12

Vapour Liquid Equilibria

CONTENTS

1 INTRODUCTION - THE IMPORTANCE OF

VAPOUR-LIQUID EQUILIBRIUM
2 IDEAL SOLUTIONS
2.1 Raoult's Law
2.2 Dalton's Law
2.3 Ideal Equilibrium Ratio
3 NON IDEAL SYSTEMS
4 EQUATIONS FOR CALCULATING
EQUILIBRIUM RELATIONS
4.1 Vapour - Liquid Calculations
4.2 Dew - Point Calculation
4.3 Bubble Point Calculation
5 SEPARATOR PROBLEMS
5.1 Gas / Oil Ratio
5.2 Oil Formation Volume Factor
5.3 Optimum Pressure of Separator System
5.4 Example of Separator Problem

LEARNING OBJECTIVES
Having worked through this chapter the Student will be able to:

Define equilibrium ratio.

Derive equations for vapour-liquid equilibrium calculations for real systems

and explain the application of the equations.

Derive and explain the use of equations to determine the dew point pressure and
bubble point pressure of a fluid mixture.

Describe in general terms the impact of separator conditions the gas-oil ratio
and oil formation volume factor.

12

Vapour Liquid Equilibria

1 INTRODUCTION - THE IMPORTANCE OF VAPOUR-LIQUID

EQUILIBRIUM
The multiphase perspectives of hydrocarbon mixtures in and produced from reservoir
accumulations are an important aspect in reservoir management, well productivity,
facility design and pipeline transport.
Predicting the relative amount of the phases and their respective physical properties
is an essential element in all of the above operations. The topic of vapour-liquid
equilibria is also at the heart of many subsequent and other process operations and
therefore there have been a range of approaches into the solution of the problem.
The behaviour in reservoirs of multicomponent mixtures and their production to
surface has provided one of the most rigorous challenges to design engineers because
of the complex and unique nature of the fluids and in many cases their behaviour near
the critical point.
Figure 1, and 2 illustrate the complex nature of oil and gas production where,
particularly in a major offshore province, as well as onshore, a number of reservoirs
produce into a common transport line and associated treatment facilities (Figure 1).
Each of the fields with their unique composition clearly contribute to a compositional
blend entering a treatment facility (Figure 2), where further separation occurs.

CUSTOMERS

ONSHORE FACILITIES

Figure 1
The total system

OFFSHORE FACILITIES

OFFSHORE FACILITIES

WELLS

WELLS

RESERVOIR

RESERVOIR

Department of Petroleum Engineering, Heriot-Watt University

CHEMICAL
FEEDSTOCK

FUEL

OIL SALES
& TAXES

TERMINAL

Composition = (TA*CA)*(TB*CB)+(TC*CC)
TA + TB + TC
Throughput = TA + TB + TC

FIELD A

FIELD C

Composition CA
Throughput TA

Composition CC
Throughput TC

FIELD B
Composition CB
Throughput TB

The allocation of revenue based on quality of product and oil injected into a common
pipeline provides a considerable challenge to metering and compositional analysis.
To the reservoir engineer, the main issues are the multiphase behaviour in the
formation and the relationship between the fluids in the reservoir and those produced
at surface conditions.
The critical element in reservoir simulation is the grid block where the saturations and
flow behaviour of the respective fluids; gas, oil and water are required. The grid block
therefore can be considered as a separator and vapour-equilibrium calculations are
required out to determine the relative amounts of the phases which lead to saturation
values and relative permeability of the phases, and the composition of these phases
which lead to important physical property values of density, viscosity and interfacial tension.
In the previous chapter the considerations of the relative amounts of gas and liquid
were considered in the simplistic two component black oil approach. In this chapter
we will consider approaches to vapour-liquid equilibrium from a compositional
model consideration both from an ideal behaviour perspective and then the consideration of real systems.
4

Figure 2
Complexity of allocation of
produced oil to supply fields

12

Vapour Liquid Equilibria

On a pressure temperature phase diagram of a multi-component mixture, the area

bounded by the bubble point and dew-point curves defines the conditions for gas and
liquid to exist in equilibrium. It is an over-simplification to describe the system as
involatile oil with associated solution gas. The behaviour of the individual components and their influence on the composition of the mixture need to be considered.
If a sample of bubble point fluid is brought to surface to separator conditions, the fluid
enters the two phase region at a temperature and pressure much lower than reservoir
conditions. In the separator the liquid and gas phases, in equilibrium, are withdrawn
separately. Large volumes of gas are formed at these separator conditions, and the
liquid volume shrinks substantially because of decreased temperature and conversion
of some of the fluid into the gas phase. The separator liquid is collected in the stock
tank, at which additional temperature and pressure drop may occur, more gas may be
released depending on the separator conditions to stock tank conditions.
If Vo is the volume of liquid at reservoir conditions and Vst is the volume of stock tank
oil. The oil formation volume factor Bo is :

Bo =

Vo
Vst

If Vg and Vst are the total volume of gas and oil collected from the separator and stock
tank. The solution gas to oil ratio is :

Rs =

Vg
Vst

The volume factors can be determined directly in the laboratory or from equilibrium
calculations.
In addition to separator calculations vapour liquid equilibrium data can be used for:

Reservoir calculations

Two phase pipeline flow calculations

Process calculations

Although phase behaviour considerations are required throughout the production

process from reservoir to refinery the context of this particular chapter is in relation
to reservoir predictions. When reservoir fluids undergo phase alteration as a result of
changes in pressure, temperature or composition it is considered that these changes are
slow and therefore the resulting separate phases are in equilibrium, i.e the properties
of the phases are not changing with respect to time.
For multicomponent phase behaviour predictions thermodynamic principles have
been applied to provide the predictive tools. Many works have been written which
Department of Petroleum Engineering, Heriot-Watt University

provide the foundation of the topic. Danesh1 in his text provides a good review of the
topic both with respect to the foundation principles and the equations used.
Vapour-liquid equilibrium calculations have been somewhat restricted to analysis of
behaviour with the separate areas, i.e. reservoir and wells, surface separation,
pipelines, onshore treatment and refininery operations. Increasingly in the modern
multidisciplinary approach to technical management there is an interest in the
integrated perspective of vapour liquid equlibrium. For example, what is the impact
on the quality of product exiting from a multifield oil transport line of a pressure
change in field X. Such integrated perspectives provide a considerable technical and
commercial challenge to the various technical disciplines which have been separately
involved.

2 IDEAL SOLUTIONS
Before we consider the behaviour of real systems we will first examine the behaviour
of an ideal solution, where no chemical interaction occurs and where no intermolecular forces occur when mixing components.
These ideal solutions result in no heating effects when ideal solutions are mixed and
the volume of the mixture equals the sum of the volumes the pure components would
occupy at the same pressure and temperature.

2.1 Raoults Law

Raoults equation states that the partial pressure of a component in the gas is equal
to the product of the mole fraction, xj in the liquid, multiplied by the vapour pressure
of the pure component pvj.
pj = xjpvj

(1)

where pj is the partial pressure of component j in the liquid with a composition xj and
pvj is the vapour pressure of the pure component j.

2.2 Daltons Law

Daltons law states that the partial pressure of a component pj is equal to the mole
fraction of that component in the gas, yj times the total pressure of the system p, i.e.
pj = yjp
(2)
where yj is the composition of the vapour and p is the pressure of the system

2.3 Ideal Equilibrium Ratio

By combining the above two laws,

yjp = xjpvj

(3)

y j pvj
=
xj
p

(4)

12

Vapour Liquid Equilibria

i.e. the ratio of the component in the vapour and liquid phases is given by the ratio of
the vapour pressure of the pure component to the total pressure of the system. This
ratio is termed the Equilibrium ratio, Kj .
If n is the total number of moles of mixture and zj is the mole fraction of component
j in the mixture.
zjn = xjnL + yjng

(5)

where nL and ng are the moles of liquid and gas such that nL + ng = n
From equation 4.

z j n = x j nL + x j

xj =

pvj
ng
p

zjn
p
nL + vj ng
p

(6)

xj by definition = 1.0
c

zjn
= 1.0
p
j =1 n + vj .n
L
g
p

xj =
j =1

(7)

Similarly:
c

zjn
= 1.0
p
j =1 n +
.
n
g
L
pvj

yj =
j =1

If a basis of one mole of mixture is used i.e. n

x =
j

y =
j

(8)

+ n L = 1.0

zj
= 1.0
pvj
1 + ng
1
p

zj
p

1 + nL
1
pvj

= 1.0

(9)

(10)

Using these equations in a trial and error method the compositions of vapour and liquid
streams in a flash separation can be determined.
Department of Petroleum Engineering, Heriot-Watt University

The equilibrium ratio Kj is defined as the ratio of the composition of j in the vapour
to liquid phase, i.e.

Kj =

yj
xj

(11)

Clearly Kj is defined at a particular pressure and temperature.

Other names for Equilibrium ratio, include K-factors, K-values, equilibrium vapour
-liquid distribution ratios.
Fugacity
Lewis2 introduced the concept of fugacity, for use in equilibrium calculations, to
extrapolate or correct vapour pressures. This is required since a pure component only
has a vapour pressure up to its critical point. The fugacity is a thermodynamic quantity
defined in terms of the change in free energy in passing from one state to another.
For an ideal gas , the fugacity is equal to its pressure, and the fugacity of each
component is equal to its partial pressure. The ratio of fugacity to pressure is termed
the fugacity coefficient, . For a multicomponet system,

fi
Pzi

(12)

All systems behave as ideal gases at very low pressures, therefore > 1 when P > 0
When fugacities are not 1 , then this gives an indication of non-ideality.
Fugacity has been imagined (Danesh)1 as a measure of the escaping tendency of
molecules from one phase to an adjacent phase. In multicomponent systems, if the
fugacity of a component in adjacent phases is the same, the two phases will be in
equilibrium with no net transfer of molecules from one phase to another. At
equilibrium therefore
fg = fL.

(13)

The fugacity coefficient, of a pure component can be calculated from the following
general equation (Danesh).
p

z 1
1 RT
ln =
P dv
dp = (z 1) ln z +

RT v
p
o

(14)

The ratio of the fugacity at the state of interest to that at a reference state is called the
activity i = fi/fio
The activity is a measure therefore of the fugacity contribution or activeness of the
component in a mixture. fi = ifio .
The ratio of activity to concentration is called the activity coefficient i, where
8

12

Vapour Liquid Equilibria

i = i/xi
Therefore fi=ixifio

(15)

3 NON IDEAL SYSTEMS

Ideal solution assumptions cannot be applied to the systems relevant to multicomponent
hydrocarbon fluids in reservoir flow, transport and processing conditions. The ideal
assumptions only apply to low pressures and moderate temperatures, chemically and
physically similar components and behaviour below the critical point.
Different methods have been developed for treating vapour-liquid equilibrium for non
ideal systems.
The previous K value is based on both ideal and ideal solutions laws. To extend the
principle of equilibrium ratio to multicomponent hydrocarbon mixtures to the
pressures and temperatures relevant to petroleum engineers, methods of treating non
ideal systems need to be established.
The subject of non ideal equilibrium ratios are treated later in the text. We assume in
this section that K values are available either from whatever source, experimental,
NGPSA data charts, or from equations of state and other predictive methods.

4 EQUATIONS FOR CALCULATING EQUILIBRIUM RELATIONS

4.1 Vapour-Liquid Calculations
The calculations for determining the amount of liquid and vapour present in a mixture
when the pressure and temperature is known are obviously important, for example, in
optimising the performance of a separator process.
The equilibrium equations which are used for a process separator are the same as those
within a grid block or element of a reservoir simulator.
Figure 3 represents such a separation element.
V

yj

T&P

zj

Figure 3
Vapour-liquid separation in
an element

xj

Department of Petroleum Engineering, Heriot-Watt University

F
L
V
zj
xj
yj

=
=
=
=
=
=

total moles of system both liquid and gas

total moles of material within liquid phase
total moles of material within vapour phase
mole fraction of jth component in the mixture
mole fraction of jth component in the liquid
mole fraction of jth component in the vapour

It is common to express the feed F as 1.0 or 100 moles and express L and V as fractions
or percentages of F.
i.e. F = 1 = L + V

(16)

For component j
zjF = xjL + yjV
For F = 1.0 mole
zj = xjL + yjV

(17)

The equilibrium ratio:

Kj =

yj
xj

(18)

By definition:
m

x j = y j = z j =1
j =1

j =1

(19)

j =1

where m is the number of components.

Replacing yj by Kjxj in (17)
zj = xjL + xjKjV
zj = xj (L + KjV)
dividing both sides by L + KjV

zj
L + K jV

xj =

(20)

and:
m

zj

x = L + K V = 1.0
j

j =1

similarly:

10

j =1

(21)

12

Vapour Liquid Equilibria

zj
= 1.0
j =1 V + L K j

yj =
j =1

(21a)

by multiplying (21) by V we get:

m

L
j =1

zj

=V

(22)

+ Kj

and (21a) in the same way:

m

j =1

zj
=V
L
+1
K jV

(22a)

These equations are the key equations in vapour-liquid equilibrium calculations and
their use is the same whether in those calculations to determine phase behaviour in a
separator or those which take place within the numerous grid blocks of a reservoir
simulator. Clearly in the latter the amount of calculations is considerable since each
grid block can be considered a separator. In a large compositional based simulation
a study thousands of grid blocks will be used.
The method of calculation is therefore as follows for each separation element:
(1)

Select Kj for each component at the temperature and pressure of the system;
(For the determination of K see the later section.)

(2)

Assume a vapour liquid split i.e. V&L such that V + L = 1.0;

(3)

Calculate either V, L, xj or yj from equation 21, 21a, 22 and 22a;

(4)

Either:
(i) check V&L calculated against assumed V or L;
(ii) determine if xj or yj = 1.0;

(5) Repeat the calculation until assumed value is calculated value or until xj and
yj = 1.0.
It can be understood therefore that in a compositional reservoir simulator a considerable amount of computational time is taken up because of these iterative calculations
at each grid block. In a black oil simulator no such iteration takes place the specific
pressure and temperature provide the direct phase values either from a PVT report or
an empirical black oil correlation.
This phase equilibrium perspective can also be used to calculate the reservoir
saturation pressures for a particular temperature, ie. the dewpoint and bubble point
pressures.

Department of Petroleum Engineering, Heriot-Watt University

11

4.2 Dew-Point Calculation

The dew-point is when the first drop of liquid begins to condense. At this point the
composition of the liquid drop is higher in heavier hydrocarbons whereas the
composition of the vapour is essentially the composition of the system: Figure 4.
Vapour
yj = Zj
Liquid Xj

Figure 4
Conditions at the Dew
Point

Vapour
Liquid

At the dew point therefore:

zj = yj

(22)

zj = xjKj

or:

The mixture at the dew-point is therefore in equilibrium with a quantity of liquid

having a composition defined by the above equation. Clearly:
m

zj
= 1.0
j =1 K j

(23)

xj =
j =1

Similarly for the bubble point.

4.3 Bubble Point Calculation

The bubble point is when the first bubble of gas appears. At this point the composition
of this bubble of gas is higher in lighter hydrocarbons whereas the composition of the
liquid is essentially the composition of the system. Figure 5.

Vapour = Yj
Liquid
Xj = Zj

Figure 5
Conditions at the Bubble
Point.

Vapour
Liquid

At the bubble point therefore:

zj = xj

(24)

or:

zj =

yj
Kj

The mixture at the bubble point is therefore in equilibrium with a quantity of liquid
having a composition defined by the above equation.
12

12

Vapour Liquid Equilibria

Also:
m

y = z K
j

j =1

= 1.0

(25)

j =1

The dew-point and bubble point when either temperature or pressure are known are
determined by trial and error techniques until the above relationships are satisfied.
The dew-point pressure or bubble point pressure are estimated, K values obtained and
equations 23 or 25 checked. If the summation 1, different pressure values are tried
until convergence is reached. When convergence is reached the respective dew point
or bubble point pressure has been obtained.

5 SEPARATOR PROBLEMS
In a separator a stream of fluid is brought to equilibrium at separator temperature and
pressure. Vapour and liquid are separated within the unit and continue as separate
streams. Several separators can be operated in series each receiving the liquid phase
from the separator operating at the next higher pressure.
Each condition of pressure and temperature at which vapour and liquid are separated
is called a stage-separation. Hence a process using one separator and a stock tank is
a two stage process a three stage process has two separators and one stock tank. (Figure 6).
Separator calculations are performed to determine the composition of products, the oil
formation-volume factor and the volume of gas released per barrel of oil and to
determine the optimum separator conditions for the particular conditions of fluid.
Using equilibrium calculations already derived we can calculate the separation
achieved at each stage, the composition of the phases separated, the gas/oil ratio, and
the oil formation volume factor.

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13

Vapor

Vent

Feed
To pipeline / tanker
Liquid
Stocktank
at P st and T st

Separator
at P sep and T sep

Two-stage separation

1st stage vapor

2nd stage vapor

Vent

Feed
To pipeline / tanker

Liquid
1st stage separator
at (P sep ) 1 and (T sep ) 1

Liquid
2nd stage separator
at (P sep ) 2 and (T sep ) 2

Stocktank
at P st and T st

Figure 6
Schematic drawing of
separation process.

Three-stage separation

5.1 Gas/Oil Ratio

Gas is removed from each stage so that the solution GOR can be calculated for each
stage or combination of stages.

Total gas / oil ratio =

sum of gas volumes (SCF)

= RT
volume of stock tank oil (bbl)

(a) Calculation for Stock Tank Oil, STO.

If n1 moles enter first stage, moles of liquid entering 2nd = n2 = n1L1.
where L1 = separation in stage one based on basis of one mole feed.
Number of moles entering third stage n3 = n2L2 = L2L1n1
If third stage is the stock tank then:
nST = L3n3 = L3L2L1n1
nST is the moles of liquid in stock tank for n1 moles into first separator:
m

n ST = n1 L i
i =1

m = number of stages
Li = mole fraction of liquid off ith stage
n1 = moles of feed to first stage
14

(26)

12

Vapour Liquid Equilibria

If n1 = 1
then:
m

(27)

n ST = L i
i =1

n ST = L i = mole fraction of STO in the feed.

i =1

(b) Calculation of Total Gas

ngi = number of moles off stage i
ng1 = V1n1
ng2 = V2n2 = V2L1n1
ng3 = V3n3 = V3L2L1n
or in general for total gas:
m

i 1

n gT = n gi = n1 Vi L j
i =1

i =1

j =1

If nj = 1
m

i 1

n gT = Vi L j
i =1

(28)

j =1

ngT = mole fraction of total gas in the feed

Total gas volume per mole of feed =ngT Vmcu ft where Vm is the molar volume

5.2 Oil Formation Volume Factor

Volume of stock tank oil per mole of feed

(VST )m =

n ST M ST
ST

(29)

MST = molecular weight of stock tank oil

nsT= moles of STO per mole of feed
ST = density of STO at standard conditions lb/bbl
Total gas to oil ratio RT =
Department of Petroleum Engineering, Heriot-Watt University

15

RT =

n gT Vm n gT VmST
=
(VST )m n ST MST

(30)

where RT is the total gas - oil ratio.

If the feed to the first stage is a single-phase liquid into its point of entry into the
production stream then Bo can be calculated.
res. = density of feed (lb/bbl)
Volume of reservoir oil per mole = Vres = Mres/res
Oil formation volume factor Bo =

Bo =

(Vres ) =
VST

M resST
res M ST n ST

(31)

where

M res = molecular weight of reservoir fluid =

lb.res
lb.mol

and

n ST =

lb.mol. stock tan k fluid

lb.mol.res.fluid

5.3 Optimum Pressure of Separator System

The operating conditions of pressure and temperature of a separator influence the
amount of gas and stock tank oil produced. Change in these valves will change the
GOR and the Bo. In quoting these values therefore it is important to keep note of the
associated separation conditions of pressure and temperature. A number of units in
series also influence these parameters. It is the role of the process designers to
optimise the operating conditions of such limits and the number of units required.
It is the equilibrium characteristics of the individual components as a function of
temperature, pressure and composition which influence these total separation
characteristics for the mixtures at each separation stage.

16

12

1.36

33.4

580

1.34

560

1.32

540

1.30

33.2

33.0

32.8

32.6

32.4

API g
ravity

600

Separator + stock tank gas-oil ratio, scf/bbl

Figure 7
Effect of separator pressure
in a two-stage separation
process
(Amyx, Bass & Whiting)

33.6

520

1.28

Total

500

tio
gas-oil ra

o lu m
Formation v

480
0

20

40
100
60
80
First-stage separator pressure, psi

r
cto
e fa

120

Formation volume factor

stock tank gravity, API at 60F

Vapour Liquid Equilibria

1.26

1.24
140

Figure 7 illustrates the influence of a change of pressure for a two-stage separation

process on GOR, Bo and the density of stock tank oil.
Equilibrium flash calculations, which the above are called, are used in many other
applications. In reservoir engineering, flash calculations are at the core of compositional
simulation.

5.4 Example of Separator Problem (McCain)4

The following example is taken from McCains text on Petroleum Fluids and the
values for K used in the calculations come from the NGPSA sources5.
Calculate the gas-to-oil ratio, stock-tank oil gravity and formation-volume factor
which will result from a two-stage separation of the hydrocarbon mixture below. Use
separator conditions of 76F and 100 psig. Assume that the mixture is a liquid at its
bubble point at reservoir conditions of 2,695 psig and 220F.

Component

Mole Fraction

Methane
Ethane
Propane
i-butane
n-butane
i-pentane
n-pentane
Hexanes
Heavier

0.3378
0.0694
0.0982
0.0133
0.0299
0.0125
0.0193
0.0299
0.3897
1.0000

Gravity API at 60F

60/60

Molecular
Weight

0.8859

263

28.2

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17

Step 1:
Calculate the composition and quantities of separator gas and liquid
using equation 21.

zj

x = L + K V = 1.0
j

Component
of feed to
separator

Component,
mole
fraction zj

C1
C2
C3
i-C4
n-C4
i-C5
n-C5
C6
C7+ *

0.3378
0.0694
0.0982
0.0133
0.0299
0.0125
0.0193
0.0299
0.3897
1.000
* Used K for C9

Equilibrium
ratio at
114.7 psia
and 76F Kj
20.8
4.07
1.16
0.495
0.343
0.142
0.108
0.0334
0.00150*

x=

V=0.42
0.03626
0.03031
0.09202
0.01688
0.04129
0.01954
0.03086
0.05033
0.67117
0.98866

zj
L+KjV
V=0.43

0.03551
0.02991
0.09188
0.01699
0.04167
0.01985
0.03131
0.05117
0.68291
1.0015

V=0.4291
0.03557
0.02995
0.09189
0.01698
0.04164
0.01978
0.03127
0.05109
0.68184
1.00001

The summation equals 1.0 when V1 = 0.4291 and L1 = 0.5709 and the compositions
of the separator gas and liquid are:
Component

C1
C2
C3
i-C4
n-C4
i-C5
n-C5
C6
C7+

xj =

zj
L+KjV

0.0356
0.0299
0.0919
0.0170
0.0416
0.0198
0.0313
0.0511
0.6818
1.0000

yj=kjxj
0.7399
0.1219
0.1066
0.0084
0.0143
0.0028
0.0034
0.0017
0.0010
1.0000

Step 2: Calculate the compositions and quantities of stock tank and liquid using
equation 21, noting that the composition of the feed to the stock tank is the composition
of the liquid from the separator.

18

12

Vapour Liquid Equilibria

Component
of feed to
separator

Component,
mole
fraction zj

C1
C2
C3
i-C4
n-C4
i-C5
n-C5
C6
C7+*

0.0356
0.0299
0.0919
0.0170
0.0416
0.0198
0.0313
0.0511
0.6818
1.0000

Equilibrium
ratio at
14.7 psia
and 76F, Kj
161
30.7
8.15
3.27
2.30
0.90
0.675
0.20
0.0089*

V=0.13

zj
L+KjV
V=0.14

V=0.1351

0.00152
0.00580
0.04593
0.01290
0.03519
0.02008
0.03279
0.05755
0.79164
1.00340

0.00157
0.00597
0.04674
0.01301
0.03538
0.02007
0.03274
0.05729
0.78720
1.00000

xj=

0.00163
0.00615
0.04763
0.01313
0.03559
0.02006
0.03286
0.05703
0.78264
0.99654

* Used K for C9

The summation equals 1.0 so VST = 0.1351 and LST = 0.8649 and the compositions of
the stock tank gas and liquid are:

xj
0.016
0.0060
0.0467
0.0130
0.0354
0.0201
0.0327
0.0573
0.7872
1.0000

yj = Kjxj
0.2534
0.1831
0.3810
0.0425
0.0814
0.0181
0.0221
0.0115
0.0070
1.0001

Step 3: Calculate the density and molecular weight of the stock tank oil.
Component
of stock
tank oil

C1
C2
C3
i-C4
n-C4
i-C5
n-C5
C6
C7+
Total

Component,
mole
fraction
xj

Molecular
weight

0.0016
0.0060
0.0467
0.0130
0.0354
0.0201
0.0327
0.0573
0.7872
1.0000

16.0
30.1
44.1
58.1
58.1
72.2
72.2
86.2
263

Mj

Weight

xjMj
0.026
0.181
2.059
0.755
2.057
1.451
2.361
4.939
207.034
220.863
C3+ = 220.656
C2+ = 220.837
MSTO = 220.863 lb
lb mole

Department of Petroleum Engineering, Heriot-Watt University

Liquid
density at
60F and
14.7 psia
oj

Liquid
volume at
60F and
14.7 psia
xjMj / oj

31.66
35.12
36.45
38.96
39.35
41.30
55.25

0.0650
0.0215
0.0564
0.0372
0.0600
0.1196
3.7472
4.1069
cu.ft. C3+
lb.mole STO

19

Density of propane plus =

220.656
lb
= 53.73
4.1069
cu ft

Weight fraction ethane in ethane plus =

Weight fraction methane in STO =

STO = 53.73

0.026
= 0.0001
220.863

From chapter 6, figure 13.

53.73
= 0.86
62.4

STO =
o

lb
cu.ft.

0.181
= 0.001
220.837

API =

141.5
131.5 = 32.8
0.861

Step 4: Calculate gas to oil ratio

R SP =

V1 lb moles sep gas

SCF sep gas 5.615
lb mole STO
STO

379

L1L ST
lb mole STO
lb mole sep gas M STO
STB

R SP = 2130

V1STO
L1L ST M STO

Similarly:

R ST =

2130 V2STO
L 2 M STO

RT = RST + RSP

R SP =

SCF
(2130)(0.4291)(53.73)
= 450
STB
(0.5709)(0.8649)(220.9)

R ST =

SCF
(2130)(0.1351)(53.73)
= 81
STB
(0.8649)(220.9)

R T = 531

SCF
STB

Step 5: Calculate the density and molecular weight of the reservoir liquid at reservoir
conditions.
20

12

Vapour Liquid Equilibria

Component Component,
of reservoir mole
liquid
fraction xj

Molecular
weight Mj

C1
C2
C3
i-C4
n-C4
i-C5
n-C5
C6
C7+

16.0
30.1
44.1
58.1
58.1
72.2
72.2
86.2
263

0.3378
0.0694
0.0982
0.0133
0.0299
0.0125
0.0193
0.0299
0.3897
1.0000

Density of propane plus =

Weight xjMj

5.405
2.089
4.331
0.773
1.737
0.902
1.393
2.577
102.491
Mor =121.699
lb / lb mole res oil
C2+ = 116.294
C3+ = 114.205

31.66
35.12
36.45
38.96
39.35
41.30
55.25

Liquid
volume at
60F and
14.7 psia
xjMj / j
0.1368
0.0220
0.0477
0.0232
0.0354
0.0624
1.8550
2.1825 cu.ft.C3+
lb.mole res oil

114.205
lb
= 52.33
2.1825
cu ft

Weight fraction ethane in ethane plus =

2.089
= 0.018
018
116.294

Weight fraction methane in reservoir oil =

po = 49.1 lb.cu ft.

Liquid
density at
60F and
14.7 psia
j

5.405
= 0.044
121.699

From figure 13, Chapter 6.

From figure 14 chapter 6

compressibility correction 49.1 + 0.8 = 49.9 at 60F and 2710 psia.
From figure 15 chapter 6
thermal expansion correction 49.19 - 3.86 = 46.04 at 220F and 2710 psia.
or = 46.04 lb/cu ft.
Step 6: Calculate formation volume factor using equation:

Bo =

M resSTO
res M STO L1L ST

Bo =

(121.7)(53.73)
(46.04)(220.9)(0.5709)(0.8649)

Bo = 1.302

res bbl
STB

Department of Petroleum Engineering, Heriot-Watt University

21

Integration of the Black-Oil and Compositional Approach

The example above illustrates the combination of the compositional based prediction
of phase volumes and associated properties and that based around the black-oil model,
centered around parameters of oil formation volume factor and gas-oil ratio. By such
a combination, the weaknesses of the simple two component black-oil model which
is at the heart of describing oil field parameters, can be overcome by using compositional
derived values rather than using perhaps inappropriate empirical correlations and
charts.
Determination of K valves
In the procedures developed, it has been assumed that values for K are available. In
the next chapter we will examine the procedures for determining K.

22

12

Vapour Liquid Equilibria

REFERENCES
(1) Danesh, A, "PVT and Phase Behaviour of Petroleum Reservoir Fluids." 1998
Elsevier. pp 105-206
(2)Prausnitz,J.M., Lichtenthaler,R.N., and d Azevedo,E.G. Molecular
Thermodynamic of Fluid -Phase Equilibria 2nd Edition, Prentice Hall Inc, NY.,
(1986)
(3) Smth,J.M. and Van Ness,H.C. Introduction to Chemical Engineering
Thermodynamics, Third Edition, McGraw-Hill ( 1975)
(4) McCain,W.D. The Properties of Petroleum Fluids Petroleum Publishing Co.
Tulsa 1973
(5) GPSA: Engineering Dat Book, Gas Processors Association. Tulsa Oklahoma, Gn
Education 1972

Department of Petroleum Engineering, Heriot-Watt University

23