initial pressure and

temperature conditions.

2. The most suitable equation of state model was identified by simulating

the constant composition expansion and constant volume depletion

tests using three equation of state models and comparing the

simulation results with the available experimental data.

59

3. The selected equation of state model was employed to describe

vaporization/condensation process for a low pressure, hydrocarbon

liquid-vapor system by elevating the temperature.

The following sections provide the detailed description of the procedure

during each of the above mentioned stages of the study. The adopted procedure

is also shown schematically in figure 3.1.

Plus Fractions

The composition of the fluids, referred as sample one and sample two,

were specified along with the initial pressure and temperature conditions. The

original composition of both the samples is listed in table 3.1. The initial

conditions for sample one and two were 5707 psig, 264 F and 5713 psig, 186 F,

respectively. In this stage, the following properties for each component were

specified for later use in the equation of state:

Molecular Weight (MW)

Critical Pressure (pc)

Critical Temperature (Tc)

Acentric Factor (co)

Specific Gravity (SG)

Normal Boiling Point Temperature (Tb).

For the well-defined pure components such as CO2, N2, Ci-Ce, all of these

properties are very well researched and widely reported in the literature.

However, this is not the case with an undefined mixture of components such as

hydrocarbon plus fractions or pseudo-components. Therefore, to characterize

the plus fractions, these fractions were divided into single carbon number (SCN)

fractions based on the molecular weight, specific gravity of the plus fractions

(table 3.2) and the fluid type. Since, it was known from the PVT experimental

60

results that both the fluids were retrograde condensate type, an exponential

molar distribution profile was specified for splitting hydrocarbon plus fractions

into single carbon number fractions. This was achieved by employing the built-

in splitting scheme of the software WinProp. This scheme estimates internally

the number of pseudo-components (SCN fractions) for the plus fractions. The

above mentioned properties of these pseudo-components were calculated from

the empirical correlations suggested by Lee and Kesler.20

The objective of this stage was to tune various equations of state to match

available experimental data and select the equation of state which produces the

closest match. Once the composition and properties of each pure and pseudo-

component were set, the following three equation of state models were used

separately to simulate the constant composition expansion test and constant

volume depletion test:

1. Peng-Robinson equation of state (PREOS).

2. Original Soave-Redlich-Kwong equation of state (SRKEOS).

3. Soave-Redlich-Kwong equation of state with the constant 'a' proposed

by Graboski and Daubert (SRKGDEOS).

For an equation of state to accurately reproduce the experimental data, it

was necessary to tune some of the equation of state parameters. This was

achieved by employing the regression procedure suggested by Agarwal et al.^^ to

tune the above mentioned equations of state. This procedure orders the

parameters, from the specified list of regression parameters, in such a way that

the most sensitive parameters are used first. The program "WinProp" has the

built-in feature that determines internally the most sensitive parameters. The

regression is performed by regressing on a small number of parameters at a time

61

(five in this study). Once a parameter reaches the maximum or minimum

allowed or does not contribute any longer to improve the match, it is replaced by

the next parameter that has not been used from the ordered list. Thus, it is

possible to specify a large set of regression parameters, and this procedure will

regress on a small number of parameters at a time, working from the most

sensitive parameters to least sensitive parameters.

The regression parameters used in this study were:

Critical pressures of pseudo-components (SCN fractions).

Critical temperatures of pseudo-components.

Acentric factors of pseudo-components.

Molecular weight of pseudo-components.

Volume shift parameter of methane and pseudo-components.

Binary interaction coefficient between CO2 and pseudo-components.

Binary interaction coefficient between methane and pseudo-

components.

Since the component properties, such as critical pressure, critical

temperature, acentric factor, and molecular weight of pseudo-components were

calculated from empirical correlations proposed by Lee and Kesler^o w^hich has a

error range o f + / - 1 0 % , a regression range of +/-10% was specified to tune these

parameters. For binary interaction coefficients, a trial and error method was

adopted to adjust these coefficients.

The experimental data used to tune the equations of state were relative

volume and equilibrium gas deviation factor data from constant composition

expansion test and retrograde liquid volume (% of hydrocarbon pore volume)

and produced gas (% of original moles) data from the constant volume depletion

test. The experimental data for samples one and two are presented in Tables 3.3

and 3.4, respectively.

62

Although, the prediction accuracy of the three equations of state models

were compared for all the above mentioned experimental data, the selection of

the equation of state model was based entirely on the accuracy of a particular

equation of state model in predicting the constant volume depletion test data

(retrograde liquid volume, produced gas). This was done because the simulation

of constant volume depletion test was used extensively in characterizing the

vaporization/condensation process in this study.

Process

The characterization of the vaporization/condensation process was

conducted at a low depleted pressure using the selected equation of state model.

Since, it was necessary to know the reservoir fluid composition at the reduced

pressure for the characterization process, a simulation of a constant volume

depletion test was conducted on the original hydrocarbon fluid to calculate fluid

compositions at specified depletion pressures (750 psia and 250 psia). These

pressures were constant throughout the vaporization/condensation process.

To check the accuracy of the calculated compositions, the CVD test was

also simulated at depletion pressures at which experimentally obtained

compositions were available. The calculated compositions were then compared

with experimental compositions, and it was assumed that the same amount of

error would be present in the composition calculated at a specified depletion

pressure. The experimental compositions were available at 715 psia for sample 1

and 619.7 psia for sample 2. It was assumed that reservoir temperature would

remain constant throughout the depletion process.

The vaporization/condensation process is shown schematically in Figure

3.2.

63

Once, the composition at the specified depletion pressure was available,

the following step-by-step procedure was adopted to characterize the

vaporization/ condensation process:

1. Flash calculations were performed on the calculated composition at the

specified depletion pressure and reservoir temperature, assuming 100

moles of fluid in place, to obtain the mole percent of liquid and vapor,

volume percent of liquid and vapor, liquid composition and vapor

composition.

2. The vaporization process was characterized by simulating the CVD

test at the depletion pressure and specified elevated temperature. The

elevated temperatures used were 700 F and 500 F for sample one and

500 F and 350 F for sample two. Different temperatures were used

for samples one and two because it was found that the fluid was

vaporizing completely at temperatures above 550 F in case of sample

two. In the laboratory CVD test, the sample of reservoir fluid is placed

in the test cell at the original pressure and temperature, and the

pressure in the cell is brought down to a specified pressure. The

reduction of pressure results in the generation of additional gas

(produced gas) which is expelled from the test cell to a separator. The

simulation of a CVD test was considered ideal for characterizing the

vaporization process in the reservoir because both generate excess gas

which is removed from the place where this gas was generated. The

difference between the CVD test and vaporization process is that in a

CVD test, the excess gases are generated due to reduction in pressure,

while, in the vaporization process, the excess gases are generated due

to an increase in temperature. The other difference is that in the CVD

test, the produced gas is sent to a separator, while, in the case of

64

vaporization, this produced gas is recombined with the depleted liquid

volume and composition at the original temperature. The output

obtained from the simulation of the CVD test were the mole percent,

and the compositions of the produced gas and liquid left in the test

cell.

3. The condensation process was characterized by moving the produced

gas from the vaporization stage to the PVT cell which is at the original

reservoir temperature and equilibrating the produced gas with the

liquid in place at the depleted pressure. It was assumed that the gas

moved from the vaporization stage displaces completely the gas in

place at the initial pressure and temperature. The overall composition

of the equilibrium liquid and vapor (produced gas and liquid in place)

was calculated by employing the following expression:

^'" U]^x~)

V ^ ' nroduced s i'/in-place

where.

z, = mole fraction of component "i" in the mixture

V '/in-place *

V '^/in-place *

depleted pressure to obtain mole percent and volume percent of the

liquid and vapor, respectively, and liquid and vapor compositions. At

this stage, the first vaporization/condensation cycle was completed.

65

5. After every vaporization/condensation cycle, the following condition

was tested:

[(Mole % of Liquid)n - (Mole % of Liquid)r,-i] < 1.0%

where,

(Mole % of Liquid)n = mole percent of liquid after "n" cycles

(Mole % of Liquid)n.i = mole percent of liquid after "n-1" cycles

This condition was applied because it was decided that the

vaporization/condensation process would be ineffective further if the

difference between the mole percent of liquid calculated after

consecutive cycles is less than one.

6. If the above condition was not satisfied, the whole process was

repeated beginning with the characterization of the vaporization

process using the new composition.

7. If the condition mentioned in step five was satisfied, then the possible

trends were observed by plotting separately mole percent of liquid and

vapor, volume percent (saturation) of liquid and vapor, overall

composition, liquid composition and vapor composition versus cycles.

Here one cycle is referred as one vaporization and condensation

process.

Once the characterization of the vaporization/condensation process for

one combination of reservoir pressure and elevated temperature was completed,

the whole process was repeated for other combinations of reservoir pressures

and elevated temperatures for both the samples and possible trends were noted.

3.4 Assumptions

The following summarizes the assumptions that were employed to

simplify the study and achieve the study objective:

66

1. To establish the fluid composition at depleted pressures, the reservoir

temperature was assumed constant during the depletion process.

2. The pressure would remain constant during the whole

vaporization/condensation process.

3. Composition and saturation of liquid and vapor phases were the same

at the initial and depleted reservoir conditions.

4. Residual liquid that appears during production would remain

immobile and could only be "produced" via vaporization.

5. A step temperature profile was assumed, i.e., the temperature

increases sharply from the initial temperature to the vaporization

temperature at the vaporization stage and decreases sharply from

vaporization temperature to the initial temperature at the

condensation stage.

6. Excess gas generated during the vaporization stage (produced gases in

the simulation of constant volume depletion tests), when placed with

the original liquid still at the original temperature, displaces the

original gas-in-place completely, i.e., total volume of produced gas

displaces completely the total volume of gas originally in place (at

initial temperature). This was accomplished by displacing moles of

gas in place with moles of produced gas.

7. The temperature increase at the vaporization stage does not result in

any change in overall composition, i.e., thermal cracking or burning

does not occur.

67

Table 3.1

Original Composition of Samples One and Two

Sample 1 Sample 2

H2S Nil Nil

CO2 2.27 0.18

N2 0.72 0.13

Ci 69.01 61.92

C2 7.69 14.08

C3 3.71 8.35

i-a 1.59 0.97

n-C4 1.78 3.41

i-Cs 1.26 0.84

n-Cs 0.75 1.48

C6 1.72 1.79

C7+ 9.50 6.85

Table 3.2

Properties of Plus Fractions

Molecular Weight 174 143

Specific Gravity 0.786 0.795

68

Table 3.3

Experimental Data for Sample 1

(psia) Volume Z-Factor Volume (% of Original

(% of HC Pore Volume) Moles)

7015 0.8955 - - -

6015 0.9396 - - -

5515 0.9696 - - -

5115 0.9989 - - -

5098 1.0004 - 0.6 -

3615 1.2304 0.904 30.8 18.709

2815 1.5016 - - -

2015 2.0501 - - -

1637 2.5256 - - -

1402 2.9617 - - -

15 - - 18.5 -

69

Table 3.4

Experimental Data for Sample 2

(psia) Volume Z-Factor Volume (% of Original

(% of HC Pore Volume) Mole)

6014.7 0.8808 - - -

5314.7 0.9158 - - -

5014.7 0.9317 - - -

4414.7 0.9690 - - -

3814.7 1.0194 - - -

3724.7 1.0299 - - -

3314.7 1.0878 - - -

3014.7 1.1496 - - -

2719.7 1.2430 - - -

2219.7 1.5246 - - -

1619.7 2.1035 - - -

1024.7 3.5665 - - -

14.7 - - 12.6 93.515

70

Set-Up Initial Data

(Composition, Component Properties)

Temperature to Calculate Xi, yi. Mole % of liquid and Vapor,

Volume % of Liquid and Vapor

at Depleted Pressure and Vaporization Temperature

Initial Conditions

Produced Gas to the Moles of Liquid Initially in Place

Reservoir Temperature to Calculate New Xi, yi. Mole % of liquid and

Vapor, Volume % of Liquid and Vapor

If, No

If, Yes

Plot Cycles Versus Mole % and Volume % of Liquid

and Vapor, Overall Composition, Liquid

Composition, Vapor Composition

Figure 3.1

Flow Diagram of Procedure Used in the Study

71

o JJ

o

p.

en

O

5 "^ (N U

O ^

u C O

X c ... CD

u CD

/ :3 ^

u CD

O CD

u a O)

u >

o

;-!

O o CD rr, PH

CI. 03 CI. o

R> cs N

O o

.4-1

> ^ 2 ^ " CD

>

c;

-d

o

.11 o

C

.2 - I( >^

U

-d U

o -d CO o

CC

U o O) N

u

411 u O

O ^ I

U (-0

.O >

JJ

U D

CD o

.1t

.4-1

(-0

PH

a .- :i3 o

^ 1^ ^

vo

O II |_H

72

CHAPTER 4

DISCUSSION OF RESULTS

characterization of vaporization/condensation process in the reservoir were

accomplished.

The equation of state model was identified by simulating a constant

volume depletion test and constant composition expansion test using three

equation of state models. The simulation results from these equations of state

were compared with experimental data, and the equation of state model that

predicted constant volume depletion test data most accurately was selected. The

characterization of the vaporization/condensation process in the reservoir was

accomplished through a combination of constant volume depletion test

simulation, and flash calculations using the selected equation of state model.

The following sections provide detailed description of results from

various stages of study.

The plus fraction of the reservoir fluid from both samples were split into

single carbon number (SCN) fractions and the SCN fraction properties were

calculated from empirical correlations proposed by Lee and Kesler.^i Plus

fractions from Sample one were split into five SCN fraction while plus fractions

from sample two were divided into four SCN fractions. The composition and

properties of SCN fractions from samples one and two are listed in Tables 4.1

and 4.2, respectively.

73

4.2 Selection of Equation of State Model

Three equation of state models were tested for accuracy in predicting

relative volume and equilibrium gas deviation factor from constant composition

expansion test simulation, and retrograde liquid volume and produced gas from

constant volume depletion test simulation.

It was found that all the equation of state models predicted relative

volume quite accurately (Figures 4.1 to 4.6) with the exception of SRKEOS and

SRKGDEOS in case of sample one (Figures 4.2 and 4.3). Among the three

models, the Peng-Robinson equation of state model was found to be most

accurate in predicting relative volume data (Figures 4.1 and 4.4). It was also

observed that none of the equation of state models were able to predict

equilibrium gas deviation factor (Figures 4.7 to 4.12) very well.

Although the accurate prediction of relative volume and gas deviation

factor were not the criterion for selection of the equation of state model, these

factors were calculated to verify the accuracy of the equation of state. The

selection of the equation of state was made on the basis of their accuracy in

predicting retrograde liquid volume and produced gas data. The results from

tested equation of state models in predicting the retrograde Hquid volume for

both sample are presented in Tables 4.3 and 4.4 and Figures 4.13 to 4.18 along

with the experimentally obtained data. It was observed from these tables and

figures that the values obtained from Peng-Robinson equation of state were the

closest to the experimental values. The results from tested the equation of state

models in predicting the produced gas for both sample are presented in Tables

4.5 and 4.6 and Figures 4.13 to 4.18 and again the Peng-Robinson equation of

state was found to be most accurate. Large errors were observed in predicting

retrograde liquid volume and produced gas from SRKEOS and SRKGDEOS in

case of sample one. These large errors were occurring probably due to inability

74

of these equation of state models in predicting accurate saturation pressures.

The error in calculating saturation pressure by these equations of state were

found to be large (Table 4.7) in case of sample one.

Based on the above mentioned results, the Peng-Robinson equation of

state model was selected to be used further in the study.

Condensation Process

The first step in characterizing the vaporization/condensation process

was to calculate fluid composition at specified depleted conditions. This was

accomplished by simulating constant volume depletion tests on the original

hydrocarbon fluid using the Peng-Robinson equation of state. Fluid

compositions were also calculated at depletion pressures at which

experimentally obtained compositions were available. The comparison between

calculated composition and experimental composition was presented in Table 4.8

for sample one and Table 4.9 for sample two. The calculated composition for

both samples was found to be very accurate, and it was assumed that

composition calculated at specified depletion pressures had the same degree of

accuracy. The calculated composition at 750 psia and 250 psia are listed in Tables

4.10 and 4.11 for samples one and two, respectively.

The vaporization/condensation process was characterized at each selected

reservoir pressure (750 psia and 250 psia) and vaporization temperature (700 F

and 500 F for sample one, 500 F and 350 F for sample two) combination. The

following were the results from the characterization process:

Variation in mole percent of liquid and vapor with every

vaporization/condensation cycle was plotted for every pressure-

vaporization temperature combination for both samples (Figures 4.19

to 4.26). The mole percent of the liquid was found to be increasing

75

with every cycle, while the mole percent of the vapor was decreasing

with cycles in all the cases. However, the extent of this trend was

different for different combination of reservoir pressure and

vaporization temperature for both samples. This trend was significant

in the cases of a relatively high depleted pressure and high

vaporization temperature (Figures 4.19 and 4.23). This trend was less

significant in the cases of either low vaporization temperature (Figures

4.20 and 4.24) or lower depleted pressure (Figures 4.21 and 4.25) and

almost non-existent in the cases of low pressure and low temperature

(Figures 4.22 and 4.26). In the case of sample one, the mole percent of

liquid was increased from 44% to 96% at high pressure and high

temperature (Figure 4.19), while at the same pressure and low

temperature the mole percent of the liquid increased from 44% to 81%

(Figure 4.20). In the case of sample two, the mole percent of liquid was

increased from 44% to 93% at high pressure and high temperature

(Figure 4.23), while at the same pressure and low temperature the mole

percent of liquid changed from 44% to 11% (Figure 4.24). This

indicates that the vaporization/condensation process was more

effective at high vaporization temperature. The mole percent of liquid

was increased from 64% to 95% at low pressure and high temperature

in case of sample one (Figure 4.21), and from 64% to 93% in case of

sample two (Figure 4.25). This increase was significant but still less

than the increase in the case of high pressure and high temperature

(Figures 4.19 and 4.23 for samples one and two, respectively). This

indicates that the vaporization/condensation process was more

effective at high temperature. Therefore, it was concluded that the best

results will be obtained if the vaporization/condensation process is

76

conducted at the high depleted pressure and high vaporization

temperature.

Variation in volume percent (saturation) of liquid and vapor with

every vaporization/condensation cycle was plotted for every depleted

pressure-vaporization temperature combination for both samples

(Figures 4.27 to 4.34). Similar trends were observed in the variation of

liquid and vapor saturation as in the cases of molar variation. In the

case of sample one, the volume percent of liquid (liquid saturation)

was increased from 21% to 90% at the high pressure and high

temperature (Figure 4.27), while at the same pressure and low

temperature the liquid saturation was increased from 21% to 59%

(Figure 4.28). In the case of sample two, the liquid saturation was

increased from 19% to 80% at high pressure and high temperature

(Figure 4.31), while at the same pressure and low temperature the

liquid saturation was changed from 19% to 49% (Figure 4.32). This

again suggests that the vaporization/condensation was more effective

at high vaporization temperature. The liquid saturation was increased

from 19% to 71% at low pressure and high temperature in case of

sample one (Figure 4.29), and from 15% to 58% in case of sample two

(Figure 4.33). This increase was significant but still less than the

increase in the case of high pressure and high temperature (Figures

4.27 and 4.31 for samples one and two, respectively). This indicates

that the vaporization/condensation process was more effective at the

higher vaporization temperature. Again, it was concluded that the

best results can be obtained if the vaporization/condensation process

is conducted at the higher depleted pressure and high vaporization

temperature. The increasing trend in liquid saturation suggests that

77

after multiple cycles, the liquid saturation may be much larger than the

residual liquid saturation for a particular media. At this stage, the

liquid may become mobile and, therefore, result in additional

recovery.

Variation in overall composition with vaporization/condensation

cycles (Figures 4.35 to 4.42) were also studied. It was found that mole

percent of the lighter components (Ci, C2) was decreasing, while that

of heavier components (SCN fractions) was increasing. The variation

in mole percent of middle components (Ca-Ce) was insignificant.

Again, these trends were more pronounced in cases of high pressure

and high vaporization temperature conditions (Figures 4.35 and 4.39)

and less pronounced at low pressure and low temperature (Figures

4.38 and 4.42).

Variation trends in liquid composition (Figures 4.43 to 4.50) and vapor

composition (Figures 4.51 to 4.58) were also studied, and it was found

that there was a perceptible decrease in mole percent of the plus

fraction in the liquid composition with cycles, while decrease in the

mole percent of methane was very marginal. The change in mole

percent of other components was found to be insignificant. This

indicated that the liquid was getting lighter with every cycle. Since

lighter liquids generally have lower viscosity compared to heavier

liquids, the mobility of the liquid will increase with cycles, thus

improving the possibility of the liquid to become mobile. In the case of

vapor composition, it was found that the mole percent of methane was

decreasing with cycles, while the mole percent of other components

was increasing. This increase was significant in the case of ethane.

78

propane and plus fractions. This indicates that the gas is getting richer

with every cycle.

Trends in variation of total number of moles in place with each cycle

(Table 4.12) were also observed. It was found that the total number of

moles were increasing with each cycle at low pressures while total

number of moles were decreasing at high pressures. This observation

was contrary to expectations that the total number of moles in place

will increase with each cycle in all cases. This expectation was made

because at the vaporization stage, a large portion of the liquid should

vaporize. Placing only the enriched gas in place with original liquid

should result in an increase in overall number of moles at the new

location. It seems that this anomaly was occurring due to assumption

that the produced gas from the vaporization stage displaces

completely the gas in place at the new location. Therefore, it is

recommended that an effort should be made to improve this

assumption.

In this study, the characterization of the vaporization/condensation

process was computer modeled as a PVT cell where it was possible to increase

the temperature of the cell by heating the cell from the outside. This type of

heating does not interfere with the overall composition of the fluid in the PVT

cell. However, in the case of actual reservoir, the temperature of the reservoir

can only be raised by either injecting the heat into the reservoir (steam injection,

hot water injection) or by creating the heat in-situ (in-situ combustion). Both of

these heating mechanisms can interfere with the composition of fluid in the

reservoir. In the case of steam injection, steam will move with produced gases at

the vaporization stage and condense into water at the condensation stage. In the

case of in-situ combustion, large amounts of combustion gases will be generated

79

at the vaporization stage along with thermal cracking of oil thus, affecting the

overall composition. Therefore, the effect of the heating mechanism should be

taken into consideration when conducting this study for an actual reservoir. The

effects of flow characteristics, primarily viscosity, of the fluids (gas and liquid) in

the reservoir should also be kept in mind when characterizing the

vaporization/condensation process for an actual reservoir.

80

Table 4.1

Composition and Properties of SCN Fractions

(Sample 1)

SCN Composition MW SG Tb Pc Tc CO

C7-C10 4.38238 113.4 0.723 384.9 27.0 563.5 0.3601

C11-C13 2.08084 161.6 0.772 461.1 20.7 641.6 0.5153

C14-C16 1.32715 207.7 0.801 519.5 17.1 697.3 0.6461

C17-C20 0.79125 257.3 0.821 573.3 14.4 745.8 0.7726

C21+ 0.91839 371.0 0.851 676.7 10.7 833.1 1.0081

Figure 4.2

Composition and Properties of SCN Fractions

(Sample 2)

SCN Composition MW SG Tb Pc Tc CO

81

Table 4.3

Comparison of Retrograde Liquid Volume Calculated By

Different EOS (Sample 1)

(psia) (% of HC Pore Volume)

Experimental Calculated

PREOS SRKEOS SRKGDEOS

5102 0.0 0 7.879 7.886

5098 0.6 0 7.882 7.888

5075 3.5 3.307 7.896 7.902

5015 9.2 11.909 7.932 7.936

4918 14.7 18.477 7.992 7.993

4723 20.9 24.1 8.118 8.113

4415 26.0 27.508 8.348 8.333

3615 30.8 29.63 9.671 9.616

2715 30.6 28.29 22.575 22.413

1815 27.7 25.464 23.979 23.791

82

Table 4.4

Comparison of Retrograde Liquid Volume Calculated By

Different EOS (Sample 2)

(psia) (% of HC Pore Volume)

Experimental Calculated

PREOS SRKEOS SRKGDEOS

4014.7 0.0 0.0 0.0 0.0

3514.7 3.3 3.335 3.32 3.324

2914.7 19.4 20.332 21.175 22.134

2114.7 23.9 24.782 25.31 25.326

1314.7 22.5 22.79 22.226 22.122

605.7 18.1 18.002 17.094 16.949

14.7 12.6 9.989 7.45 7.247

83

Table 4.5

Comparison of Produced Gas Calculated By

Different EOS (Sample 1)

(psia) (% of Original Mole)

Experimental Calculated

PREOS SRKEOS SRKGDEOS

5102 0.0 0.0 19.042 19.454

4415 6.955 7.602 24.039 24.444

3615 18.709 18.979 31.467 31.854

2715 34.922 34.834 44.963 45.303

1815 53.555 53.259 60.518 60.749

1215 66.298 66.355 71.565 71.72

715 77.132 77.43 81.044 81.14

84

Table 4.6

Comparison of Produced Gas Calculated By

Different EOS (Sample 2)

(psia) (% of Original Mole)

Experimental Calculated

PREOS SRKEOS SRKGDEOS

4014.7 0.0 0.0 0.0 0.0

3514.7 5.374 4.341 1.887 1.671

2914.7 15.438 12.189 11.638 11.481

2114.7 35.096 33.33 31.343 31.073

1314.7 57.695 54.681 51.681 51.356

605.7 76.787 75.804 73.346 75.116

14.7 93.515 95.488 96.262 96.196

Table 4.7

Comparison of Saturation Pressures Calculated By

Different EOS

Saturation Pressure

(psia)

Experimental Calculated

PREOS SRKEOS SRKGDEOS

85

Table 4.8

Comparison Between Experimentally Obtained

Composition and Composition Calculated By

PREOS at Depleted Reservoir Pressure

(Sample 1)

(Mole %)

Liquid Vapor

Experimental Calculated Experimental Calculated

CO2 0.68 0.65 2.46 2.50

N2 0.07 0.07 0.77 0.76

Ci 12.73 13.45 75.83 74.80

C2 3.88 3.63 8.20 8.60

C3 3.44 3.32 3.94 4.11

i-Q 2.14 2.20 1.65 1.69

86

Table 4.9

Comparison Between Experimentally Obtained

Composition and Composition Calculated By

PREOS at Depleted Reservoir Pressure

(Sample 2)

(Mole %)

Liquid Vapor

Experimental Calculated Experimental Calculated

CO2 0.05 0.05 0.21 0.20

N2 0.01 0.01 0.14 0.14

Ci 9.87 10.42 66.59 67.28

C2 7.13 7.26 16.06 15.85

C3 9.21 9.48 9.11 9.09

i-C4 1.80 1.81 1.01 0.96

n-O 7.54 7.47 3.31 3.19

n-Cs 5.42 5.18 1.02 1.02

87

Table 4.10

Calculated Compositions at Depleted Reservoir

Pressures and Original Reservoir Temperature

(Sample 1)

Component Composition

(Mole %)

at 750 psia at 250 psia

Overall Liquid Vapor Overall Liquid Vapor

CO2 1.69 0.64 2.50 0.99 0.22 2.38

N2 0.46 0.07 0.76 0.24 0.02 0.65

Ci 47.82 13.46 74.80 26.98 4.24 67.78

C2 6.41 3.63 8.59 4.14 1.46 8.94

C3 3.77 3.32 4.12 2.89 1.71 5.01

i-Q 1.92 2.20 1.69 1.73 1.39 2.34

88

Table 4.11

Calculated Compositions at Depleted Reservoir

Pressures and Original Reservoir Temperature

(Sample 2)

Component Composition

(Mole %)

at 750 psia at 250 psia

Overall Liquid Vapor Overall Liquid Vapor

CO2 0.14 0.06 0.20 0.08 0.02 0.19

N2 0.08 0.01 0.14 0.04 0.003 0.11

Ci 43.71 12.82 68.56 23.93 3.72 59.72

C2 12.29 8.23 15.55 8.20 3.46 16.59

C3 9.25 10.04 8.62 8.02 6.04 11.53

i-a 1.31 1.83 0.89 1.42 1.44 1.40

89

Table 4.12

Moles of Fluid in Place After Each Cycle

Sample 1 Sample 2

750 psi 750 psi 250 psi 250 psi 750 psi 750 psi 250 psi 250 psi

700 F 500 F 700 F 500 F 500 F 350 F 500 F 350 F

0 100 100 100 100 100 100 100 100

1 105.1 104.9 141.5 120.7 106.0 104.4 144.5 118.7

2 96.77 101.7 170.5 131.6 102.1 100.1 175.7 127.2

3 84.64 95.2 190.7 138.8 94.3 94.57 200.2 133.1

4 74.31 88.67 205.6 144.0 86.89 89.28 219.7 -

11 - - 237.1 - - - 285.3 -

90

"^ "in -

O

Final ROV

"^ nn

O Exp. ROV

.. o en .

C

Relative Volume

1 f^n

1 .ou -

1 .UU -

0.50 -

1000 2000 3000 4000 5000 6000 7000 8000

Pressure (psia)

Figure 4.1

Comparison of Relative Volume Data

(Sample 1, PREOS)

91

4.00

3.50

ol

3.00

o\

Final ROV

o Exp. ROV

a, 2.50 o\

E

O

>

_>

JS <> \

^ 2.00

o \

1.50 O X

o

o

()

1.00

^t>0O(

> O o

0.50

2000 4000 6000 8000 10000

Pressure (psia)

Figure 4.2

Comparison of Relative Volume Data

(Sample 1, SRKEOS)

92

4.00 1

3.50

ol

3.00

o O Exp. ROV

0) 2.50

E

O

>

0)

>

0) () \

C. 2.00

o \

1.50

O

o

(

' o o

0.50

2000 4000 6000 8000 10000

Pressure (psia)

Figure 4.3

Comparison of Relative Volume Data

(Sample 1, SRKGDEOS)

93

<)

3.50

O Exp. ROV

0) 2.50

E

3

O

>

Relative

3

1.50 \o

1.00 ^ ^22t^o_o_oj L^

-^-J )

0 50 -

1000 2000 3000 4000 5000 6000 7000

Pressure (psia)

Figure 4.4

Comparison of Relative Volume Data

(Sample 2, PREOS)

94

4.00

Pressure (psia)

Figure 4.5

Comparison of Relative Volume Data

(Sample 2, SRKEOS)

95

4.00

)

3.50

3.00

_3

O

> O E Kp. ROV

SS \o

0)

a. 2.00

1.50 V o

\sO

\v4

1.00

2222o__o__oj

^.___o_j 5

0.50 4

1000 2000 3000 4000 5000 6000 7000

Pressure (psia)

Figure 4.6

Comparison of Relative Volume Data

(Sample 2, SRKGDEOS)

96

1.10

o

1

1.05

o 1.00

n> O Exp. Gas Z

u.

(/)

V)

a.

E

o

o

\

0) 0.95

(0

O o

/

o

O /

0.90

o /

'

0.85

1000 2000 3000 4000 5000 6000

Pressure (psia)

Figure 4.7

Comparison of Z-Factor Data

(Sample 1, PREOS)

97

1.40

1

1.30

Z

1.20

O Exp. Gas Z

u

1.10 /

<1>

Q.

E 1 /

o

o / o

(A

(Q

i /

o

1.00 I

\^^ o

o 1

o

0.90 r>

o

0.80

1000 2000 3000 4000 5000 6000

Pressure (psia)

Figure 4.8

Comparison of Z-Factor data

(Sample 1, SRKEOS)

98

1.40

1.30

1

\ /

Final GasZ

1.20 f

o Exp. Gas Z

u

(Q

/

1

1.10

a ! ' / '

E : / 1

o

o

(A

ra

0

1.00

^^^ o

o^ o

0.90 o

o

0.80

1000 2000 3000 4000 5000 6000

Pressure (psia)

Figure 4.9

Comparison of Z-Factor Data

(Sample 1, SRKGDEOS)

99

1.00

!

0.95

i

1

O Exp. Gas Z

0.90 \ o

1

u \

ra

u.

0

1

J8 0.85

a.

E

o

o

(A

ra

O \

0.80

/

\ O /

/

/

0.75

^^ or

1

i

i

0.70

1000 2000 3000 4000 5000

Pressure (psia)

Figure 4.10

Comparison of Z-Factor Data

(Sample 2, PREOS)

100

1.00

0.95

-rmeai \jci9 t-

o Exp. Gas Z

0.90

u /

ra \

u.

/

i;; 0.85

0) i

a 1

E

o I

o 1

(A

ra o \

\ 1

0.80

/ o

j ^ ^ ^

1

1 o

1

0.75 1

o

i

0.70

1000 2000 3000 4000 5000

Pressure (psia)

Figure 4.11

Comparison of Z-Factor Data

(Sample 2, SRKEOS)

101

1.00

1

0.95 -

1

i

O Exp. Gas Z

0.90

\ i

u

ra

u. \ 1

\

i \

1 o

21 0.85 i \

Q.

E

o

O

(A

ra o \

CD

0.80

u

0

0.75

o

0.70

1000 2000 3000 4000 5000

Pressure (psia)

Figure 4.12

Comparison of Z-Factor Data

(Sample 2, SRKGDEOS)

102

35.0 100.0

\

\

\ A

\ A 1

30.0 1

\ 1 .^0'^'^ ^^*N.

\

\ 80.0

\ A

A Exp. Liq. Vol. i

\ A\

\ Final Prod. Gas

25.0 A /^

\ /

O Exp. Prod. Gas

A

\

o \ 1

I I

> 60.0 a

"ra

E 20.0

\

\ A\ 1

1 1

c \ a

o A / O

(A

E \

_3 \

O (Q

> 15.0 \ 3

D \ L 0)

\ 1 40.0 -

V 1 o

\

\

10.0 V

\ L^

\

< \

\

20.0

\

5.0 V

\

\

b.

0.0 0.0

1000 2000 3000 4000 5000 6000 7000

Pressure (psia)

Figure 4.13

Comparison of CVD Test Data

(Sample 1, PREOS)

103

40.0 100.0

\

35.0

\

\ Final Liq. Vol. 80.0

s

O^

30.0 A Exp. Liq. Vol.

o ^

o 25.0 ^ ^ O Exp. Prod. Gas

>

c

"5)

'LI

O

20.0

0)

E

_3

O

>

o

"3

tr

Pressure (psia)

Figure 4.14

Comparison of CVD Test Data

(Sample 1, SRKEOS)

104

40.0 100.0

1

35.0

Final Liq. Vol. |

\

* i

^\ j A Exp. Liq. Vol.

80.0

1 i

o *\ A A Final Prod. Gas

30.0 1

A

0 '\

% A

o 25.0 A

A

> k 60.0 I

"ra y ^

\^ o

c A (D

"5) ^ o A

a

O

20.0 fi)

0) (0

E

_3

A f X

1

1

1

X

O X

> >

"5 40.0^

2" 15.0 3

\x A o

% X

O \ X

\ \

\

\\

\ s

\ s

\

10.0

20.0

o

5.0

A

O

0.0 0.0

1000 2000 3000 4000 5000 6000

Pressure (psia)

Figure 4.15

Comparison of CVD Test Data

(Sample 1, SRKGDEOS)

105

30.0 1

100.0

1

' ^*s,^^^

25.0 X

Final Liq. Vol. ^

X

\ A \ 80.0

\ A Exp. Liq. Vol.

'9

1

.

20.0

^ \\ A\ O Exp. Prod. Gas

X

o X

> i \ 60.0 .

75 \ O I\ o

1 \ (D

c 1 1 a

'5) \ O

u

o 15.0 \ ! \ (A

0) V

E X

1 1

_3 X

X

! I

O

> A/

X

i \

'5

X

X i 1

40.0 ^

cr X 1 \ 3

o

o

10.0 %

\

X

\

X

X

X

\

X

X

X

\ 20.0

5.0

\0 \

%

X

X X \

1 ^ ^v

1 ^ ^ .

0.0 - " ^ ^j 0.0

1000 2000 3000 4000 5000

Pressure (psia)

Figure 4.16

Comparison of CVD Test Data

(Sample 2, PREOS)

106

30.0 100.0

25.0 -

20.0

o

>

75

c

'5

0)

15.0

E

o

>

"5

10.0

Pressure (psia)

Figure 4.17

Comparison of CVD Test Data

(Sample 2, SRKEOS)

107

30.0 100.0

t

>

1

\ i

25.0

X

X

A N. riRal Liq. vol. 80.0

\

\

\ 1

p

V

\

X

A Exp. Liq. Vol.

\

X

X

k

A

o /

> A / 0 Exp. Prod. Gas 60.0 Q.

c

75 \ 0 o

c

X a

O

"5) \\ 0)

1

V)

15.0 \

E

X \

_3

O

X

X

\ CO

> A / X

3'

"3 \ 40.0 -

X

X o

X

0

10.0

\

X

X

X

X

X

X

X

X I

20.0

X 1

X 1

5.0

1 -.O; \

! ! \

A

X \

| \ o\

X ^V

\ ^k

1000 2000 3000 4000 5000

Pressure (psia)

Figure 4.18

Comparison of CVD Test data

(Sample 2, SRKGDEOS)

108

100

4 f 1

^^,0^''''^ T

90

80

70

60 i

"""Mole % of Liquid

I 50

- * - M o l e % of Vapor 1

\

40

30

20

10

J "11

4 8

Cycles

Figure 4.19

Variation in Mole Percent of Liquid and Vapor

(Sample 1, 750 psia, 700 F)

109

90

80

70

60

Mole % of Liquid

50

Mole % of Vapor

0)

o

40

30

20

10

4 6 8 10

Cycles

Figure 4.20

Variation in Mole Percent of Liquid and Vapor

(Sample 1, 750 psia, 500 F)

110

100

- .,

90

80

70

iV

60

""Mole % of Liquid

I 50

n Mole % of Vapor

40

30

20

:

10 1

6 8 10 12

Cycles

Figure 4.21

Variation in Mole Percent of Liquid and Vapor

(Sample 1, 250 psia, 700 F)

111

20

10

r-

4

Cycles

Figure 4.22

Variation in Mole Percent of Liquid and Vapor

(Samplel, 250 psia, 500 F)

112

100 1

jO)

o

4 5 8

Cycles

Figure 4.23

Variation in Mole Percent of Liquid and Vapor

(Sample 2, 750 psia, 500 F)

113

80

' ^^^-^ )y

70

i

60

Mole % of Liquid

50

n Mole % of Vapor

I 40

^^"^^-"--^

30 ^ i

20

10

4 5 8

Cycles

Figure 4.24

Variation in Mole Percent of Liquid and Vapor

(Sample 2, 750 psia, 350 F)

114

100

90

!

80

70

f

60

6^

I 50 Mole % of Liquid

OMole % of Vapor

40

30

20

10

0

0 6 8 10 12

Cycles

Figure 4.25

Variation in Mole percent of Liquid and Vapor

(Sample 2, 250 psia, 500 F)

115

80

70

60

Mole % of Liquid

50

'Mole % of Vapor

I 40

30 -Q

-^

20

10

Cycles

Figure 4.26

Variation in Mole Percent of Liquid and Vapor

(Sample2, 250 psia, 350 F)

116

90

i

1

80

70

60

""Volume % of Liquid

50

0) BVolume % of Vapor

E

O

>

40

30

i

t

i

20 j

1

i

10

4 8

Cycles

Figure 4.27

Variation in Volume Percent of Liquid and Vapor

(Sample 1, 750 psia, 700 F)

117

80

70

60

^ ^ ^ " " ^

50

^^"^"-n

0)

I 40

"o

>

30

Volume % of Liquid

20

*Volume % of Vapor

10

8 10

Cycles

Figure 4.28

Variation in Volume Percent of Liquid and Vapor

(Sample 1, 750 psia, 500 F)

118

90

80

70

60

Volume % of Liquid

50

0) fiVolume % of Vapor

E

O

>

40

30

20

10

6 8 10 12

Cycles

Figure 4.29

Variation in Volume Percent of Liquid and Vapor

(Sample 1, 250 psia, 700 F)

119

0)

E

O

>

Cycles

Figure 4.30

Variation in Volume Percent of Liquid and Vapor

(Sample 1, 250 psia, 500 F)

120

90

80

70

60

Volume % of Liquid

50

0) ""BVolume % of Vapor ;

E

O

> 40

30

M

20

10

4 5 8

Cycles

Figure 4.31

Variation in Volume Percent of Liquid and Vapor

(Sample 2, 750 psia, 500 F)

121

90

:

80

'

70

60

Ji^,,^^^^

50

6^

0)

E

O

> 40

Volume % of Liquid

30

-*Volume % of Vapor

20

10

4 5 8

Cycles

Figure 4.32

Variation in Volume Percent of Liquid and Vapor

(Sample 2, 750 psia, 350 F)

122

0)

E

O

>

6 8 10 12

Cycles

Figure 4.33

Variation in Volume Percent of Liquid and Vapor

(Sample 2, 250 psia, 500 F)

123

90

i

1

ia u

80

i

70

60

Volume % of Liquid

50

0) OVolume % of Vapor

E

O

> 40

30

20 1 - <i **

10

Cycles

Figure 4.34

Variation in Volume Percent of Liquid and Vapor

(Sample 2, 250 psia, 350 F)

124

Figure 4.35

Variation in Overall Composition

(Sample 1, 750 psia, 700 F)

125

6 8 10 12

Cycles

Figure 4.36

Variation in Overall Composition

(Sample 1, 750 psia, 500 F)

126

30

14

Figure 4.37

Variation in Overall Composition

(Sample 1, 250 psia, 700 F)

127

30 T

2 3 4

Cycles

Figure 4.38

Variation in Overall Composition

(Sample 1, 250 psia, 500 F)

128

Ji

o

8 10

Cycles

Figure 4.39

Variation in Overall Composition

(Sample 2, 750 psia, 500 F)

129

45

40

35

30

25

0)

o

20

8 10

Cycles

Figure 4.40

Variation in Overall Composition

(Sample 2, 750 psia, 350 F)

130

J)

o

Figure 4.41

Variation in Overall Composition

(Sample 2, 250 psia, 500 F)

131

J)

o

Cycles

Figure 4.42

Variation in Overall Composition

(Sample 2, 250 psia, 350 F)

132

70 1

002

N2

50

01

02

03

40

104

o N04

105

30

N05

F06

07+

20

Figure 4.43

Variation in Liquid Composition

(Sample 1, 750 psia, 700 F)

133

70

60

002

50

N2

01

02

40 -

03

o 104

N04

30

105

N05

20 F06

07+

10

Figure 4.44

Variation in Liquid Composition

(Sample 1, 750 psia, 500 F)

134

an

70

002

60

N2

01

50

02

03

I 40 104

N04

105

30

N05

F06

20

07+

10

12 14

Figure 4.45

Variation in Liquid Composition

(Sample 1, 250 psia, 700 F)

135

3

Cycles

Figure 4.46

Variation in Liquid Composition

(Samplel, 250 psia, 500 F)

136

002

35 N2

01

02

30

03

104

25

N04

J)

o 105

20

N05

F06

15 07+

8 10

Cycles

Figure 4.47

Variation in Liquid composition

(Sample 2, 750 psia, 500 F)

137

o

8 10

Cycles

Figure 4.48

Variation in Liquid Composition

(Sample 2, 750 psia, 350 F)

138

70 1

50 002

N2

01

40 02

03

o

104

30

N04

105

N05

20

F06

07+

10

0 8 10

Cycles

Figure 4.49

Variation in Liquid Composition

(Sample 2, 250 psia, 500 F)

139

70

60

002

50

N2

01

40 02

03

J)

o

104

30 N04

105

N05

20

F06

07+

1 2

Cycles

Figure 4.50

Variation in Liquid Composition

(Sample 2, 250 psia, 350 F)

140

80 T

70

60

50

I 40

30

20

Figure 4.51

Variation in Vapor Composition

(Sample 1, 750 psia, 700 F)

141

002

60 N2

01

02

50 03

104

N04

^ 40

105

N05

30 F06

07+

20

Figure 4.52

Variation in Vapor Composition

(Sample 1, 750 psia, 500 F)

142

60

50

40

J)

o

30

20

10 ^C )( K )C )( X K )( ^^ ^

:iK

12 14

Figure 4.53

Variation in Vapor Composition

(Sample 1, 250 psia, 700 F)

143

70 1

002

50 N2

01

02

40

03

o 104

N04

30

105

N05

F06

07+

3

Cycles

Figure 4.54

Variation in Vapor Composition

(Samplel, 250 psia, 500 F)

144

70

60 002

N2

01

50 02

03

104

40

N04

J) 105

o

N05

30

F06

07+

20

10 .)K 3 F ^ )K rt H Nt

:i *-

8 10

Cycles

Figure 4.55

Variation in Vapor Composition

(Sample 2, 750 psia, 500 F)

145

70

60

0O2

N2

50 01

02

03

40 104

N04

o 105

30 N05

F06

07+

20

^( X ?( X X -X

0

8 10

Cycles

Figure 4.56

Variation in Vapor Composition

(Sample 2, 750 psia, 350 F)

146

50 002

N2

01

02

40

03

104

N04

I 30 105

N05

F06

20 07+

10

0

4 6 8 10

Cycles

Figure 4.57

Variation in Vapor Composition

(Sample 2, 250 psia, 500 F)

147

60

50

002

N2

40 01

02

03

i 30 104

N04

105

N05

20

F06

^

07+

10

1 2

Cycles

Figure 4.58

Variation in Vapor Composition

(Sample 2, 250 psia, 350 F)

148

CHAPTER 5

CONCLUSIONS

1. The vaporization/condensation process was found to be feasible.

2. The Peng-Robinson equation of state model was identified as the

most accurate model to simulate experimental data.

3. The vaporization/condensation process resulted in increased liquid

saturation. If this increased saturation was more than the residual

liquid saturation in terms of relative permeability, then liquid may

become mobile, resulting in additional recovery.

4. The vaporization/condensation process resulted in increased mole

percent of liquid and decreased mole percent of vapor.

5. The vaporization/condensation process was found to be more

effective at high reservoir pressure and high vaporization

temperature.

6. The vaporization/condensation process resulted in the decreased

mole percent of lighter components (CI, C2) and increased mole

percent of heavier components (SCN fractions) in the overall fluid

composition. The effect on middle components (C3-C6) was

insignificant.

7. Liquid and vapor compositions were affected in such a way by the

vaporization/condensation process that liquid was lighter and

vapor was enriched after the vaporization/condensation process.

149

CHAPTER 6

RECOMMENDATIONS

1. This study was conducted on only two samples of a particular fluid

type (gas condensate). Fuhire studies should be conducted on

large number of samples of different type of fluid (black oil, volatile

oil etc.) to make the study more general and the study results more

relevant.

2. Only three equation of state models were tested in this study.

Other more recent equation of state models, such as Patel-Teja,

Schmidt-Wenzel equation of state model should be tested to verify

the results.

3. It was assumed in this study that the temperature increases

suddenly from initial temperature to the specified vaporization

temperature at the vaporization stage and decreases suddenly from

vaporization temperature to initial temperature at the condensation

stage. In the actual reservoir, however, any increase or decrease of

temperature happens gradually. Therefore, an effort should be

made to quantify this assumption.

4. This study was conducted in context of a PVT cell. When

conducting the study for an actual reservoir, the flow

characteristics of the fluids in the reservoir and effects of heating

mechanism (steam injection, in-situ combustion) should be

considered.

150

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156

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