GPSA Cap 23

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GPSA Cap 23

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Physical Properties

This section contains charts, correlations, tables and proce- the property values are detailed footnotes and references for

dures for predicting physical properties of hydrocarbons and the entries in Fig. 23-2. After Fig. 23-2, this Section contains

other components of interest to the natural gas industry. Fig- procedures for estimating the Z-factor for gases and material

ure 23-1 contains the nomenclature used in this section. relating to hydrocarbon fluid densities, boiling points, ASTM

distillation, critical properties, acentric factors, vapor pres-

Figure 23-2 is a listing of the physical properties for a num- sures, viscosity, thermal conductivity, surface tension, and

ber of hydrocarbons and other selected compounds. Following gross heating value.

FIG. 23-1

Nomenclature

B = mole fraction of H2S in a sour gas stream, Eq 23-6 v = volume fraction

Bii = second virial coefficient for component i V = volumetric flow rate, real gas

id

Bij = second cross virial coefficient for components i and j V = volumetric flow rate, ideal gas

bi1/2 = summation factor for component i VABP = volumetric average boiling point, F

c = cost of gas W = mass, lbm

CABP = cubic average boiling point, F WARP = weight average boiling point, F

d = density, g/cc yi = mole fraction of component i from analysis on

gal = gallons dry basis, Eq 23-38

G = specific gravity or relative density (gas density) x = mole fraction in liquid phase

Gi = specific gravity (gas gravity) of ideal gas, MW/MWa yi(cor) = mole fraction of component i adjusted for

Giid = molecular weight ratio of component i in mixture water cont ent

Hvid = gross heating value per unit volume of ideal y = mole fraction in gas phase

gas, Btu/cu ft Z = Z-factor = PV/nRT

KW = Watson characterization factor, Fig. 23-12 Greek

k = thermal conductivity, Btu/[(hr ft2 F)/ft] = pseudo-critical temperature adjustment factor,

kA = thermal conductivity at one atmosphere, Eq 23-6

Btu/[(hr ft2 F)/ft] = MeABP/Tpc

lbm = pounds mass = density, lbm/ ft3

M = mass fraction = viscosity at operating temperature and

m = mass, lbm pressure, centi poise

MW = Molecular weight, lbm/lbmol A = viscosity at 14.7 psia (1 atm) and operating

MABP = molal average boiling point, F or R temperature, centipoise

MeABP = Mean average boiling point, F or R = factor defined by Eq 23-20

n = number of moles, (mass/MW) = surface tension, dynes/cm

p = price of real gas = acentric factor

pid = price of ideal gas = kinematic viscosity, centistokes

P = pressure, psia t = accounting period

Pc = pseudo-critical pressure adjusted for acid gas

composition, psia Subscripts r = reduced state

Pvp = vapor pressure at a reduced temperature of 0.7 a = air V = vapor

Pw = vapor pressure of water, 0.25636 psia at 60F b = boiling v = volume

R = gas constant, 10.73 (psia ft3)/(R lbmol) for c = critical w = water

all gases (Section 1 has R in other units) Superscripts

i = component i

S = specific gravity at 60/60F

L = liquid id = ideal gas

T = absolute temperature, R

m = mixture w = water

t = ASTM D-86 distillation temperature for a

pc = pseudo-critical = reference state

volumetric fraction, F or R, Eq 23-11

Tc = pseudo-critical temperature adjusted for acid

gas composition, R

23-1

FIG. 23-2

Physical Constants

23-2

FIG. 23-2 (Contd)

Physical Constants

23-3

FIG. 23-2 (Contd)

Physical Constants

23-4

FIG. 23-2 (Contd)

Notes and References for the Table of Physical Constants

23-5

FIG. 23-2 (Contd)

Notes and References for the Table of Physical Constants

23-6

FIG. 23-2 (Contd)

Notes and References for the Table of Physical Constants

23-7

FIG. 23-2 (Contd)

Notes for the Table of Physical Constants

a The molar mass for air is based upon the following com- g At saturation pressure

position expressed in mole fraction: N2(g), 0.7812; O2(g), h Refractive index of the gas

0.2096; Ar(g), 0.0092.

i Estimated value

b Calculated with the evaluated vapor-pressure equation

in the TRC Table Database (Reference 2) j Densities of the liquid at the normal boiling tempera-

c NIST REFPROP Database: Reference Fluid Thermody- ture

namic and Transport Properties (Reference 3) k Estimated 2nd virial coefficients with a corresponding-

d Sublimation point states correlation

e Estimated for the hypothetical liquid state l Extreme values of those reported in reference 12

f Temperature is above the critical temperature

A Molar mass (molecular weight) is based upon the follow- molar mass of air given in the table. The specific volume

ing atomic weights: C =12.0107; H = 1.00794; O = of an ideal gas is calculated from the ideal-gas equation.

15.9994; N = 14.00674; S = 32.066; Cl = 35.4527; J The heat capacity values for the liquid phase are not

He = 4.002602; and Ar = 39.948. rigorously Cp, but rather are along the saturation line

B Boiling point: the temperature corresponding to equi- Csat defined by: Csat = Cp - T(V/T)p(p/T)s. For liquids

librium between the liquid and vapor phases at 101.325 far from the critical temperature, Csat and Cp are nearly

kPa (or 14.696 psia). equal.

C Freezing point: the temperature corresponding to equi- K The heating value is the negative of the enthalpy of com-

librium between the crystal phase and the air-saturated bustion at 15 oC (or 60 oF) and 101.325 kPa (or 14.696

liquid at 101.325 kPa (or 14.696 psia). psia) in an ideal reaction (one where all of the gasses

D The refractive index values represent those determined are ideal). For an arbitrary organic compound, the com-

with light of wavelength corresponding to the sodium bustion reaction is:

D-line (589.26 nm).

1 CnHmOhSjNk(s, l, or g) + (n + m/4 - h/2 + j) O2(g) n

E The specific gravities of water used in the relative den- CO2(g) + m/2 H2O(g or l) + k/2 N2(g) + j SO2(g),

sity calculations were 8.3372 lb/gal at 60 oF and 999.103

kg.m-3 at 15 oC. These values are included in the FPS 1 where s, l, and g denote the phase of compound. For

and SI tables. "gross" heating values, the water formed is liquid; for

"net" heating values, the water formed is ideal gas. Val-

F The temperature coefficient of densityis related to the

ues reported are on a dry basis. To account for water in

expansion coefficient by: (r/)p/r = -(V/T)p/V in units

the heating value, see GPA 2172. The phase of the ma-

of 1/T. terial combusted is indicated in the column headings.

G Pitzer acentric factor: w = -log10(p/pc)-1, where p is at T

= 0.7 Tc. L The heat of vaporization is the enthalpy of the saturated

vapor minus the enthalpy of the saturated liquid at the

H The summation factor is (-B/RT)0.5 where B is the second boiling temperature.

virial coefficient evaluated at temperature T and R is

the gas constant. T = 15 oC for SI units and T = 60 oF for M Air required for the combustion of ideal gas for com-

FPS units. pounds of formula CnHmOhSjNk is: V(air)/V(gas) = (n +

m/4 -h/2 +j) / 0.2096.

I The density of an ideal gas relative to air is calculated

by dividing the molar mass of the gas by the average

- Reported units are based upon the following units (SI) - pressure: 6.894757 kPa = 1 pound per square inch abso-

with their equivalent corresponding FPS units: lute, psia

- mass: 453.59237 g = 1 Pound(avdp), lbm - energy: 1055.056 J = 1 British thermal unit, Btu

- length: 0.3048 meters = 1 foot, ft - Gas constant R = 8.314472 J.K-1.mol-1 or 10.7316 psia

ft3/(lbmol.oR)

- temperature: 1.8(t / oC) = (t / oF) - 32; 0 oC = 273.15 K.

All temperatures are defined by the International Tem- - 1 gal = 231 in3

perature Scales of 1990 (ITS-90). - 1 atm = 14.69595 psia = 760 torr = 101.325 kPa

- volume: 0.02831685 m3 = 1 cubic foot, ft3

23-8

FIG. 23-2 (Contd)

References for the Table of Physical Constants

1. Coursey, J. S. and Dragoset, R. A. (2001). Atomic 6. Henderson, C.; Lewis, D. G.; Prichard, P. C.; Staveley, L.

Weights and Isotopic Compositions (version 2.2.1), [On- A. K.; Fonseca, I. M. A.; Lobo, L. Q. J. Chem. Ther-

line]. Available: http://physics.nist.gov/Comp [2002, modyn. 1986, 18, 1077.

February 13]. National Institute of Standards and

7. Francis, A. W. J. Chem. Eng. Data, 1960, 5, 534.

Technology, Gaithersburg, MD. Originally published as

R.D. Vocke, Jr., Atomic Weights of the Elements 1997, 8. Wilhoit, R. C.; Marsh, K. N.; Hong, X.; Gadalla, N.;

Pure Appl. Chem., 71(8), 1593 (1999) Frenkel, M.; "Thermodynamic Properties of Organic

2. X. Yan, Q. Dong, X. Hong, and M. Frenkel, NIST/TRC Compounds and their Mixtures; Densities of Aliphatic

Table Database, NIST Standard Reference Database Hydrocarbons: Alkanes," Group IV, Volume 8, Sub-

85, Version 2002. NIST Standard Reference Data Pro- volume B: Landolt-Brnstein, 1996.

gram, Gaithersburg, MD. 9. Dymond, J. H.; Marsh, K. N.; Wilhoit, R. C.; Wong, K. C.;

3. E. W. Lemmon and M. O. McLinden, Reference Fluid "The Virial Coefficients of Pure Gases and Mixtures;

and Thermodynamic and Transport Properties (RE- Virial Coefficients of Pure Gases," Group IV, Volume 21,

FPROP), NIST Standard Reference Database 23, Ver- Subvolume A: Landolt-Brnstein, 2002. In Press.

sion 7, Beta Version, February 5, 2002. NIST Standard

10. Frenkel, M.; Kabo, G. J.; Marsh, K. N.; Roganov, G. N.;

Reference Data Program, Gaithersburg, MD.

Wilhoit, R. C.; "Thermodynamics of Organic Com-

4. Ambrose, D.; Hall, D. J.; Lee, D. A.; Lewis, G. B. J. Chem. pounds in the Gas State, Vol. I & II," TRC Data Series,

Thermodyn., 1978, 11, 1089. 1994.

5. A.H. Harvey, A.P. Peskin, and S.A. Klein, NIST/ASME 11. Zabransky, M.; Ruzicka, V.; Majer, V.; Domalski, E. S.;

Steam Properties, NIST Standard Reference Database "Heat Capacity of Liquids," J. Phys. Chem. Ref. Data,

10, Version 2.2, NIST Standard Reference Data Pro- Monograph 6, ACS/AIP, 1996.

gram, Gaithersburg, MD (2000);

12. En.gineering Sciences Data Unit, "Fire Hazard Prop-

and erties: Flash Points, Flammability Limits and Autoig-

nition Temperatures," ESDU 82030, September 1983.

W. Wagner and A. Pruss, "The IAPWS Formulation 13. Obert, Edward F.; "Internal Combustion Engines and

1995 for the Thermodynamic Properties of Ordinary Air Pollution," Harper & Row: NewYork, 1973.

Water Substance for General and Scientific Use," J.

Phys. Chem. Ref. Data, in press (2002).

Physical properties for compounds of interest for the natural other properties propagate through the figure). The reason

gas industry appear in GPA Standard 2145, Table of Physical they are fictitious is that 60 or 100 F is above the critical

Properties for Hyrdocarbons and Other Compounds of Inter- temperatures of these compounds and the liquid state does not

est to the Natural Gas Industry. exist under such conditions. In no instance is it necessary to

use these entries from a technical perspective, but they have

Figure 23-2 contains several fictitious entries: the vapor worked their ways into contractual agreements. Rather than

pressures of methane, ethane and ethene at 100 F, the refrac- cause opening of contracts, the GPSA includes these unphysi-

tive indicies of methane and ethane at 60 F, and the liquid cal values in the figure, but users should not rely upon calcu-

densities of methane at 60F (their use in calculating a few lations using these values outside of contractual agreements

Component x MW xMW M lbm lbm/gal gal v

Carbon Dioxide 0.0011 44.010 0.0484 0.0011 914 6.8199 134 0.0007

Methane 0.0214 16.043 0.3433 0.0079 6,480 2.5 2,592 0.0127

Ethane 0.3897 30.070 11.7183 0.2680 221,192 2.9696 74,485 0.3643

Propane 0.3648 44.097 16.0866 0.3679 303,647 4.2268 71,839 0.3514

Iso-butane 0.0294 58.123 1.7088 0.0391 32,255 4.6927 6,873 0.0336

Normal-butane 0.0877 58.123 5.0974 0.1166 96,217 4.8691 19,761 0.0967

Iso-pentane 0.0171 72.150 1.2338 0.0282 23,288 5.2058 4,474 0.0219

Normal-pentane 0.0182 72.150 1.3131 0.0300 24,786 5.2614 4,711 0.0230

Hexanes + 0.0706 87.436 6.1730 0.1412 116,520 5.5910 19,580 0.0958

TOTAL 1.0000 43.7227 1.0000 825,300 204,449 1.0000

23-9

and defined specifications. An example would be calculation The equation used to calculate gas density is:

of the liquid volume fractions for the components of a liquid

(MW) P

mixture. The table above comes from GPA Standard 8173: = Eq 23-2

10.73 RT

The liquid volume fraction for methane is fictitious, but ex-

perience has shown that using this calculation procedure pro- The value for R is 10.73 when pressure is psia, volume is

vides a reliable specification for the maximum liquid volume cubic feet, quantity of gas is pound moles, and temperature is

fraction for methane. R. Values of R for other combinations of units appear in Sec-

tion 1.

The theorem of corresponding states that fluids that have

COMPUTER PREDICTION METHODS the same value of reduced temperature and reduced pressure

have the same reduced volume. The reduced property is the

Computer methods that predict physical and thermody-

property divided by the value of the property at the critical

namic properties for light hydrocarbons and natural gas con-

point. Thus, according to the theorem, different fluids that

stituents are widely available. People involved in the design

have the same reduced temperature and reduced pressure

and operation of natural gas processing facilities use them

have the same Z-factor.

routinely. This section emphasizes hand calculation methods

that provide reliable estimate for thermophysical properties. Reduced Temperature, Tr = T/Tc Eq 23-3

These methods provide quick, order-of-magnitude checks to

Reduced Pressure, Pr = P/Pc Eq 23-4

evaluate more detailed procedures or when a computer is not

available. For gas mixtures, the reduced conditions can be determined

using pseudo-critical values instead of the true critical values:

Some computer results appear in the section. Using equa-

tions of state to predict properties is convenient and easy, but pseudoreduced Temperature, Tr = T/ (yiTci) = T/Tpc Eq 23-3a

such methods do not apply equally well for all properties. Ac- i

curate and reliable values result for gas phase densities, vol- pseudoreduced Pressure, Pr = P/ (yiPci) = P/Ppc Eq 23-4a

umes and Z-factors, while liquid volumes and densities are i

less accurate but still as reliable as predictions using hand-

calculation methods. Equations of state are not suitable to Any units of temperature or pressure are acceptable pro-

predict thermal conductivities, viscosities and surface ten- vided that the same absolute units are used for T as for Tc (Tpc)

sions. Computer programs cited in this section are repre- and for P as for Pc (Ppc). The "average molecular weight" for a

sentative of those widely available for prediction of physical gas mixture is

and thermodynamic properties. Inclusion of commercial prod-

ucts in the recommendations of this section does not constitute

MWavg = yiMWi Eq 23-5

i

GPA and/or GPSA endorsement of the program(s). An accu-

rate, reliable equation of state is always the most convenient Figure 23-3 illustrates calculation of pseudo-critical proper-

method for obtaining engineering accuracy gas phase proper- ties and MWavg for a typical natural gas. Estimation tech-

ties. Unfortunately, widespread availability and ease of use niques to calculate the critical temperature and pressure for

are not suitable criteria for choosing an equation of state pro- hexanes and heavier or heptanes and heavier fractions using

gram. molecular weight and specific gravity or average boiling point

and relative density are presented in this section.

Attempts to prepare a generalized plot suitable for applica-

Z-FACTOR FOR GASES tion to the low molecular weight hydrocarbons, including

methane, ethane, and propane, indicate that an error fre-

Pure Gases quently in excess of 2 to 3% is unavoidable because they devi-

The ideal gas equation of state is a convenient and often ate from the theorem of corresponding states. Figure 23-4,

satisfactory tool when dealing with gases at pressures that do prepared using pure component and gas mixture data, can

not exceed one atmosphere. The errors associated with this estimate Z (2-3% error) for pure hydrocarbon gases. Use re-

equation are about 2-3% in this pressure range. However, the duced temperature and pressure instead of pseudo-reduced

errors can escalate to hundreds of per cents at higher pres- values for pure components. At low pressures, the different

sures. compounds more nearly conform to corresponding states. The

Z-factor is approximately 1.0 at pressures below 1 atmosphere.

Section 25 presents many equations of state that represent Errors generally are 2-3% for pressures 300 psia if the gas is

the pressure-volume-temperature relationships for gases. 50 F or more above its saturation temperature at the pressure

Use of these equations for engineering calculations is compli- of concern.

cated and requires a computer or a programmable calculator

to complete the calculations in a reasonable amount of time. It is possible to determine gas volumes, densities and Z-fac-

A generalized, corresponding states plot of Z-factors is reason- tors for pure hydrocarbon and non-hydrocarbon vapors using

ably convenient and sufficiently accurate for normal engineer- P-H diagrams like those in Section 24, Thermodynamic Prop-

ing requirements. The Z-factor provides the ratio of the real erties. Interpolation between specific volume curves on a P-H

gas volume to that of the ideal gas. diagram does not yield results of high accuracy. An equation

of state provides more accurate pure component PVT proper-

PV = ZnRT = ZmRT MW Eq 23-1 ties, particularly if that equation has been fit to volumetric

The Z-factor is a dimensionless parameter, independent of data for the specific component. Tabulations of properties ob-

the quantity of gas, determined by the characteristics of the tained in this way appear in the literature.12

gas, the temperature, and the pressure. Knowing Z, calcula-

tion of PVT relationships are as easy at high pressure as at

low pressure.

23-10

Example 23-1 Pure component properties vapors that have compositions atypical of natural gases mix-

Using Fig. 24-27, the P- H diagram for propane, calculate tures or for mixtures containing significant amounts of water

the density of propane vapor at 200F and 100 psia. and/or acid gases, and for all mixtures as saturated fluids,

other methods should be employed.

Solution Steps

On the P-H diagram at the intersection of the T = 200F, P Figure 23-4 provides reasonably accurate gas Z-factors for

= 100 psia lines read v = 1.5 ft3/lbm. Then: = 1/1.5 = 0.667 natural gases with high nitrogen content, up to 50% (or even

lbm ft-3 higher) when using the molar average pseudo-criticals from

Eqs 23-3a and 23-4a. The same approach applies to gas con-

Using the EZ*THERMO90 version of the SRK91 equation of densate fluids containing appreciable amounts of heptanes

state, is 0.662 lb/ft3, from which v = (1/0.662) = 1.51 ft3/lbm. and heavier components. Critical temperatures and pres-

sures for heptane and heavier fractions can be estimated from

For propane at 200F and 100 psia using data from Fig. 24- molecular weight and relative density, or average boiling point

27. and relative density, using correlations presented in this sec-

tion.

MW P (44.10) (100)

Z = = = 0.936 Figs. 23-5, 23-6 and 23-7 provide Z-factors for low molecular

R T (10.73) (458.67 + 200) (0.667)

weight natural gases. These figures cover a wide range of mo-

The SRK calculation gives = 0.662 lb/ft3, and Z = 0.941. lecular weights (15.95 to 26.10), temperatures (-100 to l000 F)

and pressures (up to 5,000 psia). For gases with molecular

Gas Mixtures weights between those shown in Figs. 23-5 through 23-7, lin-

GPA Standard 2172, "Calculation of Gross H Value, Relative ear interpolation between adjacent charts is sufficient to com-

Density and Compressibility Factor for N Gas Mixtures from pute the Z-factors.

Compositional Analysis" contains additional information re-

garding the calculation of Z-factors for mixtures at pressures In general, Z-factors for gases with less than 5% noncon-

below 150 psia. densable non-hydrocarbons, such as nitrogen, carbon dioxide,

and hydrogen sulfide, result with less than 5% error. When the

Minor Amounts of Non-hydrocarbons Fig 23-41 molecular weight is above 20 and the Z-factor is below 0.6,

shows Z-factors for typical sweet natural gases. Using Z-fac- errors as large as 10% may occur.

tors from Fig. 23-4 should yield mixture volumes (densities)

within 2% to 3% of the true values for reduced temperatures Effect of Acid Gas Content Natural gases containing

from slightly greater than 1.0 to the limits of the chart for both H2S and/or CO2 exhibit different Z-factor behavior than do

temperature and pressure. The chart has been prepared from sweet gases. Wichert and Aziz3 present a calculation proce-

data for binary mixtures of methane with ethane, propane and dure to account for these differences. Their method uses the

butane and data for natural gas mixtures. All mixtures have standard gas Z-factor chart (Fig. 23-3) and provides accurate

average molecular weights less than 40, and all gases contain sour gas Z-factors that contain as much as 85% total acid gas.

less than 10% nitrogen and less than 2% combined hydrogen Wichert and Aziz define a "critical temperature adjustment

sulfide and carbon dioxide. Fig. 23-4 applies for temperatures factor," , that is a function of the concentrations of CO2 and

20 F or more above saturation up to pressures of 10,000 psia. H2S in the sour gas. This correction factor adjusts the pseudo-

critical temperature and pressure of the sour gas according to

Appreciable Amount of Non-Hydrocarbons Figure the equations:

23-4 does not apply for gases or vapors with more than 2% H2S

and/or CO2 or more than 20% nitrogen. Use other methods for Tc = Tc Eq 23-6

FIG. 23-3

Calculation of Pseudo-critical Temperature and Pressure for a Natural Gas Mixture

Mole Pseudocritical Pseudocritical

Critical Critical Molecular Molecular

Component Fraction, Temperature, Pressure,

Temperature, Pressure, Weight, Weight,

yi Tpc, R Ppc, psia

Tci, R Pci, psia MW yi MW

CH4 0.8319 343.0 285.3 666.4 554.4 16.043 13.346

C2H6 0.0848 549.6 46.6 706.5 59.9 30.070 2.550

C3H8 0.0437 665.7 29.1 616.0 26.9 44.097 1.927

iC4H10 0.0076 734.1 5.58 527.9 4.01 58.123 0.442

nC4H10 0.0168 765.3 12.86 550.6 9.25 58.123 0.976

iC5H12 0.0057 828.8 4.72 490.4 2.80 72.150 0.411

nC5H12 0.0032 845.5 2.71 488.6 1.56 72.150 0.231

nC6H14 0.0063 913.3 5.75 436.9 2.75 86.177 0.543

Tpc = 392.62 Ppc = 661.57 MWm = 20.426

G = 20.426/28.9625 = 0.705

23-11

FIG. 23-4

Compressibility Factors for Natural Gas1

23-12

FIG. 23-5

Compressibility of Low-Molecular-Weight Natural Gases11

23-13

FIG. 23-6

Compressibility of Low-Molecular-Weight Natural Gases11

23-14

FIG. 23-7

Compressibility of Low-Molecular-Weight Natural Gases11

23-15

Pc Tc the pseudo-critical temperature adjustment factor from Fig.

Pc = Eq 23-7

Tc + B (1 B) 23-8 and use it to adjust the values of critical temperature and

pressure. The reduced temperature and reduced pressure are

calculated using the adjusted values. The Z-factor is then

Figure 23-8 presents the pseudo-critical temperature ad-

available from Fig. 23-4.

justment factor. To use the factor, calculate the pseudo-critical

temperature and pressure using the procedure outlined ear- Example 23-2 A sour natural gas has the composition shown

lier. Include the H2S and CO2 in this calculation as well as in the following table. Determine the Z-factor for the gas at

hydrocarbon and other non-hydrocarbon constituents. Read 100F and 1000 psia.

FIG. 23-8

Pseudocritical Temperature Adjustment Factor3, , F

23-16

Solution Steps using apparent densities for the gaseous components ethane

The first step is to calculate the pseudo-critical temperature and methane. Then they corrected the resulting pseudo-den-

and pseudo-critical pressure for the sour gas. Read the sity at 60F and 14.7 psia for pressure using a hydrocarbon

pseudo-critical temperature adjustment factor from Fig. 23-8 liquid compressibility chart and for temperature using a ther-

as 29.8F. The adjusted pseudo-critical temperature is: mal expansion chart (Fig. 23-17). Experience with crude oils

and rich absorber oils showed this correlation could predict

densities within 1 to 4% of experimental data.

Tc = 433.9 29.8 = 404.1 R The original correlation did not have a procedure for han-

The adjusted pseudo-critical pressure is: dling significant amounts of non-hydrocarbons and had a

fairly narrow applicable temperature range of 60F to 240F.

(826.9) (404.1) The following procedures and charts are generally applicable

Pc = = 761.7 psia

433.9 + 0.2 (1 0.2) (29.8) to liquids containing components heavier than pentanes (gas

saturated or subcooled) at pressures up to 10,000 psia and

The pseudo-reduced temperature and pseudo-reduced temperatures from 100F to 600F. This procedure can han-

pressure are: dle significant amounts of non-hydrocarbons (up to 20% N2,

80% CO2, and 30% H2S).

100 + 459.67

Tr = = 1.385 1. Set up a calculation table as shown in the example in Fig.

404.1

23-16.

1000 2. Calculate the density of propane and heavier (C3+) or, if

Pr = = 1.313

761.7 H2S is present, of H2S and heavier (H2S+) components,

assuming additive volumes.

Z = 0.831 (Fig. 23-4)

Densityof CO2 and (N2S +)

(The EZ*THERMO90 version of the SRK gives Z = 0.838.)

Weight C3 + (or H2S +) components

= Eq 23-8

HYDROCARBON FLUID DENSITIES Vol C3 + (o r H2S +) components

3. Determine the weight percent of (N2 + C2) in the (N2 +

Fig. 23-9 presents saturated fluid densities (liquid and va- C2+) fraction.

por) for hydrocarbons and liquid densities for some mixtures.

Fig. 23-10 is a plot of relative density as a function of tempera- 100 [Wt (N2 + C2)]

Wt % (N2 + C2) = Eq 23-9

ture for petroleum fractions. Wt (N2 + C2 +)

Figure 23-11 contains subcooled liquid hydrocarbon densi- 4. Use Fig. 23-14 to determine the pseudo-density of the (N2

ties from 50 F to +140 F. Corrections to liquid hydrocarbon + C2+) fraction. Enter with the C3+ (or H2S plus) density

densities caused by high pressure appear in Fig. 23-15. from Step 2 in the upper left of the chart and go horizon-

tally to the line (interpolate if necessary) representing

Figure 23-12 presents specific gravities for petroleum frac-

the weight % (N2 + C2) , then look up and read the

tions with temperature ranging from 0 F to l000 F and with

pseudo-density of the (N2 + C2+ along the top of the chart.

pressures from atmospheric to 1500 psia. The petroleum frac-

tion is identified within the center grid by two of three char- At temperatures below 20F, ethane can be included in

acteristics API gravity at 60 F, the Watson characterization Step 2 and only N2 used in Steps 3 and 4.

factor, KW, or the mean average boiling point. Fig. 23-18 con- 5. If CO2 is not present, go to Step 6. If it is present, then

tains the mean average boiling point, the API gravity and an account for it on an additive volume basis:

ASTM D-86 distillation of the petroleum fraction. The char-

acterization factor, KW, is defined in the inset example that Densityof CO2 and (N2 + C2 +)

illustrates use of Fig. 23-12.

Wt CO2 + Wt (N2 + C2 +)

Fig. 23-13 contains the specific gravity of paraffinic hydro- = Eq 23-10

Vol CO2 + Vol (N2 + C2 +)

carbons at their boiling points or bubble points. The no-

mograph applies to mixtures as well as to single components. where

Alignment points for paraffinic mixtures and pure compo- Wt (N2 + C2 +)

nents vary according to molecular weight. Vol (N2 + C2 +) =

Density (N2 + C2 +)

Fig. 23-13 generally predicts specific gravities within 3% of

6. Calculate the weight percent methane Wt methane

measured values for paraffinic mixtures. However, the accu-

racy is somewhat less for mixtures having: 100 (Wt methane)

Wt % methane = Eq 23-11

Reduced temperatures above 0.9. total Wt

Molecular weights less than 30 (low temperature region) 7. Enter the top of Fig. 23-14 with the pseudo-density from

and where methane is a significant part of the liquid. Step 4 or 5 as appropriate, and drop vertically to the line

Density of Saturated and Subcooled Liquid Mixtures (interpolation may be required) representing the weight

Standing and Katz1 proposed a versatile, manual proce- percent methane. Read the pseudo-density of the mix-

dure to calculate the density of gas-saturated and subcooled ture (60F and 14.7 psia) on the right side of the chart.

hydrocarbon liquid mixtures. The basic method proposed uses 8. Correct the pseudo-density to the actual pressure using

the additive volume approach for propane and heavier compo- Fig. 23-15. Add the correction to the pseudo-density

nents at standard conditions, then corrected this ideal volume from Step 7.

23-17

FIG. 23-9

Hydrocarbon Fluid Densities2, 3, 19

23-18

FIG. 23-10

Approximate Specific Gravity of Petroleum Fractions

23-19

FIG. 23-11

Effect of Temperature on Hydrocarbon Liquid Densities19

23-20

FIG. 23-12

Specific Gravity of Petroleum Fractions

23-21

FIG. 23-13

Specific Gravity of Paraffinic Hydrocarbon Mixtures

23-22

FIG. 23-14

Pseudo Liquid Density of Systems Containing Methane and Ethane

23-23

FIG. 23-15 9. Correct the density at 60F and pressure to the actual

Density Correction for Compressibility of temperature using Fig. 23-17. Add the correction to the

Hydrocarbon Liquids density from Step 8.

This procedure is not valid in the critical region. Mixtures

at temperatures greater than 150 F that contain more than

60 mol% methane or more than 80 mol% CO2 are problem

areas. Outside the near-critical region, calculated densities

usually are within 5% of experimental data35 and errors are

rarely greater than 8%. The best accuracy occurs for mixtures

containing mostly C5+ with relatively small amounts of dis-

solved gaseous components (errors are usually less than 3%).

Note that densities of C2+, C3+, CO2+, or C4+ mixtures can be

calculated by this procedure at various temperatures and

pressures, and that the gaseous components need not be pre-

sent.

Example 23-3 Fig. 23-16 illustrates the procedure outlined

above.

Wt of C3 + 44.836 lbm

Density of C3 + = =

Vol o f C3 + 1.0128 ft3

= 44.275 lbm/ft3

100 (0.567)

Wt % C2 in C2 + = = 1.25%

0.567 + 44.836

45.403 + 17.485

Density of CO2 + = = 45.75 lbm/ft3

(45.403/44.0) + 0.3427

Wt% of CH4 in Total = 100(3.352)/66.241 = 5.1%

Pseudo-density of mixture at 60F and 14.7 psia from

Fig. 23-14 = 42.9 1bm/ft3

Pressure correction to 1760 psia from Fig. 23-15 = +0.7

Density at 60F and 1760 psia = 42.9 + 0.7 = 43.6 lb/ft3

Temperature correction to 120 F from Fig. 23-17 = -1.8

Density at 120 F and 1760 psia = 43.6- 1.8 = 41.8 lb/ft3

FIG. 23-16

Calculation of Liquid Density of a Mixture at 120F and 1760 psia

Mole Molecular Density (60F),

Component Weight, lb Volume, cu ft

Fraction Weight lb/cu ft

Methane 0.20896 16.043 3.352

Carbon Dioxide 0.39730 44.010 17.485 51.016 0.3427

Ethane 0.01886 30.070 0.567

Propane 0.02387 44.097 1.053 31.619 0.0333

n-Butane 0.03586 58.123 2.084 36.423 0.0572

n-Pentane 0.02447 72.150 1.766 39.360 0.0449

n-Hexane 0.01844 86.177 1.589 41.400 0.0384

n-Heptane 0.02983 100.204 2.989 42.920 0.0696

n-Octane 0.02995 114.231 3.421 44.090 0.0776

n-Decane 0.18208 142.285 25.907 45.790 0.5658

n-Tetradecane 0.03038 198.394 6.027 47.815 0.1260

23-24

FIG. 23-17

Density Correction for Thermal Expansion of Hydrocarbon Liquids

250

200

600

550

Density at 60 F minus density at temperature, lb per cu ft

180 500

450

160

400

350

140

300

120 275

250

100 225

200

180

160

140

80 120

100

80

60 F

60

40

40 20

0

-20

20 -40

-60

0 -80

-100

-20

-40

Density at 60 F, lb per cu ft

23-25

Density from EZ*THERMO version of SRK using Example 23-4 Determine the mean average boiling point

Costald92 = 41.815 lb/ft3. (MeABP) and the molecular weight for a 56.8 API petroleum

fraction with the following ASTM distillation data.

Experimental density35 at 120F and 1760

psia = 41.2 lb/ft3 % Over Temperature, F

IBP 100

Error = (41.8 - 41.2)/41.2 = 0.015, or 1.5%

5 130

10 153

BOILING POINTS, CRITICAL 20 191

PROPERTIES, ACENTRIC FACTOR, 30 217

VAPOR PRESSURE 40 244

50 280

Boiling Points 60 319

Fig. 23-18 shows the interconversion between ASTM D-86 70 384

distillation 10% to 90% slope and the different boiling points 80 464

used to characterize fractions of crude oil to determine the 90 592

properties; VARP, WARP, CARP, MeARP, and MABP. On the

basis of ASTM D-86 distillation data, the volumetric average EP 640

boiling (VARP) point is:

IBP = initialboiling point EP = end po int

VARP = (t10 + t30 + t50 + t70 + t90)/5 Eq 23-12

where the subscripts 10, 30, 50, 70, and 90 refer to the volume Slope = (592 153)/80 = 5.49

percent recovered during the distillation. The 10% to 90%

slope used as the abscissa in Fig. 23-18 is: VABP = (153 + 217 + 280 + 384 + 592)/5 = 325F

slope = (t90- t10)/(90 -10) Eq 23-13 Refer to Fig. 23-18. Read down from a slope of 5.49 to the

interpolated curve to 325 F in the set drawn with dashed lines

To use the graph, locate the curve for the distillation VARP in (MeABP). Read a correction value of 54 on the ordinate.

the appropriate set for the type of boiling point desired. For Then

the known 10-90% slope, read a correction for the VABP from

the selected VABP curve. MeABP = 325 54 = 271F

FIG. 23-18

Characterizing Boiling Points of Petroleum Fractions (From API Technical Data Book)

23-26

The significance of the various average boiling points, inter- Acentric Factor

conversion of D-86 and D-1160 A8TM distillations, and the

calculation of true-boiling point and atmospheric flash curves The acentric factor, , is often a third parameter in corre-

from A8TM distillation data are in Chapters 3 and 4 of the API sponding states correlations. Figure 23-2 tabulates it for pure

Technical Data Book.36 hydrocarbons. The acentric factor is a function of Pvp, Pc, and

Tc. It is arbitrarily defined as

Molecular weight can be calculated from Eq 23-14 using Me-

ABP in R and S (specific gravity at 60F): = -log(Pvp/Pc)Tr=0.7-1.0 Eq 23-17

MW = 204.38 (T0.118)(S1.88) e(0.00218T - 3.075 S) Eq 23-14 This definition requires knowledge of the critical (pseudo-

critical) temperature, vapor pressure, and critical (pseudo-

This relationship is valid in the molecular weight range of critical) pressure.

70 to 720; the MeABP range of 97 to 1040 F; and the API range

of 14 to 93. The average error is about 7%. Eq. 23-14 works For a hydrocarbon mixture of known composition that con-

best for molecular weights above 115; it tends to over-predict tains similar components, a reasonably good estimate for the

below this value. acentric factor is the molar average of the individual pure com-

ponent acentric factors:

Example 23-5 Calculation of molecular weight.

From Example 23-4: = yi i Eq 23-18

i

S = 0.7515 for 56.8 API

If the vapor pressure is not known, can be estimated38 for

MeABP = 271 + 460 = 731R pure hydrocarbons or for fractions with boiling point ranges of

50F or less using:

Using Eq 23-14,

3 log Pc log 14.7

MW = 204.38(731)0.118 (0.7515)1.88 e[(0.00218)(731) (3.075)(0.7515)] = 1.0 Eq 23-19

7 (Tc Tb) 1

= 127.0

Example 23-7 Acentric factor.

Critical Properties

A narrow-boiling petroleum fraction has a VABP of 418F,

Critical properties are of interest because they are used to an ASTM slope of 0.75 and an API gravity of 41. Estimate its

find reduced conditions of temperature and pressure as re- acentric factor. To use Eq 23-19 we need the average boiling

quired for corresponding states correlations. Pseudo-critical point (MeABP); the pseudo-critical temperature (a function of

properties are used in many corresponding states correlations MABP); and the pseudo-critical pressure (a function of Me-

for mixtures. ABP).

The following equations taken from the API Technical Data From Fig. 23-18, the correction to VABP for mean average

Book36a,b estimate pseudo-critical temperature and pressure is 3F; the correction for MABP is 5F. Note that for narrow-

for petroleum fractions (pseudo, or undefined components): boiling fractions, all boiling points approach the volumetric

Ppc = 3.12281(109) T-2.3125 S 2.3201 Eq 23-15 average. Then, MeABP = 415F and MABP is 413F.

Tpc = 24.2787 T0.58848 S0.3596 Eq 23-16 From Eq. 23-15, the pseudo-critical pressure is:

These equations are in terms of T = MeABP (R) and specific T = 415 + 460 = 875 R

gravity, S, at 60 F. Both of these correlations are valid over

the range of 80 to 690 molecular weight; 70 to 295F normal S for 41 API = 141.5/(131.5 + 41) = 0.871

boiling point; and 6.6 to 95 API. Ppc = 3.12281(109) (875)-2.3125(0.871)2.3201 = 356 psia

Example 23-6 Pseudo-critical temperature and pressure.

From Eq 23-16, the pseudo-critical temperature is:

Take the previous mixture (from Example 23-4) with:

Tpc = 24.2787(875)0.58848(0.871)0.3596 = 1244 R

VABP = 325 F 3 log (356) log (14.7)

= 1.0 = 0.407

MeABP = 271F 7 (1244/875) 1.0

API = 56.8

MW = 127 (Ex. 23-5) Vapor Pressure

ASTM D-86, 10% to 90% Slope = 5.49 The vapor pressures of light hydrocarbons and some com-

Find its pseudo-critical temperature. mon inorganics in the temperature range below 100F appear

Solution Steps in Fig. 23-19. Vapor pressures at higher temperatures, up to

600F, are in Fig. 23-20 for the same compounds. Note that,

From Fig. 23-18 with ASTM D-86 slope = 5.49 find a VABP

except for ethylene and propylene, the hydrocarbons are all

correction of about 85F (extrapolated from the left-hand

normal paraffins.

group).

MABP = 325- 85 = 240F

VISCOSITY

Use Eq 23-16 to calculate the pseudo-critical temperature:

Tpc = 24.2787 (271 + 460)0.58848 Figures 23-21 through 23-29 give the viscosity of hydrocar-

(0.7515)0.3596 = 1062 R or 602 F bon liquids and vapors, water, steam, and miscellaneous gases.

Figure 23-21 gives data on hydrocarbon liquids. Figures 23-

For this 56.8 API fluid, estimate the pseudo-critical pres- 22, 23-23 and 23-24 present data on hydrocarbon gases. To

sure, using Eq 23-15 and MeABP = 271F: correct for pressure, adjust the gas viscosity from Fig. 23-22

Ppc = 3.12281(109) (271 + 460)-2.3125 (0.7515)2.3021 = 386 psia from atmospheric pressure using Fig. 23-24, or read directly

23-27

FIG. 23-19

Low-Temperature Vapor Pressures for Light Hydrocarbons

23-28

FIG. 23-20

High-Temperature Vapor Pressures for Light Hydrocarbons

23-29

FIG. 23-21

Viscosities of Hydrocarbon Liquids

23-30

FIG. 23-22

Viscosity of Paraffin Hydrocarbon Gases at One Atmosphere

from Fig. 23-23. Figure 23-24 is better when the reduced tem- Hence, the viscosity at 1000 psia and 100F is:

perature is greater than 1.0. Figure 23-28 gives the viscosity

of hydrocarbon liquids containing dissolved gases. Note that = (1.21) (0.0105) = 0.0127 centipoise

Fig. 1-7 gives conversion factors for viscosity. The method of Dean and Stiel41 is best for calculating the

viscosity of a gaseous mixture with large amounts of non-hy-

Calculation of Gas Mixture Viscosity drocarbons. This method is particularly useful for handling

Example 23-8 Determine the viscosity of a gas at 1,000 psia natural gas with high CO2 content. Compared to 30 CO2-N2

and 100 F with the properties: MW = 22, Tc = 409R, Pc = 665 mixtures, this method has an average deviation of 1.21% at

psia. pressures up to 3525 psia. The method uses a factor, , defined

as:

Solution Steps

Gid = 22/28.9625 = 0.760

From Fig. 23-22 at 100 F:

A = 0.0105 centipoise Eq 23-20

Then:

100 + 459.67 1000

Tr = = 1.37 Pr = = 1.50 If Tr > 1.5, then

409 665

Note: If the composition of the gas is available, calculate the A = 166.8(10-5)(0.1338 Tr -0.0932)5/9 Eq 23-21

pseudo-critical temperatures and pressures as outlined in this

If Tr 1.5,

section.

Because Tr > 1.0, Fig. 23-24 is better than Fig. 23-23 to obtain A = 34.0(10-5) (Tr8/9 ) Eq 23-22

the correction for elevated pressure to the viscosity at one at-

mosphere. In either case, A is A divided by .

From Fig. 23-24: Equations 23-20 through 23-22 predict the viscosity of pure

gases as well as mixtures. To apply the Dean and Stiel41

/A = 1.21 method to mixtures, calculate the pseudo-critical volumes, Z-

23-31

FIG. 23-23

Hydrocarbon Gas Viscosity

23-32

FIG. 23-24

Viscosity Ratio vs. Pseudoreduced Temperature

Viscosity of Miscellaneous Gases One Atmosphere Viscosity of Air43, 44, 45

23-33

FIG. 23-27 Because Tr > 1.5, the expression for A is Eq 23-21.

Water Viscosity at Saturated Conditions A = 166.8(10-5)(0.1338 Tr - 0.0932)5/9

= 166.8(10-5) [(0.1338) (1.517) -0.0932]5/9

= 48.91(10-5)

= 0.01138 centipoise

Using Fig. 23-22 and correcting for the nitrogen and carbon

dioxide content of this mixture gives a = 0.0116 cp. This is a

good check. Had this example contained a 20% N2 content, the

N2 range of Fig. 23-22 would be exceeded and dictate use of

the Dean and Stiel method. When conditions fall within the

limits of Fig. 23-23, use this figure and not the Dean and Stiel

correlation.

Viscosity of Petroleum Fractions

Mid-Boiling Point Method The viscosity of a crude oil

or crude oil fraction can be estimated if the mid-boiling point

and gravity are known:

Mid-boiling point is defined as the boiling point at 50% vol-

ume distilled.

= Ae(1.8B/T) Eq 23-27

A = (101.78Tb-0.175 29.263)KW/B Eq 23-28

In (B) = 4.717 + 0.00292 Tb Eq 23-29

Example 23-10 At l00F and 210F find the viscosity of a

heavy condensate having a mid-boiIing point of 325F and a

specific gravity of 0.7688.

Solution Steps

3

325 + 459.67

KW = = 11.99

0.7688

ln(B) = 4.717 + 0.00292(325 + 459.67) = 7.01

B = 1105.7

factors, and temperatures using the Prausnitz and Gunn42

mixing rules: A = [ 101.78(325 + 459.67)-0.175 29.263](11.99/1105.3)

= 0.02645

The same constants apply at 100F and at 210F.

Vcm = yiVci Eq 23-23

i h = 0.02645e[1.8(1105.7)/559.67 ]= 0.926 cs at 100F

h = 0.02645e[1.8(1105.7)/669.67 ] = 0.517 cs at 210F

Zcm = yiZci Eq 23-24

The reported experimental values are 0.93 and 0.52 centis-

i

tokes, respectively.

Tcm = yiTci Eq 23-25

i THERMAL CONDUCTIVITY

ZcmRTcm Thermal conductivity for natural gas mixtures at elevated

Pcm = Eq 23-26

Vc m pressure can be calculated from an atmospheric value and a

pressure correction. Figs. 23-31 through 23-36 present low

Example 23-9 For a temperature of 50 F and a pressure of pressure thermal conductivity data for gases developed from

300 psia, estimate the viscosity of a mixture of 80 mol% meth- published data51, 54. The pressure correction of Lenoir et al.52

ane, 15 mol% nitrogen, and 5 mol% carbon dioxide. Fig. 23-30 shown in Fig. 23-32 applies to these low pressure data. The

summarizes the calculations: thermal conductivity of liquid paraffin hydrocarbons appears

Pcm = ZcmRTcm/Vcm = (0.2877)(10.73)(335.9)/1.562 = in Fig. 23-35 and the thermal conductivity of liquid petroleum

663.4 psia fractions appears in Fig. 23-36.

Example 23-11 Find the thermal conductivity of a natural

Substituting from the calculation table in Fig. 23-30 into Eq gas at 700 psia and 300 F with properties MW = 25, Tc = 440

23-20: R and Pc = 660 psia.

= (5.4402)(335.9)1/6/[(19.237)1/2(663.4)2/3 = 0.043 Solution Steps

Tr = T/Tcm = 509.7/335.9 = 1.517 From Fig. 23-31, at 300F:

23-34

FIG. 23-28

Liquid Viscosity of Pure and Mixed Hydrocarbons Containing Dissolved Gases at 100F and One Atmosphere

23-35

FIG. 23-29 ductivity of each component at the given temperature is read

46, 47 from the charts provided and the thermal conductivity of the

Viscosity of Steam

mixture is determined by the "cube root rule56. This rule is

applicable to mixtures of simple gases; it does not apply to

mixtures containing CO2 because its thermal conductivity

goes through a maximum.

Eq 23-30

deviation of 2.7%. The method of Li55 based upon volume frac-

tions works best for the thermal conductivity of a liquid mix-

ture.

Example 23-12 Find the thermal conductivity of the gase-

ous mixture shown in Fig. 23-37 at 200 F and one atmos-

phere.

km = 0.05774/2.822 = 0.0205 Btu/[(hr ft2 F)/ft]

No simple correlations exist for the transport properties of

viscosity and thermal conductivity. For pure components, the

best approach is a complicated equation with many constants

that must be fit to experimental data, or extensive tables. Var-

gaftik62 and Touloukian65 each have extensive collections of

experimental data.

SURFACE TENSION

The interior molecules of a liquid exert an inward force of

attraction upon the surface molecules that tends to minimize

the surface area of the liquid. The work required to enlarge

the surface area by one square centimeter is the surface free

energy. The perpendicular force in the liquid surface, called

kA = 0.0248 Btu/[(hr ft2 F)/ft] surface tension, exerts a force parallel to the plane of the sur-

face. Surface tension is an important property for wetting,

Tr= (300 + 459.67)/440 = 1.73 foaming, emulsification, and droplet formation and is used in

Pr = 700/660 = 1.06 the design of fractionators, absorbers, two-phase pipelines,

and in reservoir calculations.

From Fig. 23-32:

Pure Components

k/kA = 1.15 Figure 23-38 provides the surface tension of pure hydrocar-

2 bons as a function of temperature.

k = (1.15) (0.0248) = 0.0285 Btu/[(hr ft F)/ft]

Stiel and Thodos53 present another method for estimating Mixtures

thermal conductivity. To determine the thermal conductivity Surface tension for binaries of known composition at or near

of a gaseous mixture of defined components, the thermal con- amospheric pressure may be calculated78 using:

FIG. 23-30

Calculation of Viscosity of a Gas Mixture

Tci, R Vci, ft3/lb Zci =

Fraction, yi Weight, MWi psia ft3/lb mole 10.73 Tci

CH4 0.80 16.043 667.0 343.0 0.0988 1.59 0.2882

N2 0.15 28.013 492.8 227.2 0.0510 1.43 0.2891

CO2 0.05 44.010 1069.5 547.4 0.0342 1.51 0.2749

Mixture 1.00 19.237 335.9 1.562 0.2877

MWcm = yi MWi Tcm = yi Tci Vcm = yi Vci Zcm = yi Zci

23-36

FIG. 23-31 FIG. 23-33

Thermal Conductivity of Natural and Hydrocarbon Gases Thermal Conductivity of Miscellaneous Gases

at One Atmosphere (14.696 psia) at One Atmosphere59, 60, 61, 62

FIG. 23-32

Thermal Conductivity Ratio for Gases

FIG. 23-34

Thermal Conductivity of Hydrocarbon Gases

at One Atmosphere67, 68, 69

23-37

FIG. 23-35

Thermal Conductivity of Liquid Paraffin Hydrocarbons

FIG. 23-36

Thermal Conductivity of Liquid Petroleum Fractions58

23-38

m = (12)/(1x2 + 2x1) Eq 23-31 would condense). It is a common misconception that the net

The presence of inert gases, such as N2 and CO2, in the liquid heating value applies to industrial operations such as fired

phase tends to lower the surface tension of the liquid. When heaters and boilers. While the flue gases from these operations

the concentration of inert gases in the liquid exceeds 1.0 mol%, do not condense, the net heating value does not apply directly

estimated values of surface tension may be 5 to 20% higher because the gases are not at 60F. Were the gases to cool to

than actual values for the mixture. 60F, some of the water would condense while the remainder

would saturate the gases. It is possible to use either the gross

or net heating value in such situations taking care to utilize

GROSS HEATING VALUE OF the hypothetical state properly.

NATURAL GASES Cost of Gas comes from a simple accounting equation

A complete compositional analysis of the mixture permits

calculation of the gross heating value, specific gravity, and Z- Eq 23-33

factor of a natural gas mixture. Some definitions are in order This equation shows that for custody transfer it is not nec-

before starting this discussion. It is necessary to understand essary to use real gas heating values (real gas heating values

the concepts: real gas, ideal gas, gross heating value (higher could be calculated from the ideal gas values using well known,

heating value, higher calorific value), net heating value (lower but computationally intense methods). If the price is set by

heating value, lower calorific value), hypothetical state. contract, it is possible to set either a real gas price or an ideal

Real Gas refers to an actual fluid in its vapor phase. It gas price. For the former, it is necessary to use real gas values;

is possible to collect samples of these fluids and to measure for the latter, the ideal gas values are correct. Because it is

their thermophysical properties. much simpler to obtain the ideal gas values, it is preferable to

establish contracts based upon the ideal gas values. The ideal

Hypothetical State refers to a definition of a fluid in a gas flow rate comes from the real gas flow rate

state that cannot actually exist, e.g. methane as a liquid at 60

F and 14.696 psia. Methane cannot be in its liquid phase at Eq 23-34

this temperature and pressure, but such a state, when defined,

can be used in calculations. Unfortunately, it is not possible because the Z-Factor is the ratio of the real gas volume to the

to find an unambiguously suitable numerical value for meth- ideal gas volume.

ane properties at these conditions. This paragraph represents the justification for using the

Ideal Gas refers to a hypothetical state in which a fluid GPA property tables for custody transfer. The GPA tables pre-

behaves in a particularly simple manner. A simple equation sent ideal gas properties that are more accurate to use in mix-

of state describes an ideal gas exactly. The ideal gas is a useful ture calculations and easier to present in tables than real gas

concept even if the state cannot be achieved because an unam- properties.

biguous path exists to reach the state starting with a real fluid. Z-Factor when dealing with custody transfer of natural

Gross Heating Value by definition is the total energy gas, it is common to use a simple equation of state for calcula-

transferred as heat in an ideal combustion reaction at a stand- tions because the base pressure (at which transfer occurs by

ard temperature and pressure in which all water formed ap- definition) is near atmospheric. The equation is

pears as liquid. The gross heating is an ideal gas property in Z = 1+ BP / RT Eq 23-35

a hypothetical state (the water cannot all condense to liquid

because some of the water would saturate the CO2 in the prod- It is common to assume that

ucts):

2

N

Hvid = yiHvidi Eq 23-32

B RT = xi bi Eq 23-36

i

i = 1

Values for Hvid and MWi are in Fig. 23-2.

and

Calculation of the ideal energy flow requires multiplication

of the gross heating value by the ideal gas volumetric flow rate bi =

B / RT Eq 23-37

of gas for the time period. To employ a real gas flow to calcu-

late the ideal energy flow requires converting the real gas flow This Z-Factor is sufficiently accurate at low pressure for cal-

rate to the ideal gas flow rate by dividing by the Z-factor. Often culations involving natural gas mixtures.

the heating value Hvid appears in tables divided by the Z-fac-

tor in preparation for multiplying by the real gas flow rate. Specific gravity (also termed relative density or gas grav-

Thus, Hvid/Z is the ideal gross heating value per unit volume ity) by definition is the ratio of gas density (at the tempera-

of real gas. Note that the Z-factor must be determined for the ture and pressure of the gas) to the density of dry air (at the

natural gas mixture and then divided into the gross heating air temperature and pressure).

value of the mixture. It is not correct to divide each pure com- G = / a = (PTaZa / PaTZ) (MW / MWa) Eq 23-38

ponent gross heating value by the pure component Z-factor

and then take the molar average. The ideal gas specific gravity is the ratio of the molecular

weight of the gas to the molecular weight of dry air.

Net Heating Value by definition is the total energy

transferred as heat in an ideal combustion reaction at a stand- Gid = MW/MWa

ard temperature and pressure in which all water formed ap-

pears as vapor. The net heating is an ideal gas property in a For a mixture

hypothetical state (the water cannot all remain vapor because,

after the water saturates the CO2 in the products, the rest Gid = yiGidi Eq 23-39

i

23-39

FIG. 23-37

Calculation of Thermal Conductivity

Thermal

Mole Molecular 3 3 3

Component

Fraction

Conductivity

Weight

MWi (yi

MW i) (yi ki

MWi )

Btu/[(hr sq ft F)/ft]

CO2 0.10 0.0127 44.010 3.530 0.3530 0.00448

H2S 0.20 0.0136 34.076 3.242 0.6484 0.00882

N2 0.05 0.0175 28.013 3.037 0.1519 0.00266

CH4 0.60 0.0258 16.043 2.522 1.5132 0.03904

C2H6 0.05 0.0176 30.070 3.109 0.1555 0.00274

Total 1.00 2.8220 0.05774

FIG. 23-38

Surface Tension of Paraffin Hydrocarbons85

23-40

The specific gravity G is measured and is generally used to FIG. 23-39

calculate the molecular weight ratio Gid when the gas compo-

sition is not available. Specific Heat for 0.58 Specific gravity gas (16.7 MW)

actual measurement conditions or serious errors in Gid can

occur.

water, but the component analysis is on a dry basis, the com-

ponent analysis must be adjusted to reflect the presence of

water. The mole fraction of water in the mixture is estimated

from the definition of relative humidity:

yw = hgPw P = nw (1 + nw)

(on a one mole basis) Eq 23-41

rated gas). Rearranging Eq 23-41 for the moles of water:

nw = yw (1 + yw) Eq 23-42

FIG. 23-40

1 1

yi(cor) = yi

1 + n = yi 1 + y /(1 y = (1 yw)yi Specific Heat for 0.75 Specific gravity gas (21.6 MW)

w w w)

Eq 23-43

i Eq 23-44

i

nent, and the summation contains the water term, the heating

value becomes:

w Eq 23-45

i

a heating value (the ideal enthalpy of condensation), we as-

sume that the water carried by wet gas (spectator water) does

not condense while we assume that the water formed by the

reaction does condense.

sufficient for custody transfer purposes because the contract-

ing parties can agree to accept the hypothetical state for the SPECIFIC HEAT

gross heating value. When trying to model actual situations,

the question becomes more complex. It is obvious that all the Figs. 23-39 and 23-40 present specific heat curves for two

water formed in a reaction cannot condense because in a situ- different gas mixtures. These curves are not based on experi-

ation in which both air and gas are dry, some of the reaction mental data but were developed using calculated values from

water must saturate the product gases while the remainder a process simulator. These charts should give reasonable re-

condenses. It is possible to account for these effects, but those sults for quick calculations of sensible heating/cooling.

interested should consult GPA Standard 2172, "Calculation of

Gross Heating Value, Relative Density and Compressibility

Factor for Natural Gas Mixtures from Compositional Analy-

sis," for the analysis. This standard contains additional de-

tails and examples covering all these calculation methods.

GPA 2172 contains a listing of the Basic source code for a com-

puter program to perform the calculations.

23-41

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23-43

NOTES:

23-44

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