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Pressure,Volume,Temperature(PVT)Behaviour

Pressure, Volume,
Temperature (PVT) Behaviour

1998 AEA Technology plc - All Rights Reserved


Nat Gas Lec 1.pdf

Lecture

Lecture
The Pressure, Volume, Temperature (PVT) Behaviour module
introduces you to some of the basic concepts needed in the Gas
Processing industry. You will learn to use the GPSA databooks to
determine PVT behaviour and properties for Gas Processing Streams.

Learning Objectives
Once you have completed this module, you will understand the
following concepts:

Concept of the Mole


Ideal and Real Gas Laws
PVT behaviour
Equations of State
Calculation of heating value for natural gas

Terminology
Calorimeter
An apparatus which is used to determine the heating value of a
combustible material.

Compressibility Factor
A factor, usually expressed as "Z", which gives the ratio of the actual
volume of gas at a given temperature and pressure to the volume of gas
when calculated by the ideal gas law.

Lecture

Critical Pressure
The vapour pressure of a substance at its critical temperature.

Critical Temperature
For a pure component, the maximum temperature at which the
component can exist as a liquid.

Gas Constant (R)


The constant multiplier in the Ideal Gas Law. Numerically, R=PV/T, if V
is the volume of one mole of an ideal gas at temperature T and
pressure P.

Gross Heating Value


Gross heating value, MJ/m3, is the amount of energy transferred as
heat, upon the combustion of one standard cubic metre of gas in an
ideal combustion reaction, at standard pressure and temperature, with
all combustion products cooled to the standard temperature and all
water formed during the combustion process being condensed.

Latent Heat of Condensation


Amount of enthalpy (energy) per unit mass, required to change phase
from liquid to vapour. Energy must be supplied to vaporize; it is
released on condensation.

Net Heating Value


Net heating value, MJ/m3, is the amount of energy transferred as heat
in an ideal combustion reaction, but with the water formed in the
combustion remaining in the vapour phase.

Relative Density
The Relative Density of a gas is the ratio of the densities of the gas and
air both at standard conditions of 15C and 101.325 kPa (abs).

Lecture

Theoretical Foundations
Concept of the Mole

Molar mass of gas industry


compounds is given in
Fig. 23-2, Column A.

Natural gas is a fluid that will fully occupy the space in the vessel or pipe
in which it is contained. At low pressures, in the order of one or two
atmospheres, the volume of an amount of gas will vary inversely with
absolute pressure at constant temperature (Boyles Law), and in
proportion to absolute temperature at constant pressure (Charles
Law). It is also accepted that at the same pressure and temperature, a
given volume of any gas will contain the same number of molecules as
the same volume of any other gas (Avogadros hypothesis). This leads
to the concept of the "mole", with the symbol "mol". For engineering
purposes, a mole is simply an amount of mass of any substance (solid,
liquid or gas), which has the same number of molecules as a mole of
any other substance. By assuming the molar mass of one element
(0.012 kg of Carbon for example), the relative mass of a mole of all other
elements and compounds (having the same number of molecules as
0.012 kg of Carbon) can be determined. The molar mass of compounds
encountered in the gas industry is given in Fig. 23-2, Column A in the
Data Book, in kilograms per kilomole (kg/kmol).

The equivalent molar mass of natural gas mixtures is calculated on a


weighted mole fraction basis, using the molar mass of each individual
compound and multiplying by the mole fraction of that compound in
the gas mixture. The relative molecular mass of gas is designated by the
letter M. The relative molecular mass of air is 28.9625, making the
molar mass of air 0.0289625 kg per mole. In natural gas engineering,
the ratio of the molar mass of gas to that of air is frequently used. This
ratio is called "gas gravity" in British units and "relative density" in SI
units. It is usually designated by the letter G, and since the ratio of
molecular masses is the same as the ratio of molar masses, then:
M
G = ------------------28.9625
M = 28.9625 G

Lecture

Ideal / Real Gas Laws


The relationships among pressure, volume, temperature (PVT) and
number of moles can be combined and expressed by the Ideal Gas Law
in terms commonly used in the gas industry:
PV = nRT ,
where: P = absolute pressure, kPa
V = volume, m3
n = number of kilomoles
3
8.3145 kPa m
R = Gas Constant, ---------------------------------------kmol K
T = absolute temperature, K (= 273.15 + C)
When dealing with gas systems, the mole fraction of a gas mixture is
equal to the volume fraction, as it is assumed that any mole of gas will
occupy the same volume as any other mole of gas at the same pressure
and temperature. This is not the case for liquid mixtures, that is to say,
when dealing with liquids, the mole fraction differs from the volume
fraction.

See Fig. 23-3, Column E for


data on liquid volume per
kmol.

At low pressures, the Ideal Gas Law is reasonably accurate in describing


the PVT behaviour of gases. When gases are compressed, their
molecular volumes and intermolecular forces cause deviations from
ideal behaviour. To account for this deviation from ideal behaviour for
real gases, the concept of a dimensionless "deviation factor", normally
referred to as the "compressibility factor", has been introduced into the
Ideal Gas Law. This factor has been given the designation "Z", and is
commonly referred to as the Z factor in natural gas calculations. The
Ideal Gas Law is transformed to the Real Gas Law by adding the Z
factor:
PV = ZnRT , with all terms as defined above.

Lecture

Equations of State

Equations of State are


available in Section 25, page
25-7.

Other, more complex equations have been developed in the last 50


years or more, to account for molecular volumes and molecular
attractive forces. These are generally called "Equations of State". One
of the most popular and accurate equation of state for describing the
behaviour of natural gases is the Peng-Robinson equation of state
which was developed at the University of Alberta in 1975. Since
equations of state are difficult to handle without computers, no further
discussion on equations of state will be provided in this section.
Equations of state and their use in HYSYS are discussed in more detail in
the Workshop section of this Module.

PVT Behaviour
Since gas is a compressible fluid, it is necessary to agree on standard
conditions of pressure and temperature, for expressing any amounts of
gas in terms of volumes at the standard or reference conditions. The
standard conditions of pressure and temperature for determining
standard volumes of gas are the following:
In this course standard
conditions are 101.325 kPa
and 15C.

Standard pressure: 101.325 kPa (abs)


Standard temperature: 15C or 288.15 K
Standard volume : Sm3 (cubic metre of gas at a pressure of 101.325 kPa
(abs) and 15C
In all natural gas engineering calculations, the estimation of the PVT
behaviour is a requirement. Without the use of a computer, chart
methods are available to perform these tasks. Before the advent of the
computer and the development of the powerful software programs that
are nowadays available to virtually every engineer, all of the design
calculations were made using chart approximations for determining
the properties and PVT relationships of natural gas. These notes will
explain what calculations are necessary, and how to perform them
without computers.

Lecture

Z Factor
The Z factor is one of the most frequently calculated properties in any
engineering calculation dealing with natural gas. The determination of
the Z factor by chart methods is based on the concept of the "Law of
Corresponding States". This law postulates that at the same ratio of
pressure and temperature to the critical pressure and temperature, all
gases have the same volumetric deviation from ideal volume. The ratio
of pressure to critical pressure is called the "reduced pressure". The
"reduced temperature" is arrived at in a similar manner.
P
P r = ----Pc

Reduced values are always


based on absolute pressure
and temperature.

T
T r = ----Tc
where: P = pressure at which Z is to be determined, kPa (abs)
T = temperature at which Z is to be determined, K
Pc = critical pressure, kPa (abs)
Tc = critical temperature, K
Pr = reduced pressure, ratio
Tr = reduced temperature, ratio
Once the reduced values have been determined, the Z factor is
obtained from the Z factor chart for natural gas, which is given in
Fig. 23-4 of the Data Book. The critical properties of pressure and
temperature for each compound are given in Fig. 23-2, page 23-2, of
the Data Book.

Fig. 23-4: Z Factors.


Fig. 23-2: Critical temperature
and pressure.

As we have seen in the introduction, natural gas is a mixture of many


compounds, so to apply the Law of Corresponding States to natural gas
mixtures, it is necessary to determine a substitute for the critical
pressure and critical temperature of a pure gas. A method was
proposed by Kay, which is based on the mole fraction weighted average
pressure and temperature of the gas mixture.

Lecture

The result is a pseudo-critical pressure and pseudo-critical


temperature for a particular gas mixture. These pseudo-values are then
used as if they were the true critical values of pressure and temperature
for the mixture which, strictly, they are not.
P pc =

Yi Pci

T pc =

Yi Tci

where: Ppc = pseudo-critical pressure of gas mixture, kPa (abs)


Pci = critical pressure of compound "i" in the gas mixture,
kPa(abs)
Tpc = pseudo-critical temperature of gas mixture, K
Tci = critical temperature of compound "i" in the gas
mixture, K
Yi = concentration of compound "i" in the gas mixture, mole
fraction.

The Z factor chart in Fig. 23-4


of the Data Book is only valid
for sweet natural gas.

When natural gas contains significant amounts (more than one


percent) of H2S or CO2, then the Z factor obtained from Fig. 23-4 will
suffer in accuracy. This was experienced in western Canada many years
ago, when the sour gas pools were discovered. Companies took
samples of gas from sour wells and had laboratories determine a matrix
of Z factors for such sour gases. Various attempts were made to develop
new correlations for estimating the Z factor for sour gases in the 1950s
and 1960s. In 1970, Wichert and Aziz published their research work,
which was done at the University of Calgary, on new computer
methods for estimating the Z factor for sour gases.

While three methods were developed by Wichert-Aziz, two have found


general acceptance. The third method, a modification of a method for
Z factor calculation developed by Pitzer et al., has the drawback of
requiring the storage of two matrices of factors used in the
determination of the Z factor. This uses up computer storage, and
requires interpolation to extract the appropriate factors at the desired
conditions of pseudo-reduced pressure and temperature. As a result,
the Wichert-Aziz modification of the Pitzer et al. Z factor calculation
method has not proven as popular. The other two methods are virtually
as accurate, and are described in the following pages.

Lecture

Wichert-Aziz Modification of the


Redlich-Kwong Equation of State
Redlich and Kwong (R-K) proposed an equation of state in 1949 which
has gained popularity, as it is relatively simple yet accurate when
compared to more complex equations. It has also been modified by
others over the years to further enhance its accuracy. Equations of state
are suited for computer use as the need for storing data is low, and is
usually limited to very basic data, such as critical pressures and
temperatures of the components making up the gas mixture.

The Wichert-Aziz modification of the R-K equation of state requires the


determination of a parameter, 2 , as follows:
2

2 = 15 ( A A ) + 4.167 ( B

0.5

B ) , with units of C

where: A = mole fraction (H2S + CO2) in sour gas mixture,


B = mole fraction H2S.

The critical temperature (in Kelvin)of each component in the gas


mixture is then adjusted by subtracting the value of 2 , and each
component critical pressure (in kPa) is adjusted as follows:
T ci = T ci 2
P ci = Pci ( T ci ) T ci
where:

Tci and Pci are critical temperature, in K, and critical


pressure, in kPa (abs), of component "i" in the gas
mixture, and T ci and Pci are the adjusted critical
conditions for each compound.

The adjusted critical values are used to calculate the constants in the
R-K equation with the mixing rules as proposed by Redlich and Kwong.
An adjustment to the temperature, T, (in K), at which Z is to be
determined is necessary in the pressure range 0 to 17.24 MPa, as
follows:
T = T + 1.94 ( P 2760 2.1 10

P )

10

Lecture

Modification of the Standing-Katz (S-K)


Chart Method
The S-K chart method for estimating the compressibility factor for
sweet natural gases was the only method that was in widespread use
until the advent of the computer. It seemed appropriate to develop a
modification for this method to make the chart applicable for sour
gases also. The method that was developed involves adjusting the
pseudo-critical properties of the gas mixture, so that the resulting
pseudo-reduced pressure and temperature can be used to look up the Z
factor on the S-K chart.

The adjustment is applied to the pseudo-critical pressure and


temperature of the gas mixture, rather than to the critical properties of
the individual components, as is the case in the modification of the R-K
equation method. In the modification of the S-K chart method, the
adjustment parameter, 3 , is calculated as follows:
3 = 66.667 ( A

0.9

1.6

) + 8.333 ( B

0.5

B ) , with units of C

where: A = mole fraction (H2S + CO2) in sour gas mixture


A chart has been developed for
3 , which is shown in
Fig. 23-8.

B = mole fraction H2S


The pseudo-critical pressure and temperature, which are calculated by
Kays molar average rules, are then adjusted as follows:
T pc = T pc 3

Ppc T pc
P pc = ------------------------------------------------T pc + B ( 1 B ) 3
where:

Tpc and Ppc are the pseudo-critical temperature and


pressure of the gas mixture, and T pc and P pc are the
adjusted pseudo-critical values.

The adjusted pseudo-critical temperature and pressure are then used


to determine the pseudo-reduced temperatures and pressures for the
conditions at which the Z factor is to be determined from the S-K chart.

10

Lecture

11

Application of the method should be limited to sour natural gases that


have methane as the major constituent of the hydrocarbon
components of the gas mixture. The method can be used for sour
natural gases containing up to 80 vol % total acid gas.

Example
What is the compressibility factor of the sour gas mixture of the
composition shown below at a pressure of 6895 kPa (abs) (1000 psia)
and 37.8 C (100 F)?
1. Calculate the pseudo-critical properties by the molar average
method:
Comp.*

Mole Fr.

Tc,K

Pc,kPa

P c, kPa

y i P ci

N2

0.0304

126.21

3.84

3398

103.3

CO 2

0.0287

304.11

8.73

7374

211.6

H2 S

0.2327

373.37

86.88

8963

2085.7

C1

0.5601

190.56

106.73

4599

2575.9

C2

0.0820

305.41

25.04

4880

400.2

C3

0.0345

369.77

12.76

4240

146.3

iC 4

0.0085

407.82

3.47

3640

30.9

nC 4

0.0110

425.10

4.68

3784

41.6

iC 5

0.0000

460.35

0.00

3381

0.0

nC 5

0.0071

469.65

3.33

3365

23.9

C6

0.0028

506.4

1.42

3030

8.5

C7

0.0022

539.2

1.19

2740

6.0

Totals

1.0000

258.07

5633.9

0L[WXUH5/5RELQVRQ-UDQG5+-DFRE\%HWWHU&RPSUHVVLELOLW\)DFWRUV
+\GURFDUERQ3URFHVVLQJ$SULOSS

11

12

Lecture

2. From Fig. 23-8 of the Data Book, obtain the pseudo-critical


temperature adjustment factor, 3 :
3 : for CO 2 = 2.87 % and H 2S = 23.27 %, 3 = 16.1 C

3. Calculate the adjusted pseudo-critical temperature, T pc , where


T pc = T pc 3 :
T pc = 258.07 16.1 = 241.97K

4. Calculate the adjusted pseudo-critical pressure, Ppc , where


P pc T pc
and B= mole fraction H2S
P pc = -------------------------------------------------T pc + B ( 1 B ) 3
= 5224.2 kPa (abs)
(5633.9 241.97 )
P pc = ---------------------------------------------------------------------------------------------(258.07 + 0.2327 ( 1 0.2327 ) 16.1 )
5. Calculate the pseudo-reduced temperature, T pr , and the pseudoreduced pressure, P pr , using the adjusted pseudo-critical values:
( 37.8 + 273.15 )
T
T pr = ---------- = --------------------------------------- = 1.29
241.97
T pc

6895
P
P pr = ---------- = ---------------- = 1.32
5224.2
Ppc

6. From Fig. 23-4 of the Data Book, at Ppr = 1.32 and T pr = 1.29 ,
Z = 0.775
*Experimental Z = 0.774.

12

Lecture

13

AGA # 8 (1992) Method

The method contained in the


1992 edition of AGA #8 is
highly accurate for sweet as
well as for sour natural gases.

The American Gas Association (AGA) has conducted research to


develop a method for accurately calculating the Z factor for pipeline
quality natural gas. In 1985, AGA published report AGA # 8, which
developed a highly accurate method for estimating the Z factor for
natural gas. However, this method limited the H2S content to about
1 vol %. Upon further research, AGA released the second edition of
AGA # 8 in 1992.

AGA # 8 (1992) presents a very complex calculation method, which can


only be done by computer. The list of the computer source program in
FORTRAN 77 is included in the AGA # 8 (1992) report, which can be
obtained from AGA. A diskette containing the program is also available
at a nominal additional cost.

Table 1.1 provides a comparison of experimental and calculated Z


factors for a sour gas mixture. The calculations include a comparison
with results obtained by HYSYS, using the Peng Robinson and the
Soave-Redlich-Kwong equations of state.

13

14

Lecture

TABLE 1.1
Comparison of Experimental* and Calculated Z Factors
Exp.

W-A

W-A

AGA
#8

HYSYS

HYSYS

Pressure
psia/kPa
(abs)

Temp.
F / C

S-K
Chart

R-K

(1992)

PR

SRK

258/1779

100/37.8

.962

.961

.961

.963

.955

.963

377/2599

100/37.8

.945

.943

.943

.946

.935

.947

547/3772

100/37.8

.921

.920

.919

.922

.907

.924

785/5413

100/37.8

.889

.887

.886

.889

.870

.892

1111/7660

100/37.8

.847

.847

.845

.846

.824

.853

1558/10742

100/37.8

.798

.801

.798

.796

.774

.810

* Mixture 14, R.L. Robinson Jr. and R. H. Jacoby, Better Compressibility Factors, Hydrocarbon
Processing, April 1965, pp. 141-145.
Composition (mole fr.): He 0.0, N 2 0.0077, CO 2 0.0144, H 2 S 0.1630, C 1 0.7948, C2 0.0153,
C 3 0.0048, C 4+ 0.0

Derivations of the Real Gas Law


On the basis of the Real Gas Law, PV = ZnRT, many useful formulas can
readily be derived that find application in natural gas engineering. One
of the most basic relationships is the relative volume of a certain
amount of gas at one set of conditions of pressure and temperature as
compared to another set:
P1 V1
P2 V 2
---------------- = ---------------Z1 T1
Z2 T 2
Other useful formulas that can be derived from the Real Gas Law are
the following:

14

Lecture

15

1. Volume of one kilomole of gas at Standard Conditions of P and T:


Molar volume = Z 1 n R T 1 P1 = 1 1 8.3145 288.15 101.325
= 23.64 m3/kmol
2. Actual volume when volume at Standard Conditions is known:
0.352 V 1 Z T
, m3
V 2 = --------------------------------------P

3. Standard volume of gas, when volume at P and T is known:


2.84 V P- , m3
V 1 = ------------------------ZT

4. Gas density at P and T:


0.120 P M
v = ------------------------------- , kg/m3
ZT
3.48
P G- , kg/m3
v = -------------------------ZT

5. Superficial gas velocity in pipes or vessels:


5.187 Q Z T
v = -------------------------------------- ,m/s
2
PD

15

16

Lecture

where: P = pressure, kPa (abs.)


T = absolute temperature, K
V = volume, m3
V1 = volume @ standard condition of 101.325 kPa and 288.15
K, Sm3
V2 = actual volume at P and T, m3
D = internal diameter, mm
Q = flow rate at standard conditions, Sm3/day
n = number of kilomoles
Z = compressibility factor for gas at P and T
3
8.3145 kPa m
R = ---------------------------------------kmol K
M = relative molecular mass of gas, kg
G = relative density = M / 28.9625

Problem 1-1
The Z factor for the Sales Gas in Table A of these Notes is 0.843 at 10C
and the relative density of the gas is 0.628. The composition for Sales
Gas from Table A is included here:

16

Lecture

17

TABLE A
Sales Gas Compositon
Component

Mole Percent

H2

0.01

He

0.00

N2

0.55

CO2

0.88

H2S

0.00

C1

89.30

C2

6.25

C3

2.35

iC4

0.21

nC4

0.32

iC5

0.05

nC5

0.08

C6

0.00

C7+

0.00

TOTAL

100.00

Determine the following:


a) The volume of gas at standard conditions stored in a pipeline 10 km
long and with an internal diameter of 260 mm, at a pressure of 6000 kPa
and a temperature of 10C.
b) The density of the gas in the pipeline, in kg/m3.
c) The velocity of the gas flowing through the line, in km/h, at a sales
6
gas rate of 3 10 Sm3/d (3 000 000 Sm3/d).

17

18

Lecture

Heating Value of Natural Gas


Throughout the world, natural gas is mostly burned to generate heat for
industrial, commercial and domestic applications. Other uses, such as
driving electric generators or automobiles, also make use of the heat
energy of natural gas. Thus it is very important for the consumer to
know what the energy content is of the natural gas that is being bought.

The heating value of natural gas has been defined in several ways, and it
is important to understand the differences between the various
definitions of heating value, namely:
gross heating value, dry,
gross heating value, wet,
net heating value, dry,
net heating value, wet.
Additionally, the terms "ideal gas" or "real gas" have to be used to
further classify the heating value, making it necessary to define these
terms.

Gross Heating Value


Gross heating value, MJ/m3, is the amount of energy transferred as
heat, upon the combustion of one standard cubic metre of gas in an
ideal combustion reaction, at standard pressure and temperature, with
all combustion products cooled to the standard temperature, and all
water formed during the combustion process being condensed. If the
gas does not contain any water vapour, the heating value is on a dry
basis. If the gas is fully saturated with water vapour at standard
conditions, the heating value is on a wet or saturated basis. The term
ideal assumes that the gas behaves as an ideal gas, and therefore the
compressibility factor is 1. Real gas has a compressibility factor less
than 1.

18

Lecture

19

The relationship between compressibility factor, Z, ideal gas and real


gas heating values (HV) is:
HV real = HVideal Z

Net Heating Value

Many years ago


instrumentation such as the
"calorimeter" were used for
actually determining the
heating value.

Net heating value, MJ/m3, is the amount of energy transferred as heat


in an ideal combustion reaction, as defined above, but with the water
formed in the combustion remaining in the vapour phase. The
difference between gross and net values is the Latent Heat of
Condensation of the water produced in the combustion process.

The heating value of natural gas can readily be calculated from the gas
analysis. The heating value can then be expressed in gross, net, dry,
wet, ideal, or real terms, as described above.

The gross heating values and respective net values for pure methane,
ethane and propane for an ideal gas at standard pressure 101.325 kPa
(abs) and a temperature of 15C, dry basis, are shown in the following
table:
C1

C2

C3

Gross

37.708 MJ/m3

66.065 MJ/m3

93.963 MJ/m3

Net

33.949 MJ/m3

60.429 MJ/m3

86.418 MJ/m3

19

20

Lecture

To obtain the heating value of a natural gas, it is necessary to determine


the mole fraction weighted heating value, using the heating value of
each component from the Data Book. When determining the heating
value of gas on a "wet" basis, the calculation procedure of GPA 2172
should be followed.
The Gas Processors Association (GPA) of the United States has published
several standards which are available at a nominal cost. A list of the
standards and various research reports is provided on pages 1-13 to 1-32
of the Data Book.

Problem 1-2
Determine the Gross Heating Value per Sm3 of the Sales Gas in Problem
1-1, in terms of ideal gas, dry basis.

20