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Pressure,Volume,Temperature(PVT)Behaviour

Pressure, Volume,

Temperature (PVT) Behaviour

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:

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.

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, 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.

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, 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

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).

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

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.

data on liquid volume per

kmol.

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

available in Section 25, page

25-7.

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 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

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. 23-2: Critical temperature

and pressure.

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

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

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.

of the Data Book is only valid

for sweet natural gas.

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.

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

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.

determination of a parameter, 2 , as follows:

2

2 = 15 ( A A ) + 4.167 ( B

0.5

B ) , with units of C

B = mole fraction H2S.

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:

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

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.

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

A chart has been developed for

3 , which is shown in

Fig. 23-8.

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:

pressure of the gas mixture, and T pc and P pc are the

adjusted pseudo-critical values.

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

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

temperature adjustment factor, 3 :

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

T pc = T pc 3 :

T pc = 258.07 16.1 = 241.97K

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

1992 edition of AGA #8 is

highly accurate for sweet as

well as for sour natural gases.

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.

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.

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

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

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

2.84 V P- , m3

V 1 = ------------------------ZT

0.120 P M

v = ------------------------------- , kg/m3

ZT

3.48

P G- , kg/m3

v = -------------------------ZT

5.187 Q Z T

v = -------------------------------------- ,m/s

2

PD

15

16

Lecture

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

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

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, 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

gas heating values (HV) is:

HV real = HVideal Z

instrumentation such as the

"calorimeter" were used for

actually determining the

heating value.

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

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

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