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Fundamentals of Natural Gas Processing

TABLE 1.9 Maximum Levels of Major Contaminants of Common Liqueed Products Concentrations are in ppmw unless specied otherwise.
H2S High-ethane raw streams Ethanepropane mixes HighPurity ethane Commercial propane Commercial butane Commercial butanepropane mixes Propane HD-5 50 #1a 10 #1 #1 #1 #1 Total Sulfura 200 143 70 185 140 140 123 CO2 3,500 3,000 5,000 O2 H2O No freeb No freeb No freeb Pass testc Pass testc

1,000 5

a Concentration acceptable provided the copper strip test, which detects all corrosive compounds, is passed. The #1 represents the passing score on the copper-strip test, D1838-05 Standard Test Method for Copper Strip Corrosion by Liqueed Petroleum (LP) Gases. Eckersley and Kane (2004) discuss sample handling problems related to the test. b Limit is no free water present in product. c Moisture level must be sufciently low to pass the D2713-91(2001) Standard Test Method for Dryness of Propane (valve freeze method), which corresponds to roughly 10 ppmw. Source: Engineering Data Book (2004).

depending upon contractual agreement. Water content specications are less stringent for propane and butane because liquid pressures are lower, and hydrate formation is not such a threat. However, as Table 1.9 indicates, the water level in some propane products must pass a dryness test, which ensures that the water content is sufciently low (< 25 ppmw) to avoid hydrate formation when water is vaporized through an orice (see Chapter 3). Complete specications for these products and others are available in GPA standards.

1.7 COMBUSTION CHARACTERISTICS 1.7.1 HEATING VALUE

One of the principal uses of natural gas is as a fuel, and consequently, pipeline gas is normally bought and sold (custody transfer) on the basis of its heating value. Procedures for calculating the heat effect in any chemical reaction are found in standard texts on thermodynamics (e.g., Smith et al., 2001). Determination of the heating value of a fuel involves two arbitrary but conventional standard states for the water formed in the reaction: 1. All the water formed is a liquid (gross heating value, frequently called higher heating value [HHV]) 2. All the water formed is a gas (net heating value, frequently called lower heating value [LHV])

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The gas industry always uses the gross heating value in custody transfer. Obviously, the numerical difference between the two heating values is the heat of condensation of water at the specied conditions. Both states are hypothetical because the heating value is normally calculated at 60F and 1 atm (15.6C and 1.01 atm), standard conditions for the gas industry, and, thus at equilibrium, the water would be partially liquid and partially vapor. A common practice is also to assume ideal gas behavior, and consequently, the heating values commonly calculated and reported are representative of, but not identical to, the values obtained when the fuel is burned in an industrial or residential furnace. Heating values for custody transfer are determined either by direct measurement, in which calorimetry is used, or by computation of the value on the basis of gas analysis. The method is set in the sales contract. The formulas for the calculation of ideal gas gross heating values, on a volumetric basis are (Gas Processors Association, 1996)
n id Hv (dry) =

x H
i i =1 n i =1

id
vi

(1.1)

id Hv ( sat ) = (1 xw )

x H
i

id vi

(1.2)

id The equations assume that the gas analysis is given on a dry basis, that H v is the ideal gross heating value (see Appendix B), and that the mole fraction of water is xW when the gas is saturated at the specied conditions. The mole fraction can be calculated from

xw =

Pw Sat Pb

(1.3)

The vapor pressure of water at 60F (15.6C), the common base temperature, is 0.25636 psia (1.76754 kPa). The most commonly used base pressures, Pb, and the values of (1 xW) are listed below.
Pb(psia) 14.50 14.65 14.696 14.73 15.025 1 xW 0.9823 0.9825 0.9826 0.9826 0.9829

The situation regarding water is further complicated by the fact that gas analyses are normally given on a dry basis, even though the gas may be partially or fully saturated with water. Consequently, heating value may be calculated on a dry basis, wet (saturated) basis, or, if the humidity is known, a partially saturated basis.

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Fundamentals of Natural Gas Processing

TABLE 1.10 Calculations with Heating Values Obtained from Appendix B

Mole % Helium Nitrogen Carbon dioxide Hydrogen sulde Methane Ethane Propane Butanes as isobutane Pentanes and heavier as hexane Totals 0 3.2 1.7 3.3 77.1 6.6 3.1 2.0 3.0 100.0
id H vi Btu/scf id x i H vi

0.0 0.0 0.0 637.1 1010.0 1769.7 2516.2 3252.0 4756.0

0 0 0 21.0 778.7 116.8 78.0 65.0 142.7 1202.2

A complete discussion of heating value calculations, including correction of the ideal gas values to the real-gas state by use of calculated compressibility factors (z), is available in GPA Standard 2172-96 (Gas Processors Association, 1996).
Example 1.2 Calculate the heating value of the Alberta gas given in Table 1.4. Assume the heating value for the butanes to be that of isobutene, and for the C5+ fraction, use pure hexane. Table 1.10 shows the calculations with heating values obtained from Appendix B. This mixture has a gross heating value of 1,202.2 Btu/scf (44,886 kJ/Sm3). Note that credit is not given for the heating value associated with H2S in contractual situations. It is unlikely that a gas stream with 3.3% H2S would be burned.

1.7.2 WOBBE NUMBER

In gas appliances, maintenance of the same combustion characteristics are desirable when one gas composition is switched to another. Several factors must be considered, but one of the more important considerations is maintenance of the same heat release at the burner for a given pressure drop through a control valve. This combustion characteristic is measured by the Wobbe number, dened as the gross heating value (Btu/scf) of the gas divided by the square root of the specic gravity (the ratio of the density of the gas divided by the density of air; both densities evaluated at the same pressure and temperature). Two gases with the same Wobbe number are interchangeable as far as heat release at the burner is concerned. WB = (gross heating value)/(specic gravity)1/2, with the specic gravity correcting for ow through an orice. The Wobbe number normally has a value between 1,100 and 1,400. The Wobbe number is calculated from

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the gross heating value (Btu/scf) and specic gravity of the mixture, not from an average of the Wobbe numbers of the constituents of the mixture. In Europe a value of 1400 is generally required. Some typical Wobbe numbers are
Methane Ethane Propane 80% methane + 20% ethane 95% methane + 5% ethane 1,360 1,740 2,044 1,443 1,381 Btu/scf Btu/scf Btu/scf Btu/scf Btu/scf

Wobbe numbers are often adjusted by blending the natural gas with air. For example, one distribution company maintains a Wobbe number between 1,130 and 1,280 for gas distribution to its residential customers by blending air with the natural gas in three blending stations. A typical set of operating conditions for one of the air-blending stations is given below.
Inlet Wobbe Inlet Btu/scf Inlet specic gravity Normal outlet Wobbe Peak day outlet Wobbe 1,335 1,080 (40,324 kJ/Sm3) 0.654 1,210 1,280

Because air blending also changes the heating value of the gas, a balance must be maintained between the Wobbe number and the gross heating value. The Wobbe number is more commonly used in Europe. However, it will become more important in the United States in the future as LNG importation increases. Heating values for LNG can be much higher than typical sales gas from a gas plant in the United States.

REFERENCES
Anonymous, Harnessing Abundant Gas Reserves, Africa Recovery, United Nations, 13 (1) 1999, http://www.un.org/ecosocdev/geninfo/afrec/vol13no1/jun99.htm, Retrieved August 2005. BP Statistical Review of World Energy 2005. http://www.bp.com/genericsection.do?categoryId=92&contentId=7005893 Cannon, R.E., The Gas Processing Industry, Origins and Evolution, Gas Processors Association, Tulsa, OK, 1993. Collett, T., Natural Gas Hydrates: Vast Resource, Uncertain Future, U.S. Geological Survey Fact Sheet FS-021-01, 2001, http://pubs.usgs.gov/fs/fs021-01/, Retrieved October 2005. Eckersley, N. and Kane, J.A., Designing customized desulfurization systems for the treatment of NGL streams, in the Proceedings of the Laurance Reid Gas Conditioning Conference, Norman, OK, 2004. Energy Information Administration, U.S. Department of Energy, Natural Gas 1998, Issues and Trends, 1999, www.eia.doe.gov/oil_gas/natural_ gas/ analysis_publications/ natural_gas_1998_issues_and_trends/it98.html, Retrieved September 2005.

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