Phase Behaviour of Multicomponent Mixtures

Phase Behaviour of
Multicomponent Mixtures

1998 AEA Technology plc - All Rights Reserved

Nat Gas Lec 2.pdf

Lecture

Lecture
The Phase Behaviour of the Multicomponent Mixtures module
introduces you to the behaviour of gas mixtures and the use of Phase
Envelopes to predict such behaviour.

Learning Objectives
Once you have completed this module you will understand:

How to use a Phase Envelope to determine gas mixture

behaviour
Concepts of dewpoint, bubble point and retrograde
condensation
How to recombine gas and liquid samples to create a mixture

Terminology
Bubble Point
The lowest temperature at a specified pressure at which the first stable
vapour forms above a liquid.

Cricondenbar
The highest pressure at which liquid and vapour phases can exist at
equilibrium in a multicomponent system.

Cricondentherm
The highest temperature at which liquid and vapour phases can exist at
equilibrium in a multicomponent system.

Lecture

Dewpoint
The temperature at any given pressure at which liquid initially
condenses from a gas or vapour. It is specifically applied to the
temperature at which water vapour starts to condense from a gas
mixture (water dewpoint), or at which hydrocarbons start to condense
(hydrocarbon dewpoint).

Retrograde Condensation
A phenomenon that occurs when the temperature of a mixture is
between the cricondentherm and the critical point, and the sample is
at the dewpoint pressure. With retrograde condensation, hydrocarbon
liquids will form as the pressure is lowered.

Theoretical Foundations
Vapour / Liquid Equilibria
In Module 1, the liquid/vapour behaviour of single compounds was
explained. When two or more compounds form a mixture, the vapour/
liquid behaviour is influenced greatly by the composition of the
mixture. Additionally, in gas systems such as natural gas, there is a
range in the temperature, at constant pressure, over which the mixture
is either totally in the liquid phase or totally in the vapour phase. This is
illustrated in Figure 2.1, which is a phase diagram of a 50 % binary
mixture of methane and propane. At the pressures and temperatures
on the right hand side of the diagram, all of the material is in the vapour
phase, and on the left hand side of the diagram, all of the material is in
the liquid phase. Within the envelope formed by the lines, the mixture
exists in both liquid and vapour phases.

Lecture

Fig. 2.1

At 4000 kPa, for example, the mixture is in the vapour phase if the
temperature is greater than 40C. By cooling the mixture from say
60C at a constant pressure of 4000 kPa, the line on the right side of the
phase envelope would be intersected at about 40 C. This means that at
this temperature and pressure, the first droplets of liquid would form.
This point is called the dewpoint temperature of this particular
mixture, corresponding to this pressure. If a different pressure had
been selected, then a different dewpoint temperature would have been
obtained. The line connecting all of the dewpoints is called the
dewpoint line.

The critical point of a mixture

is the temperature and
pressure at which the
dewpoint and the bubble
point lines meet.

As the mixture is further cooled, the path proceeds to the left inside the
envelope. By removing heat from the mixture, more of the material will
liquefy, until the line on the left side of the diagram is reached. At this
point, all of the material is in the liquid phase. This is the bubble point
temperature at this particular pressure. The heat removed is the latent
heat of condensation, or vaporization, if we had started on the left side,
where the mixture is in the liquid phase. The line connecting all of the
bubble point temperatures is called the bubble point line.
Since natural gas is a mixture of many distinct compounds, the
behaviour of the natural gas mixture will vary greatly with composition,
pressure and temperature. Figure 2.2, for example, shows the
pressure-temperature diagram for the Solution Gas mixture of Table A.

Lecture

As can be seen, the two-phase envelope differs considerably from that

of the binary system displayed in Figure 2.1. The dewpoint line curves
over the top of the diagram and continues to the left.
Fig. 2.2
Certain terms are generally
applied to some aspects of this
type of diagram, which are
also illustrated on page 1-3 of
the Data Book.

Retrograde condensation is the phenomenon that occurs when the

temperature of a mixture is between the cricondentherm and the
critical point, and the sample is at the dewpoint pressure. By lowering
the pressure, some condensation will initially occur as the pressure is
lowered into the two-phase region. Retrograde condensation is the
formation of hydrocarbon liquids as the pressure is lowered. It occurs
in a limited range of pressures and temperatures between the critical
point and the cricondentherm.

All natural gas mixtures can be totally liquefied, if sufficiently cooled.

In gas processing, it is sometimes necessary to cool the gas mixture at
elevated pressure to liquefy a portion of the mixture, and recover some
of the heavier components such as propane, butane, etc. Thus it is
necessary to predict not only the dewpoint temperature at a given
pressure, but also the composition of a partially condensed natural gas
mixture.

Lecture

The vapour/liquid (V/L) equilibria calculations fall into three types of

calculation:

dewpoint calculation
bubble point calculation
flash calculation
To perform any of these calculations, the composition of the mixture
(feed) must be known, and either the pressure or the temperature at
which the dewpoint or bubble point calculation is to be performed
must also be given. For flash calculations, the feed composition and
the pressure and temperature within the two-phase envelope must be
given. The unknown in this type of calculation is the fraction of the
feed that will liquefy, and the compositions of the liquid and vapour
phases resulting from the partial condensation of the feed.

K-Value
The concept on which these calculations are based is the vapour/liquid
equilibrium constant, K, which is defined as:
K = yx
where: K = vapour/liquid equilibrium constant
y

= mole fraction of component in the vapour phase

= mole fraction of component in the liquid phase.

The theoretical basis for this concept comes from combining Raoults
Law and Daltons Law as they apply to ideal liquids and gases:
pi = Pi xi
pi = P yi
where: p i = partial pressure in vapour phase due to component "i"
Pi = vapour pressure of component "i" at system temperature
xi = mole fraction of component "i" in the liquid phase
P = total pressure of two-phase system
yi = mole fraction of component "i" in the vapour phase.

Lecture

The value of p i is the same in both equations. For any compound in a

two-phase system at constant pressure and temperature, the following
relationships can be developed:
Pi xi = P yi
yi xi = Pi P = K

Equilibrium constants for

hydrocarbons are found in
Section 25.

V/L calculations are best

performed on a computer,
where K values are determined
by equations of state.

The K values are provided in charts with pressure and temperature as

the variable parameters. Additionally, the concept of convergence
pressure is also used to account for variations in composition.
Convergence pressure of a mixture is the true critical pressure for the
particular composition. At the convergence pressure, there is no
separation between liquid and gas, and therefore the two-phase
calculations can only be done at pressures less than the convergence
pressure.
Since convergence pressure depends mainly on the
composition of the liquid phase, in addition to temperature, it is
necessary to assume a convergence pressure, perform the flash
calculation, and then check the assumed convergence pressure.

The eleventh edition of the Data Book in SI units has a limited selection
of K data charts. An example of a flash calculation is presented in
Fig. 25-3 of the Data Book, using these charts. This edition of the Data
Book does not explain the check of the convergence pressure.

Problem 2-1
The Sour Gas Condensate Gas of Table A is produced to a plant.
Determine the dewpoint temperature of this gas at 7000 kPa. Use the
20.7 MPa convergence pressure charts for the K values in Section 25 of
the Data Book. The composition for Sour Gas from Table A is included
here:

Lecture

TABLE A
Sour Gas Compositon
Component

Mole Percent

H2

0.00

He

0.00

N2

0.38

CO2

2.62

H2S

7.09

C1

75.41

C2

5.33

C3

3.74

iC4

1.22

nC4

0.92

iC5

0.51

nC5

0.38

C6

0.19

C7+

2.21

TOTAL

100.00

Problem 2-2
The Sour Gas Condensate Gas of Table A is produced into a plant inlet
separator at 7000 kPa and 30 C, at a total well effluent (vapour
equivalent) rate of 1400 000 Sm3/d. Determine the gas composition,
the condensate composition and the gas and condensate rates leaving
the inlet separator.
A sample flash calculation is given on page 25-4 of the Databook.

Lecture

Recombination Calculations
Flash calculations estimate the fractions of a two-phase system when
liquid and vapour phases form, as well as the composition of each
phase. When wet gas wells are produced, especially gas condensate
wells, the fluids arrive at the wellhead in both liquid and vapour phases.
To be able to analyze the reservoir behaviour of these fluids, or to
design a gas processing plant, it is necessary to determine the
combined composition of the fluids in the reservoir. This is done by
performing recombination calculations.
When gas condensate wells are tested, great care is taken to obtain
good, representative samples of all gas and liquid streams from the
sampling points on the test equipment. Such test equipment is
indicated in Figure 2.3 on the next page.

Fig. 2.3

Lecture

11

Accurate rates of flow of each fluid are also required. When the samples
are obtained by trained technicians, it is necessary to also complete a
sample data sheet, which must show the following:

well name and location

perforated interval being tested
name of zone
temperature of fluid at sample point
pressure of fluid at sample point
date
sample point location on equipment

Duplicate samples are usually taken near the end of a test, when the
flow rate has been steady for a few hours. These samples are then sent
to a laboratory for analysis. A routine 14 component analysis is done
on the gas samples, and a complete analysis of the liquids, up to C30 is
usually done. These compositions, together with the flow rates during
the time of sampling, provide the basis for performing the
recombination calculations.

To simplify the calculation process, a tabulation as shown in Table 2.1

can be used. It is necessary to convert all rates either to moles per time
unit such as hour or day, or to standard cubic metres per time unit. In
Table 2.1, the flow rates of all compounds are expressed in 103 Sm3/d..
Subsequently they are totalled, to yield the overall composition, x, as
well as the relative molecular mass, M, and the pseudo-critical
properties.

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Lecture

Problem 2-3
A four-point AOF test was conducted on a new gas well, which
produced gas and condensate of the following compositions:

Compound

Mole Fr. Gas

Mole Fr. Cond.

HP Separator

LP Separator

N2

0.0015

0.0005

0.0000

CO2

0.0131

0.0201

0.0023

C1

0.8660

0.6965

0.0275

C2

0.0886

0.1971

0.0490

C3

0.0207

0.0637

0.0626

iC4

0.0024

0.0070

0.0185

nC4

0.0027

0.0077

0.0296

iC5

0.0012

0.0027

0.0275

nC5

0.0013

0.0026

0.0374

C6

0.0006

0.0009

0.0443

C7+

0.0019

0.0012

0.7013

Totals

100.0000

100.0000

100.0000

Determine the combined fluid composition for these streams. Other

information based on test and fluid compositions is as follows:

12

Stabilized gas rate, H.P. Separator: 300 000 Sm3/d

Stabilized gas rate, L.P. Separator: 4060 Sm3/d
Separator liquid from L.P. Separator: 39.54 m3/d
Molar mass of L.P. Separator liquid: 0.096 kg/mol
Density of separator liquid: 689 kg/m3

Table 2.1

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Lecture

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