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A THESIS
IN
PETROLEUM ENGINEERING
IN
PETROLEUM ENGINEERING
^ Approved
May, 1998
i^^^o ACKNOWLEDGEMENTS
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
VI
LIST OF TABLES
Vll
LIST OF FIGURES
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
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
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
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
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.
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.
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.
14
ny = (2.3)
A-B
where
i *
-.(^,-lJ
'Z,(A:,-I)"
i
/K) = Z ny{K,-\) +\
=0 (2.4)
( \ -^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,
^ - ^ . ^ ' ' ^
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.
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.
20
P "" p repulsive " p attractive (2.11))
a = Q, '- (2.12)
Pc
RZ
b=Q , ^ (2.13)
Pc
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
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
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)
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
27
k,. = 0.17985 + 2.6958^; +10.853(yt;)' (2.43)
(2.44)
" " 2e.e
' ./
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
(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:
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)
7ci+
31
ai-as = coefficients as given by Ahmed.^^
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)
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)
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.
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,
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
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.
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.
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
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.
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)
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.
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
43
V, = - ^ (2.121)
V, = - ^ ^ (2.122)
and
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.
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.
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.
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
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.
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
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
Table 3.2
Properties of Plus Fractions
68
Table 3.3
Experimental Data for Sample 1
6015 0.9396 - - -
5515 0.9696 - - -
5115 0.9989 - - -
2015 2.0501 - - -
1637 2.5256 - - -
1402 2.9617 - - -
15 - - 18.5 -
69
Table 3.4
Experimental Data for Sample 2
5314.7 0.9158 - - -
5014.7 0.9317 - - -
4414.7 0.9690 - - -
3724.7 1.0299 - - -
3014.7 1.1496 - - -
2219.7 1.5246 - - -
70
Set-Up Initial Data
(Composition, Component Properties)
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
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.
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
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)
82
Table 4.4
Comparison of Retrograde Liquid Volume Calculated By
Different EOS (Sample 2)
83
Table 4.5
Comparison of Produced Gas Calculated By
Different EOS (Sample 1)
84
Table 4.6
Comparison of Produced Gas Calculated By
Different EOS (Sample 2)
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)
86
Table 4.9
Comparison Between Experimentally Obtained
Composition and Composition Calculated By
PREOS at Depleted Reservoir Pressure
(Sample 2)
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
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
(
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
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.
20.0
0)
E
_3
O
>
o
"3
tr
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
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
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
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
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
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
149
CHAPTER 6
RECOMMENDATIONS
150
REFERENCES
2. Martin, J.J., "Cubic Equation of State - Which?," Ind. Ene. Chem. Fund.,
18(2), 1979, pp. 81-97.
151
9. Bjorlykke, O. P., and Firoozabadi, A., "Measurement and Computation of
Retirograde Condensation and Near-Critical Phase Behavior," SPE 20524,
Presented at the 65* Annual Technical Conference of the Society of
Petroleum Engineers held in New Orleans, LA, September 23-26,1990.
11. Amyx, James W., Bass, Daniel M., Jr. and Whiting, Robert L., Petroleum
Reservoir Engineering - Physical Properties, McGraw-Hill Classic
Textbook Reissue, McGraw-Hill Book Company, New York, 1988
12. Campbell, John M., Gas Conditioning and Processing, Volume 1: The
Basic Principles, Seventh Edition, Campbell Petroleum Series, Norman,
Oklahoma, 1992.
16. Standing, M. B., "A set of Equations for Computing Equilibrium Ratios of
a Crude Oil/Natural Gas System Below 1000 psia," Journal of Petroleum
Technologv, September 1979, pp. 1193-1195.
17. Leland, T. W., "Phase Equilibria and Fluid Properties in the Chemical
Industry," DECHEMA, 1980, pp. 283-333.
18. Benedict, W., Webb, G. B., and Rubin, L. C , "An Empirical Equation for
Thermodynamic Properties of Light Hydrocarbons and Their Mixtures. I.
Methane, Ethane, Propane, and Butane/' J. Chem. Phys., Volume 8,1940,
pp. 334-345.
152
20. Lee, B. I., and Kesler, M. G., "A Generalized Thermodynamic Correlation
Based on Three-Parameter Corresponding States," AIChE Journal,
Volume 21,1975, pp. 510-527.
22. Peng, D., and Robinson, D., "A New Two Constant Equation of State,"
Industrial and Engineering Chem. Fund., 1976, Vol. 15, No. 1, pp. 59-64.
23. Redlich, O., and Kwong, J., "On The Thermodynamics of Solutions. An
Equation of State . Fugacities of Gaseous Solutions," Chemical Reviews,
Vol. 44,1949, pp. 233-247.
24. Zudkevitch, D., and Joffe, J., "Correction and Prediction of Vapor-Liquid
Equilibria with the Redlich-Kwong Equation of state," AIChE Tournal,
Volume 16(1), 1970.
29. Vidal, J., and Daubert, T., "Equation of State - Reworking the Old Forms,"
Chem. Eng. Sci., 1978, Vol. 33, pp. 787-791.
30. Graboski, M. S., and Daubert, T., "A Modified Soave Equation of State for
Phase Equilibrium Calculations 1. Hydrocarbon System," Ind. Eng. Chem.
Process Pes. Dev., 1978, Vol. 17, pp. 443-448.
153
31. Elliot, J., and Daubert, T., "Revised Procedure for phase Equilibrium
Calculations with Soave Equation of State," Ind. Eng. Chem. Process Pes.
Dev., 1985, Volume 23, pp. 743-748.
32. Peneloux, A., Rauzy, E., and Freze, R., "A Consistent Correlation for
Redlich-Kwong -Soave Volumes," Fluid Phase Equilibria, 1982, Vol. 8, pp.
7-23.
33. Nikos, v., et al., "Phase Behavior of Systems Comprising North Sea
Reservoir Fluids and Injection Gases," Journal of Petroleum Technology,
November 1986, pp. 1221-1233.
34. Stryjek, R., and Vera, J. H., "PRSV: An Improved Peng-Robinson Equation
of State for Pure Compounds and Mixtures," Canadian J. Chem. Eng.,
April 1986, Volume 64, pp. 323-333.
35. Stryjek, R., and Vera, J. H., "PRSV: An Improved Peng-Robinson Equation
of State with New Mixing Rules for Strongly Nonideal Mixtures,"
Canadian J. Chem. Eng., April 1986, Volume 64, pp. 334-340.
38. Schmidt, G., and Wenzel, H., "A Modified Van der Waals Type Equation
of State," Chem. Eng. Sci., 1980, Volume 135, pp. 1503-1512.
39. Patel, N., and Teja, A., "A New Equation of State for Fluids and Fluid
Mixtures," Chem. Eng. Sci. Volume 37, No. 3, pp. 463-473,1982.
41. Valderrama, J. O., and Cisternas, L., "A Cubic Equation of State for Polar
and Other Complex Mixtures," Fluid Phase Equilibria, Volume 29, pp.
431-438,1986.
154
42. Valderrama, J. O., "A Generalized Patel-Teja Equation of State for Polar
and Non-Polar Fluids and Their Mixhires," J. Chem. Eng., Volume 23(1),
1990, pp. 87-91.
43. Pedersen, K. S., Fredenslund, Aa., and Thomassen, P., Properties of Oils
and Natural Gases. Gulf Publishing Company, Houston, Texas, 1989.
44. Reid, Robert C , Prausnitz, John M., Poling, Bruce E., The Properties of
Gases & Liquids, Fourth Edition, McGraw-Hill Book Company, New
York, USA, 1987.
45. Danesh, A., Dong-Hai, Xu, and Todd, A. C , "Comparative Study Of Cubic
Equation of State for Predicting Phase Behavior and Volumetric Properties
of Injection Gas-reservoir Oil Systems," Fluid Phase Equilibria, Volume
63,1991, pp. 259-278.
46. Coats, K. H., and Smart, G. T., "Application of a Regression Based EOS
PVT Program to Laboratory Data," SPE Reservoir Engineering, May 1984,
pp. 277-299.
47. Agarwal, R. K., Li, Y., and Nghiem, L., "A Regression Technique with
Dynamic Parameter Selection for Phase Behavior Matching," SPE
Reservoir Engineering, February 1990, pp. 115-120.
49. Merril, R. C , Hartman, K. J., and Creek, J. L., "A Comparison of Equation
of State Tuning Methods," SPE 28589, Presented at the 69* Annual
Technical Conference of the Society of Petroleum Engineers held in New
Orleans, Louisiana, September 25-28,1994.
50. Merril, R. C , and Newley, T. M. J., "A Systematic Investigation into the
Most Suitable Data for the Development of Equation of State for
Petroleum Reservoir fluids," Fluid Phase Equilibria, Volume 82,1993, pp.
101-110.
155
52. Pedersen, K. S., Thomassen, P., and Fredenslund, Aa., "On the Dangers of
Tuning Equations of State Parameters," Chemical Engineering Science,
Volume 43,1988, pp. 269-278.
53. Hariu, O., and Sage, R., "Crude Split Figured by Computer,"
Hvdrocarbon Proces., April 1969, pp. 143-148.
54. Katz, D., "Overview of Phase Behavior of Oil and Gas Production,"
Tournal of Petroleum Technology, June 1983, pp. 1205-1214.
55. Ahmed, T., Cady, G., and Story, A., "A Generalized Correlation for
Characterizing the Hydrocarbon Heavy Fractions," Paper SPE 14266,
Presented at the 60* Annual Technical Conference of the Society of
Petroleum Engineers held in Las Vegas, September 22-25,1985.
56. HYSIM User's Guide, Hyprotech Limited, Calgary, Alberta, Canada, 1991.
156
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