Vapour Liquid Equilibrium

Reservoir Engineering I
PCB2023
Vapor Liquid Equilibrium

Dr. Mohammed Abdalla Ayoub
Lesson outcomes
At the end of this class students should be able

to :
Identify the importance of VLE
Apply the Ideal and non- Ideal Solution
Determine Compositions & Quantities of the

Equilibrium Gas & Liquid Phases.
Calculate the saturation pressure of the
mixture
2
Importance of Vapour Liquid Equilibrium
Multiphase aspects of hydrocarbon mixtures are important

part of reservoir management.
Reservoir flow & well productivity,

facility design
and pipeline transport.
Predicting relative amounts of phases and their physical
properties is an important part.
Behavior of multicomponent mixtures in reservoirs and their

production to surface is a serious challenge.
3
VLE Data,. Intro.
The most accurate and reliable source of obtaining data on

equilibrium conditions and the phases is laboratory studies,
including compositional analysis and reservoir fluid studies.
practical limitations: cost, time, and limited amount of sample

availability.
In the absence of such laboratory studies, calculation methods are

relied upon, and these methods are called phase equilibrium or
vaporliquid equilibrium (VLE) calculations.
VLE Data,. Intro.
The input data for the VLE calculations consist of the overall
composition of the reservoir fluid, pressure and temperature

conditions, and the properties of the individual components (defined
as well as pseudo-components and plus fractions).
Based on such input data, VLE calculations typically involve the

determination of saturation pressures (bubble or dew points),
equilibrium phase compositions, volumes, compressibility factors
Total
Production
System
Complexity of allocation
of produced oil to supply
fields
Main issues to reservoir

engineer.
Multiphase behavior relative
permeability etc.
Volumes between reservoir
and surface.
Physical properties of gas and
oil in reservoir and at surface
7
Vapor-liquid equilibrium
Quick definitions:
A mole is what
6.02x1023 molecules
weigh.
MW=no. mass units
(1.6x10-24 g) a molecule
weighs
Phase diagram defines area bounded by bubble point and dew point
curves where two phases exist.
Too simple to describe as in volatile oil and solution gas.
Throughout the production process from the reservoir

through the separator to the stock tank conditions, large
volumes of gas are generated from the reservoir oil.
The oil shrinks.
VO
Oil formation volume factor Bo
VST
Solution gas to oil ratio
VG
RS
VST
Volume factors can be determined directly in the laboratory
or from equilibrium calculations
Besides separator calculations vapor

liquid equilibrium calculations used for.
Reservoir calculations
Two phase pipeline flow calculations

Process calculations
10
Vapor-liquid equilibrium calculations
The grid
block of a
simulator
can be
considered
to be the
separator of
a process
unit.
11
Vapor-liquid equilibrium calculations
VLE calculations have been restricted to separate areas;

reservoirs and wells, surface operations, pipelines,
onshore treatment and refinery operations
Increasing trend is the integration of this to determine
for example impact of a change in a reservoir parameter

on refinery or pipeline outputs.
12
Ideal solutions
An ideal solution is a solution for which:
1.
Mutual solubility results when components are mixed.
2.
No chemical interaction occurs upon mixing, and
3.
The intermolecular forces of attraction and repulsion are
the same between the unlike and like molecules.
13
Ideal Mixtures
Ideal mixtures of gases or liquids are those in which there is

insignificant interaction between various constituents, which is
generally the case at low pressures for simple mixtures.
Although, petroleum reservoir fluids are not ideal mixtures.
Equilibrium ratio is on the basis of two important laws, namely,

Raoults and Daltons law
14
Ideal solutions
Raoults Law
Partial pressure of a given component in a multicomponent system is the
product of its mole fraction in the liquid phase and its vapor pressure.
pi X i Pvi
Pi : The partial pressure of component i in the gas phase

Xi : The mole fraction of component i in the liquid phase
Pvi : The vapor pressure of component i at the given
temperature
Daltons Law
For an ideal gas mixture, the partial pressure of a component is the
product of its mole fraction and the total system pressure
pi Yi P
P: The total system pressure

Yi : The mole fraction of component i in the vapor phase
15
Ideal Equilibrium Ratio

Equilibrium ratio is the ratio of the composition in the vapor phase to
that of the liquid phase. Regardless of the overall composition of the

hydrocarbon mixture, the equilibrium ratio is only a function of the
system pressure and temperature.
The vapor pressure of a component is only a function of temperature
From Raoults and Daltons Laws
Yi
Pvi
K i Eqilibrium Ratio
Xi
P
----------(1)
Although, on the basis of vapor pressures and the system pressure,

equilibrium ratios for various components can be determined.
16
Equilibrium Ratio
Ki is defined at a particular pressure and
temperature
Other names: K-factors, K values, equilibrium
vapor liquid distribution coefficients
17
Concept of PT Flash
nv moles of vapor having
composition Yi and nL moles of
liquid having composition Xi.
This particular process, resulting
in the splitting of the feed or a
hydrocarbon
equilibrium
mixture
vapor
and
into
liquid
phases at a given pressure and

temperature, is called PT flash.
Almost all petroleum reservoir fluids undergo this type of PT flash
process either in the reservoir, production tubing, or on the surface.
18
Concept of PT Flash, cont.

By definition, the overall material balance on the feed and the equilibrated
vapor and liquid phases lead to
n=nL+nV
----------(2)
A similar material balance equation can also be written in terms of the ith
component of the mixture:
Zi n = Xi nL + Yi nV
----------(3)
Zin: moles of component i in the feed
XinL: moles of component i in the equilibrium liquid phase

YinV : moles of component i in the equilibrium vapor phase
19
Compositions & Quantities of the Equilibrium

Gas & Liquid Phases of an Ideal Solution
Equations (2) and (3) can be further simplified by considering the basis of
1mol of feed, that is, n = 1:
nL+nV=1
Xi nL + Yi nV = Zi
---------(5)
Xi (1 nV) + Ki Xi nV = Zi
---------(6)
Combining Equations 1, 4, and 5
So
---------(4)
Zi
Xi
1 nv K i 1
---------(7)
20

Also by definition of mole fraction
n
Zi
Xi
1 .0
i 1
i 1 1 n v K i 1
Similarly
n
---------(8)
Zi Ki
Yi
1 .0
i 1
i 1 1 n v K i 1
---------(9)
21

On the basis of the given mole fraction of the feed Zi and the calculated
equilibrium ratio Ki from Equation 1 (from vapor pressure at a given
temperature and the system pressure), the only unknown that remains in
Equation 8 or 9 is the moles of the equilibrium phase vapor nV.
However, considering the nature of these equations, a trial-and-error

solution is required in either case.
Since the calculations are based on 1mol of feed, a trial value of nV between 0
and 1 is chosen.
If the selected value of nV results in the summation of 1 in Equation (8) or (9),

the moles of equilibrium liquid phase and the compositions of all the
components in the equilibrium vapor phase and the liquid phase can then be
calculated. If the summation does not equate 1, a new iteration cycle may be
22
needed.
Flash Functions
Alternatively, Equations (8) and (9) can be written as follows (called the flash
functions):
n
Zi
X i 1 0, or,
1 0
i 1
i 1 1 n v K i 1
n
----(10)
Zi Ki
Yi 1 0, or,
1 .0 0
i 1
i 1 1 n v K i 1
----(11)
Those eqs. may result in unpredictable trends in the vicinity of nV = 0 and nV = 1.

23
Rachford and Rice

Is considered as mathematically much more robust compared to
Equation (10) or (11) and is thus commonly used or preferred in

VLE calculations:
Z i K i 1
Yi X i 0, or,
0
i 1
i 1
i 1 1 n v K i 1
n
----(12)
It needs to be solved iteratively in such a way that a certain value

of nV will satisfy the condition of the right-hand side resulting in a
value of zero.
24
25
Compositions & Quantities of the Equilibrium Gas &

Liquid Phases of an Ideal Solution
Example:
Calculate the compositions and quantities of the gas and liquid when 1.0
lb. mole of the following mixture is brought to equilibrium at 150oF and
200 psia. Assume ideal-solution behavior.
Component
Composition, mole
fraction
Propane
0.610
n-Butane
0.280
n-Pentane
0.110
1.000
Zi Ki
Yi
1 .0
i 1
i 1 1 n v K i 1---------(8)
By trial and error, determine the value of nv which satisfies the equation
26

component
Composition of
mixture (mole
fraction), Zi
Vapor
pressure
@150oF, Pvi
Propane, c3
0.610
350
n-Butane, nC4
0.280
105
n-Pentane, nC5
0.110
37
1.000
Composition of
the gas, mole
fraction, Yi
Composition of
the liquid, mole
fraction, Xi
0.76896
0.439406
0.19493
0.371296
0.035201
1.000
0.190274
1.000
The summation equals 1 for nv =0.517651; thus there are 0.482349 moles of
liquid and 0.517651 moles of vapor for each mole of total mixture. The
compositions for vapor and liquid are given in the last two columns.
27
Calculation of the Bubble-Point Pressure of an Ideal

Solution
The bubble point is the point at which the first bubble of gas is formed.
For all practical purposes, the quantity of gas is negligible.
nv to be equal to zero and nL to be equal to the total moles of the

mixture.
Substituting of nv 0, nL 1 (assuming the basis to be 1 mole of feed)

and p=pb into equation
n
i 1
i 1
Z i X i 1 .0
---------(13)
28
Calculation of the Bubble-Point Pressure of an Ideal

Solution
Thus the equilibrium is established for the newly formed gas

phase
n
Y Z K
i 1
i 1
1.0
---------(14)
by substituting the value of Ki from Equation (1)

n
Pvi
Zi
1 .0
Pb
i 1
Or
---------(15)
Pb Z i Pvi
---------(16)
i 1
Its a simple molar mixing rule that uses mole fractions and vapor
pressures of individual components.
29
Calculation of the Dew-Point Pressure of an Ideal

Solution
At the dew-point pressure, the quantity of liquid essentially is negligible.
p=pd, nL0 and nv 1 (assuming the basis to be 1mol of feed)

n
Z Y
i 1
i 1
1 .0
---------(17)
and thus, the equilibrium is established for the newly formed liquid phase
n
Zi
Xi
1 .0
i 1
i 1 K i
---------(18)
by substituting the value of Ki from Equation (1)

n
Zi
1 .0
i 1 Pvi Pd
---------(19)
Pd
1
n
Z i Pvi
i 1
---------(20)
Summary
At the end of this class students managed to :
Identify the importance of VLE
Apply the concept of Ideal Solution
Determine Compositions & Quantities of the

Equilibrium Gas & Liquid Phases for ideal solutions.
Calculate the saturation pressure of the mixture.

31
End of Chapter 5
32

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Reservoir Engineering I

Vapor Liquid Equilibrium

At the end of this class students should be able

Identify the importance of VLE

Apply the Ideal and non- Ideal Solution

Determine Compositions & Quantities of the

Importance of Vapour Liquid Equilibrium

Multiphase aspects of hydrocarbon mixtures are important

Reservoir flow & well productivity,

and pipeline transport.

Predicting relative amounts of phases and their physical

properties is an important part.

Behavior of multicomponent mixtures in reservoirs and their

VLE Data,. Intro.

The most accurate and reliable source of obtaining data on

practical limitations: cost, time, and limited amount of sample

In the absence of such laboratory studies, calculation methods are

vaporliquid equilibrium (VLE) calculations.

VLE Data,. Intro.

composition of the reservoir fluid, pressure and temperature

Based on such input data, VLE calculations typically involve the

equilibrium phase compositions, volumes, compressibility factors

Main issues to reservoir

Too simple to describe as in volatile oil and solution gas.

Throughout the production process from the reservoir

The oil shrinks.

Volume factors can be determined directly in the laboratory

or from equilibrium calculations

Besides separator calculations vapor

Two phase pipeline flow calculations

Vapor-liquid equilibrium calculations

Vapor-liquid equilibrium calculations

VLE calculations have been restricted to separate areas;

onshore treatment and refinery operations

Increasing trend is the integration of this to determine

for example impact of a change in a reservoir parameter

Mutual solubility results when components are mixed.

No chemical interaction occurs upon mixing, and

The intermolecular forces of attraction and repulsion are

the same between the unlike and like molecules.

Ideal mixtures of gases or liquids are those in which there is

Although, petroleum reservoir fluids are not ideal mixtures.

Equilibrium ratio is on the basis of two important laws, namely,

Pi : The partial pressure of component i in the gas phase

P: The total system pressure

Ideal Equilibrium Ratio

that of the liquid phase. Regardless of the overall composition of the

From Raoults and Daltons Laws

Although, on the basis of vapor pressures and the system pressure,

phases at a given pressure and

Concept of PT Flash, cont.

Zin: moles of component i in the feed

XinL: moles of component i in the equilibrium liquid phase

Compositions & Quantities of the Equilibrium

Combining Equations 1, 4, and 5

Compositions & Quantities of the Equilibrium

Compositions & Quantities of the Equilibrium

However, considering the nature of these equations, a trial-and-error

If the selected value of nV results in the summation of 1 in Equation (8) or (9),