Natural Gas 1

Natural Gas
Liqueed Petroleum Gas and Methane are separate keywords. For Upstream Processing of Natural Gas, see
Oil Rening and Gas Production; for Substitute Natural Gas, see Gas Production.
Georg Hammer, (Mobil Erdgas Erdol GmbH), Celle, Federal Republic of Germany (Chap. 1)

Torsten Lubcke, Mobil Erdgas Erdol GmbH, Celle, Federal Republic of Germany (Chap. 2)
Roland Kettner, Mobil Erdgas Erdol GmbH, Celle, Federal Republic of Germany (Chap. 2)
Robert N. Davis, Air Products and Chemicals, Inc., Allentown, PA 18195-1501, United States (Chap. 3)
Herta Recknagel, Ruhrgas AG, Essen, Federal Republic of Germany (Chap. 4)
Axel Commichau, Mobil Europe Gas Inc., The Hague, Netherlands (Chap. 5)
Hans-Joachim Neumann, German Petroleum Institute, Clausthal Zellerfeld, Federal Republic of Germany
(Chap. 6)
Barbara Paczynska-Lahme, Consultant, Osterode, Federal Republic of Germany (Chap. 6)

1. Introduction . . . . . . . . . . . . . . 2 2.7.3. Incineration . . . . . . . . . . . . . . . 26

1.1. Composition . . . . . . . . . . . . . . 2 2.8. Example of an Integrated Plant . 26
1.2. Physical Properties . . . . . . . . . . 2 3. Liquefaction . . . . . . . . . . . . . . 29
1.3. Combustion Properties . . . . . . . 7 3.1. Physical Properties of LNG . . . . 29
1.3.1. Caloric Value . . . . . . . . . . . . . 7 3.2. History . . . . . . . . . . . . . . . . . 29
1.3.2. Wobbe Index . . . . . . . . . . . . . . 7 3.3. Production . . . . . . . . . . . . . . . 30
2. Treating . . . . . . . . . . . . . . . . . 7 3.3.1. Baseload Liquefaction Processes . . 30
2.1. Objectives of Natural Gas Treat- 3.3.2. Peak-Shaving Liquefaction Pro-
ing . . . . . . . . . . . . . . . . . . . . 9 cesses . . . . . . . . . . . . . . . . . . . 33
2.2. Natural Gas Wells and Field In- 3.4. Storage . . . . . . . . . . . . . . . . . 33
stallations . . . . . . . . . . . . . . . . 10 3.5. Transportation . . . . . . . . . . . . 34
2.3. Processing Steps During Produc- 3.5.1. Peak Shaving . . . . . . . . . . . . . . 34
tion . . . . . . . . . . . . . . . . . . . . 10 3.5.2. Baseload . . . . . . . . . . . . . . . . . 34
2.3.1. Use of Sulfur Solvents . . . . . . . . 10 3.6. Safety Aspects . . . . . . . . . . . . . 35
2.3.2. Removal of Mercury . . . . . . . . . 12 4. Transmission, Storage, and Distri-
2.3.3. Dehydration . . . . . . . . . . . . . . . 13 bution . . . . . . . . . . . . . . . . . . 36
2.3.4. Removal of Hydrocarbons . . . . . . 16 4.1. Transportation . . . . . . . . . . . . 37
2.4. Removal of Carbon Dioxide and 4.1.1. Pipeline Transmission . . . . . . . . 37
Sulfur Components . . . . . . . . . 17 4.1.2. LNG Transportation . . . . . . . . . . 37
2.4.1. Absorption Processes . . . . . . . . . 17 4.1.3. Gas Transmission Pipeline Design . 38
2.4.1.1. Physical Absorption Process . . . . 17 4.1.4. Increase in Capacity . . . . . . . . . . 39
2.4.1.2. Chemical Absorption Processes . . 18 4.1.5. Transient Flow in Gas Transmission
2.4.1.3. Physical Chemical Absorption Systems . . . . . . . . . . . . . . . . . 40
Processes . . . . . . . . . . . . . . . . 19 4.2. Storage . . . . . . . . . . . . . . . . . 40
2.4.2. Liquid Oxidation Processes . . . . . 20 4.2.1. Determination of Storage Require-
2.4.3. Adsorption Processes . . . . . . . . . 21 ments . . . . . . . . . . . . . . . . . . . 40
2.4.3.1. Adsorption of Carbon Dioxide . . . 21 4.2.2. Storage Systems . . . . . . . . . . . . 42
2.4.3.2. Adsorption of Hydrogen Sulde . . 22 4.2.3. Optimized Storage Planning . . . . . 43
2.5. Membrane Processes . . . . . . . . 22 4.3. Distribution . . . . . . . . . . . . . . 44
2.6. Cryogenic Natural Gas Separa- 5. Economic Aspects . . . . . . . . . . 45
tion . . . . . . . . . . . . . . . . . . . . 23 6. Testing and Analysis . . . . . . . . . 47
2.7. Recovery of Sulfur . . . . . . . . . . 24 6.1. Analysis of Natural Gas Composi-
2.7.1. Claus Process . . . . . . . . . . . . . . 24 tion . . . . . . . . . . . . . . . . . . . . 47
2.7.2. Tail-Gas Cleanup Processes . . . . . 25 6.1.1. Sampling . . . . . . . . . . . . . . . . 47

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a17 073
2 Natural Gas

6.1.2. Gas Chromatography . . . . . . . . . 47 6.2.2. Caloric Value . . . . . . . . . . . . . 49

6.1.3. Analysis of Nonhydrocarbons . . . 48 6.2.3. Molecular Mass . . . . . . . . . . . . 49
6.2. Determination of Physical Proper-
6.2.4. Dew Point . . . . . . . . . . . . . . . . 49
ties . . . . . . . . . . . . . . . . . . . . 49
6.2.1. Density . . . . . . . . . . . . . . . . . . 49 7. References . . . . . . . . . . . . . . . 50

The entire topic was coordinated by Axel Main Impurities. In many areas the natural
Commichau. gas recovered is sour, which means that it con-
tains appreciable quantities of hydrogen sulde
and carbon dioxide. Although larger quantities
1. Introduction of carbon dioxide are undesirable because they
make the transport of natural gas more costly,
Natural gas is a mixture of gaseous hydrocar-
diminish its combustion qualities, and have a
bons with varying quantities of nonhydrocar-
corrosive effect under certain conditions, carbon
bons, which are normally considered impurities.
dioxide can be tolerated in percentage levels.
Natural gas is often associated with liquid hydro-
In contrast, hydrogen sulde concentrations in
carbons (i.e., condensate and crude oil).
salable gas must be reduced below 3 ppm be-
Natural gas formed during many epochs in
cause of its high toxicity. Furthermore, it is very
the history of earth and accumulated after mi-
corrosive in combination with water and, when
grating from its place of origin to subsurface de-
burned, produces sulfur dioxide, which is also
posits in porous or fractured layers of many ge-
toxic and corrosive. Therefore, sour gas is gen-
ologic formations ( Oil Rening). Natural gas
erally desulfurized or sweetened to reduce the
is recovered with wells that are drilled into these
hydrogen sulde content to traces (clean gas).
deposits. Worldwide annual production amounts
to ca. 2.81012 m3 . Estimated gas reserves are
Higher Hydrocarbons and Water Vapor.
on the order of 1501012 m3 (see Chap. 5).
Natural gas may contain larger quantities of
higher hydrocarbons than shown in Table 1 (so-
1.1. Composition called rich or wet gas) and, in addition, is sat-
urated with water vapor under natural condi-
Usual Composition. Natural gas is com- tions. These constituents can condense at lower
posed mainly of methane, ethane, propane, and temperature and higher pressure and thereby
butane. In addition, it usually contains minor impair the transport and use of natural gas.
quantities of heavier hydrocarbons and varying Under certain conditions, water and gas can
amounts of gaseous nonhydrocarbons such as form icelike solids, so-called hydrates (see Sec-
nitrogen, carbon dioxide, and hydrogen sulde. tion 1.2). Therefore, the proportion of condens-
A typical composition is given in Table 1. able constituents is normally decreased substan-
Table 1. Typical composition range of natural gas tially by refrigeration, adsorption, or absorption
processes before the natural gas (then called lean
Compound Molar fraction or dry gas) is transmitted through pipelines or
Hydrocarbons liqueed.
Methane 0.75 0.99
Ethane 0.01 0.15
Propane 0.01 0.10
n-Butane 0.00 0.02 1.2. Physical Properties
Isobutane 0.00 0.01
n-Pentane 0.00 0.01 Molar Mass. Table 2 shows the molar mass
Isopentane 0.00 0.01 of the commonly occurring components of nat-
Hexane 0.00 0.01
Heptane plus higher hydrocarbons 0.00 0.001 ural gases. The apparent molar mass M a of a gas
Nonhydrocarbons mixture such as natural gas is equal to the sum
Nitrogen 0.00 0.15 of the molar fraction yi times the molar mass Mi
Carbon dioxide 0.00 0.30
Hydrogen sulde 0.00 0.30
of each component:
Helium 0.00 0.05
 Natural Gas 3

Ma = y i Mi (1)
= nM/V (4)
Table 2. Physical properties of natural gas components at STP[4] For a gas mixture such as natural gas, the molar
mass M in Equation (3) is replaced by the appar-
Compound Molar mass Molar Density , Relative
M, volume V , density d ent molar mass, M a , and z is the compressibility
kg/kmol m3 /kmol kg/m3 ( air = 1) factor of the gas mixture at the temperature and
Methane 16.043 22.360 0.7175 0.5549 pressure conditions of interest.
Ethane 30.069 22.191 1.355 1.048 The relative density d (see Table 2) (tradi-
Propane 44.096 21.928 2.011 1.555 tionally designated specic gravity) of a gas is
n-Butane 58.123 21.461 2.708 2.094
Isobutane 58.123 21.550 2.697 2.086
the ratio of its density to the density of dry air at
n-Pentane 72.150 20.90 3.452 2.670 standard conditions:
Isopentane 72.150 21.06 3.426 2.650
gas
n-Hexane 86.177 20.10 4.29 3.315 d= (5)
n-Heptane 100.203 18.3 5.48 4.235

air
Nitrogen 28.0134 22.403 1.2504 0.9671 For a gas mixture, the relative density can also
Carbon dioxide 44.0098 22.261 1.9770 1.5290
Hydrogen sulde 34.076 22.192 1.5355 1.1875
be calculated from the apparent molar mass M a
Helium 4.0026 22.426 0.17848 0.1380 of the gas mixture divided by the molar mass of
air (28.963):
Compound is in liquid state at STP.
Ma
d= (6)
28.963
Molar Volume and Ideal-Gas Law. The
volume occupied by an ideal gas depends on the
temperature, pressure, and number of molecules Critical Temperature and Pressure of Nat-
present. It does not depend on the type of ural Gas Components. The critical tempera-
molecules (ideal-gas law). ture T c is the temperature above which a gas
The volume of 1 kmol of an ideal gas at STP cannot be liqueed even if high pressure is ap-
(273.15 K, 0.101325 MPa) can be calculated, by plied. At the critical temperature a gas can be
using the ideal-gas law, to be 22.414 m3 . The ef- liqueed by application of a certain minimum
fective molar volumes at STP for common nat- pressure, the critical pressure pc . The volume of
ural gas components are shown in Table 2. The 1 kg of a gas at this critical point is the criti-
calculation may also be employed for gas
mix- cal volume V c ; the reciprocal value of V c is the
tures if the apparent molar mass, M a = yi Mi , critical density
c .
is used in computing the number of kilomoles n. The critical constants for the primary con-
stituents of natural gases are given in Table 3.
Density and Relative Density. The density The critical temperature and pressure are con-
of several components of natural gas is given stants for each species.
in Table 2. The density of a gas mixture can
be calculated by the same procedure described Table 3. Critical constants of natural gas components [5]
in Equation (1). For deviating temperature and Compound pc , T c, V c, c ,
pressure conditions, or when the ideal-gas law MPa
C 103 m3 /kg kg/m3
cannot be applied, the density of a gas under any Methane 4.60 82.55 6.1709 162
conditions can be calculated from the real-gas Ethane 4.88 32.25 4.9218 203
law: Propane 4.24 96.65 4.6035 217
n-Butane 3.80 152.05 4.3872 228
pV = z nRT (2) Isobutane 3.65 134.95 4.5248 221
n-Pentane 3.37 196.45 4.2134 237
where z is the so-called compressibility factor Isopentane 3.38 187.25 4.2411 236
n-Hexane 2.97 234.25 4.2934 233
(see page 4). n-Heptane 2.73 267.05 4.3112 232
With Equation (2) the density of a gas can be Nitrogen 3.39 146.95 3.1949 313
calculated from the relationship Carbon
dioxide 7.38 31.05 2.1359 468

= pM/z RT (3) Hydrogen
sulde 8.94 100.05 2.8903 346
where V and n in Equation (2) are replaced by Helium 0.227 267.96 14.3143 69.9
4 Natural Gas

Principle of Corresponding States. Proper- the ratio ug /uga is plotted as a function of the
ties of gases can be correlated if they are com- pseudoreduced temperature and pressure.
pared at corresponding values of absolute tem-
perature and pressure. The critical state of a gas
is used as reference point, and so-called reduced
values are obtained. The following terms are em-
ployed:

pr = p/pc ,Tr = T /Tc , andVr = V /Vc

where T c , pc , and V c are the critical point con-

ditions, and T , p, and V are the values of the
system, respectively.
If the principle of corresponding states is ap-
plied to a mixture of gases, pseudocritical tem-
peratures and pressures are dened as the molar Figure 1. Viscosity of parafn hydrocarbon gases at
average critical temperatures and pressures of 101.3 kPa as a function of molar mass [6]
the components: [( F32)/ 1.8 = C] (Copyright Society of Petroleum Engi-
neers, 1954)
ppc = yi pci
Tpc = yi Tci

where the subscript pc designates the pseudo-

critical values of the gas mixture, ci the critical
values of the components, and yi is the molar
fraction of component i. The pseudocritical pres-
sure and temperature are then used to determine
the pseudoreduced conditions:

ppr = p/ppc
Tpr = T /Tpc

Although they are convenient for correlating

purposes the pseudocritical values have no phys-
ical signicance.

Viscosity. For an ideal gas, the pressure and
temperature dependence of viscosity is opposite
to that of liquids; the viscosity of an ideal gas in-
creases with increasing temperature and is inde-
pendent of pressure. Actual hydrocarbon gases,
however, deviate from ideal behavior and ap-
proach that of liquids; their viscosity increases
with increasing pressure, and decreases with
increasing temperature at intermediate or high
pressure.
Figure 1 is employed for estimating the dy-
namic viscosity uga of natural gases composed
primarily of hydrocarbons at atmospheric pres-
sure [6]. The presence of carbon dioxide, hydro-
gen sulde, and nitrogen increases the viscosity.
The viscosity ug at any desired temperature and
pressure can be obtained from Figure 2, where
Figure 2. Viscosity ratio as a function of pseudoreduced
temperature [6] (Copyright Society of Petroleum Engineers,
1942)
Compressibility of Real Gases. At higher
pressure the attractive or repulsive forces bet-
ween gas molecules become important because
the molecules possess nite volumes. The as-
sumptions for ideal-gas behavior are then no
longer valid; consequently, the real-gas law
(Eq. 2) was formulated by introducing a propor-
tionality term (the compressibility factor) to the
ideal-gas law. Compressibility factors for natu-
ral gases are determined by laboratory measure-
ments, estimated by correlations, or calculated
by equations of state.

Figure 3. Compressibility factor of natural gases as a function of pseudoreduced pressure and temperature [7] (Copyright
Society of Petroleum Engineers, 1942)
Figure 3, which was developed by Standing
and Katz [7] from data collected on methane
and natural gases in the range of up to 56 MPa
and 121 C, presents a correlation between com-
pressibility factors and pertinent pseudoreduced
temperatures and pressures. Correlations are
also available for pressures and temperatures
above these ranges [2, 3].
The specic p V T relationship of uids is
described mathematically by equations of state.
These equations number in the hundreds, rang-
ing from those for a specic pure compound to
generalized forms that claim to relate the prop-
erties of multicomponent mixtures. Well-known
examples are the van der Waals equation [8] with
the modications of Redlich and Kwong [9],
Natural Gas 5
Soave [10], and Peng and Robinson [11] and
the virial equation. The van der Waals type of
equation of state can be solved directly for the
compressibility factor z. The most reliable meth-
ods for typical natural gases are those of Robin-
son and Jacoby [12], and Hall and Yarbor-
ough [13].
Well-known virial equations are the Bene-
dict Webb Rubin equation [14] and the Star-
ling Hon [15] extension of the Benedict
Webb Rubin equation. The European Gas Re-
search Group (GERG) and the van der Waals In-
stitute at Amsterdam carried out an extensive re-
search project [16] to develop a virial equation of
state for the accurate prediction of compressibil-
ity factors for natural gas mixtures. They used
6 Natural Gas
the virial equation solved for the compressibility
factor z and truncated after the third term:
z= 1+B (T )
M + C (T )
2M at which the rst innitesimal bubble of gas is
where
M is the molar density,
M = 1/V M , and
B and C are the second and third virial coef-
cients, which depend on temperature and gas
composition. With this equation, compressibil-
ity factors can be predicted within the range 0 to
12 MPa and 8 to 62 C, which deviate < 0.1 %
from experimental data.
Condensation Behavior of Heavier Hydro-
carbons.
Figure 4. Phase diagram of a hydrocarbon system of xed
composition
Phase Diagram. Figure 4 shows the phase
diagram of a natural gas system. It represents
the phase changes with temperature and pres-
sure for a particular constant composition, and
designates the pressure and temperature regions
in which only gas or liquids can occur and those
in which they coexist at equilibrium. The two-
phase region or envelope is enclosed on the
left side by the bubble point curve up to the crit-
ical point C and from there on, via the points of
maximum pressure Cp and maximum tempera-
ture CT , by the dew point curve.
The bubble point curve designates the points
formed from the liquid phase, and the dew point
curve indicates the points at which the rst in-
nitesimal drop of liquid condenses from the
gaseous phase. The critical point C ( juncture
of bubble and dew point curves) is the point
at which all intensive properties of gas and liq-
uid phases are identical. The pressure pc and the
temperature T c at this point are the critical values
of the gas mixture. The cricondenbar point Cp is
dened as the maximum pressure at which two
phases can exist in equilibrium. In natural gas
systems this point lies right of the critical point
C. The cricondentherm point CT is dened as
the maximum temperature at which two phases
can exist in equilibrium.
Retrograde Condensation. The dashed lines
within the two-phase envelope of Figure 4 are
liquid-content lines commonly represented by
volume percent liquid lines. They originate at
the critical point C and are intersected by a line
connecting the critical point C with the maxi-
mum temperature point CT . This line separates
the two-phase envelope in two regions. In the
lower region the gas mixture behaves as ex-
pected: At constant or decreasing temperature,
the liquid content in the gas mixture increases
with increasing pressure. The behavior of the
gas mixture in the two-phase region above the
connection line C CT is quite different. At con-
stant temperature, the liquid content in the gas
mixture increases with decreasing pressure, and
in the range between the critical pressure and the
maximum pressure, the liquid content increases
at a pressure drop even when the temperature
increases.
This phenomenon, called retrograde conden-
sation, may seriously impair the transport of nat-
ural gas through pipelines because liquid slugs
can be formed if the higher hydrocarbons have
not been removed sufciently. The condensa-
tion behavior of natural gas can be determined
by employing equations of state or by laboratory
measurements [17].
Gas Hydrates. Gas hydrates are icelike
solids composed of water and hydrocarbons.
Hydrocarbons ranging from methane to cyclo-
pentane are known to form hydrates. The for-
 Natural Gas 7
Table 4. Caloric values of natural gas components at STP [19]
mation of hydrates depends on pressure, tem-
perature, molecular size, and concentration of Compound Gross caloric Net caloric
the component. Generally, hydrates form at high value, MJ/m3 value, MJ/m3
pressure and low temperature, but they can oc- Methane 39.819 35.883
cur as high as 30 C and below 0.7 MPa. Hy- Ethane 70.293 64.345
drate formation can be predicted from empirical Propane 101.242 93.215
n-Butane 134.061 123.810
vapor solid equilibrium ratios, empirical cor-
Isobutane 133.119 122.910
relations, and laboratory measurements [18]. n-Pentane 169.19 156.56
To avoid the formation of gas hydrates in Isopentane 167.53 154.99
pipelines, the water vapor content of natural n-Hexane 208.70 193.38
n-Heptane 265.22 245.99
gas is commonly reduced by dehydration before Hydrogen sulde 25.336 23.353
transport. Lowering the water dew point to 5
to 8 C in relation to the maximum transmis- Compound is in liquid state at STP.

sion pressure, is a common stipulation in gas

specications.
1.3. Combustion Properties
1.3.1. Caloric Value
The caloric or heating value of natural gas is
dened as the heat evolved by complete com-
bustion of a unit quantity of dehydrated gas with
pure oxygen at 0.101325 MPa. The initial tem-
perature of gas and oxygen is 25 C. The ue gas
resulting from the combustion process is cooled
to the same temperature.
In determining the total caloric value, also
called the gross caloric value (higher heating
value), all the water formed in the combustion
process is condensed to the liquid state. For de-
termination of the net caloric value (lower heat-
ing value), all the water formed by the combus-
tion reaction remains in the vapor state: i.e., the
gross and net caloric values differ in the con-
densation enthalpy of water. The caloric value
is expressed in megajoules per cubic meter or,
occasionally, kilowatt-hours per cubic meter.
Caloric Value of Gas Mixtures. The
caloric value of natural gas can be calculated
from the molar composition and the caloric val-
ues of the components:
H = yi Hi
where yi is the molar fraction of component i, Hi
is the gross or net caloric value of component
i. Table 4 shows caloric values for commonly
occurring components of natural gas.
1.3.2. Wobbe Index
When burned at the same pressure, natural gases
with different compositions generate the same
amount of heat per time unit if their caloric val-
ues divided by the square root of their relative
densities (Wobbe index) are equal. The Wobbe
index can be referred to the gross or net caloric
value:
Wgross,net = Hgross,net / d
Since gas burners tolerate only limited uctua-
tions in the heating value of fuel gas, these uc-
tuations must be restricted. Therefore, natural
gas specications generally stipulate ranges that
are dened by Wobbe index rather than heating
values [20]. Consequently, certain gas streams
may require blending before sales, or separate
pipeline networks may be operated on different
gas streams with deviating Wobbe index levels.
2. Treating
Natural gas is produced at the well site in com-
positions of considerable variety. The objectives
of natural gas treatment are correspondingly di-
verse. The composition range that must be en-
compassed is shown in Table 5 for selected ex-
amples.
Besides its primary constituent methane, nat-
ural gas may contain various amounts of impu-
rities, which lead to varying problems during
production and transportation:
 8
Table 5. Composition of natural gas

Source Methane, Ethane, Propane, Butane, Higher Nitrogen, Carbon Hydrogen Elemental Organic Helium, Mercury,
hydrocarbons, dioxide, sulde, sulfur, sulfur,
vol % vol % vol % vol % vol % vol % vol % vol % g/m3 ppm vol % mg/m3

Netherlands,
Groningen a 81 2.8 0.4 0.2 0.1 14.3 0.9 0.03 0.002
Norway, Ekosk b 85 8.4 2.9 1 0.15 0.4 2 10 ppm 1
Federal Republic of
Germany, Sohlingen c 85 1.5 0.07 0.03 2 g/m3 C8+ 12.5 0.5 0.03 15

Natural Gas
Indonesia, Arund 75 5.5 2.3 1.1 0.75 0.3 15 100 ppm 0.2
United States,
Panhandle, Tx. e 73.2 6.1 3.2 1.6 0.6 14.3 0.3 0.7
Federal Republic of
Germany, Wustrow f 43 0.6 0.1 56 0.3 0.04
Federal Republic of
Germany,
Sud-Oldenburg g 77 0.1 7 8 8 0.5 3 200
fomer states of USSR, Tenguiz h 42 8.5 5.2 3.3 22 0.8 2.6 16 1000 ppm
Canada, Bearberry i 4 1 5 90 80

a
Sweet gas with low caloric value, only adjustment of water dew point.
b
Natural gas with high caloric value, H2 S conversion to COS at molecular sieve.
c
Mercury removal, C3+ separation by low temperature separation and adsorption.
d
Liquefaction, separation of gas condensate, CO2 H2 S Hg removal.
e
Helium production.
f
Nitrogen separation, CO2 removal.
g
Sour gas, use of sulfur solvent, H2 S, CO2 scrubber, sulfur production.
h
Condensate, LPG, sulfur recovery, removal of organic sulfur compounds.
i
Ultrasour gas, only for sulfur production.

Water. Condensed water forms solid hy-
drates with hydrocarbons or hydrogen sulde,
or in addition leads to liquid slugs in pipelines
and to corrosion [21].
Higher Hydrocarbons. If natural gas con-
tains higher concentrations of C2+ hydrocar-
bons, the recovery of liquid petroleum gas (LPG)
and gas condensate is economically important.
The desired Wobbe index (see Section 1.3.2) and
caloric value could also require a reduction in
the concentration of higher hydrocarbons. Even
very low concentrations of higher hydrocarbons
can condense in pipelines (retrograde condensa-
tion). These condensed hydrocarbons can attack
plastic pipes and control devices.
Hydrogen Sulde. Hydrogen sulde to-
gether with free water can cause corrosion, par-
ticularly stress corrosion and hydrogen-induced
cracking. Removal of hydrogen sulde is per-
formed almost exclusively in centralized treat-
ment plants.
Carbon Dioxide. Carbon dioxide together
with free water causes pitting corrosion in car-
bon and low-alloy steels. Some natural gases
that contain signicant amounts of CO2 must
be treated to increase the methane concentration
prior to sales.
Sulfur. Gases containing hydrogen sulde
can also contain elementary sulfur as vapor.
Some gas elds, primarily in Canada, Germany,
and the United States, contain such high quanti-
ties that the sulfur, depending on pressure, tem-
perature, and gas composition, can precipitate
and plug the production pipe, which then be-
comes blocked. Furthermore, elemental sulfur
and free water are corrosive.
Mercury. Natural gas can contain mercury
in concentrations up to several milligrams per
cubic meter, the bulk of which exists in ele-
mental form. Separated liquid mercury causes
mercury-induced corrosion in pipes and ttings,
corrosion damage to aluminum heat exchangers
in cryogenic plants, and damage to measuring
and control valves containing nonferrous metals
by amalgam formation. Mercury must also be
removed because of its toxicity.
Natural Gas 9
Other Components. In Alabama, for exam-
ple, cyclic hydrocarbons such as adamantane
and diamantane are found in natural gas; these
compounds are inclined to sublime and must be
removed by injection of oil.
Some gases contain high amounts of nitro-
gen, which must be separated to obtain a sales
gas with the required combustion properties.
Recovery of Components with Economic
Value. Another important factor is whether ad-
ditional components must be removed to meet
product specications, or whether the recovery
of these products is of economic interest. Exam-
ples of the latter include the recovery of helium,
the production of sulfur from sour gas, and the
recovery of LPG and hydrocarbon condensates.
A special case is so-called ultrasour gas (see line
9 of Table 5). In this case the main interest is not
to produce a fuel gas but rather to provide a feed-
stock in the production of sulfur. In Canada, pro-
duction of gas with a hydrogen sulde content
of 90 % began. In addition, the removal of car-
bon dioxide for enhanced oil recovery in crude
oil production should be mentioned.
By contrast, if these components are present
only in trace amounts they are not removed be-
cause of economic reasons, but rather to avoid
corrosion, environmental, or production prob-
lems.
The individual process by which undesired
gas contaminants can be eliminated depends on
the composition of the gas, the amount and type
of contaminant, and ultimately whether a salable
pure gas must be delivered at the well or whether
the gas is piped to a processing plant.
2.1. Objectives of Natural Gas Treating
Two objectives must be met in treating natural
gas:
Adjustment to the required quality standards
Recovery of byproducts
The main objective worldwide is production
of a sales gas of pipeline standard. In this respect,
both the extent of removal of undesirable com-
ponents and the range of conditioning measures
are predetermined.
Natural gas treating can take place both di-
rectly at the well and in centralized plants.
10 Natural Gas
Treating at the well is always necessary when
the gas cannot be transported to a processing
plant by pipeline without hazard. To avoid cor-
rosion, sour gas is often dehydrated at the well
so that free water can no longer condense in the
pipeline. The recovery of sulfur and the sep-
aration of nitrogen, carbon dioxide, or helium
are carried out in centralized plants, to which
streams of different wells are fed. The same
holds true for liquefaction of natural gas, recov-
ery of LPG, and removal of higher hydrocar-
bons.
2.2. Natural Gas Wells and Field
Installations
Installations at individual gas wells must fulll
the following objectives:
to guarantee trouble-free gas ow in the produc-
tion pipes and surface equipment;
to separate or, if necessary, treat coproduced liq-
uids;
to condition the gas for transportation to the pro-
cessing plant;
to meet the required feed quality for the pipeline
distribution network; and
to protect the production pipes and eld instal-
lations from corrosion.
The type and design of plants are determined
by:
type and concentration of accompanying sub-
stances in the gas;
behavior of the gas during pipeline transporta-
tion; and
applicable sales specications.
Basic Flow Diagram of Natural Gas Treat-
ing. A ow diagram for the most important treat-
ment steps is shown in Figure 5 (see next page).
To prevent deposition of elemental sulfur, which
can occur, for example, in some sour gas wells,
solvents are pumped into the production pipe.
Corrosion inhibitors can also be introduced in
the same way. On the surface, liquids condensed
under the well-head ow conditions are sepa-
rated. After being depressurized and cooled to
collection pipe conditions, further condensate is
precipitated. If necessary, separated condensate
must be treated further ( phase separation, sta-
bilizing, stripping). If large amounts of forma-
tion water occur or considerable amounts of liq-
uids (inhibitors, sulfur-dissolving agents) are in-
jected during sour gas production, hydrogen sul-
de may be released during depressurization and
transportation of these liquids. Emissions can be
minimized by high-pressure liquid stripping or
by recompression of the ashed gas. When no
further condensable hydrocarbons are present,
the gas is dehydrated to a dew point equal to or
below the dew point specied for pipeline trans-
portation.
Whereas sweet gas can be fed directly from
the well site to the distribution network, sour gas
is usually treated further in a centralized plant
serving several gas elds. If pressure at the pro-
duction well is low, compressors are installed
upstream of the pipeline network or treatment
plant.
For wet gases (see Section 1.1), both the dew
point of hydrocarbons and that of water must
be lowered. After the injection of hydrate in-
hibitors (e.g., glycols, methanol), water vapor
and higher hydrocarbons are condensed by re-
ducing the temperature [22].
If reduced pressure in the downstream
pipeline system causes retrograde hydrocarbon
condensation, adsorption processes are used for
further removal of higher hydrocarbons [23].
Various adsorbents are available to remove
traces of mercury; activated charcoal impreg-
nated with sulfur is particularly useful.
2.3. Processing Steps During Production
2.3.1. Use of Sulfur Solvents
If elemental sulfur is present in the reservoir,
sour natural gases are enriched with sulfur to a
greater or lesser extent. The ability of the gas
to absorb sulfur depends strongly on pressure,
temperature, and gas composition [24]. Cooling
and pressure reduction during production mini-
mize the solubility of sulfur and lead to its pre-
cipitation; at low temperature, solidication and
blockage of the pipe may occur. These problems
are generally overcome by injection of suitable
solvents into the production equipment which
permits sulfur to be removed with the injected
liquid, either chemically bound or physically

Figure 5. Treating of natural gas
- Flow sheet for treatment of sweet gas
Additional steps required for treatment of sour gas
dissolved. Two different reliable processes are
applied:
Polysulde Process [25]. By the addition
of aqueous ammonia or monoethylamine solu-
tions, sulfur is dissolved, in the presence of hy-
drogen sulde, as polysulde and separated at
the surface in a liquid separator. The sulfur-laden
liquid can be regenerated at ca. 150 C. Ammo-
nia or amine, water, hydrogen sulde, and car-
bon dioxide are dissolved in the condensed water
and reinjected into the well. Sulfur is precipi-
tated as a liquid and removed from the bottom
of the regenerating column.
Natural Gas 11
With this process, only a single liquid phase
occurs above ground. Traces of ammonia or
amine cause no problems in the downstream
treatment. For gases with a high carbon dioxide
content the process can be employed only under
certain conditions. In this case the alkaline media
cannot dissolve sufcient hydrogen sulde for
the formation of polysulde. This solvent also
cannot be employed in the presence of formation
water containing alkaline-earth metal chlorides
because the calcium carbonate and magnesium
hydroxide formed cause blockages that can be
dissolved only by acid treatment. Specic mea-
sures are necessary to prevent down-hole tubing
corrosion.
12 Natural Gas
Physical Solvents [26]. In the production of
sour gas, sulfur may also be physically dissolved
by means of suitable hydrocarbons. A suitable
solvent must have the following properties:
no reaction with formation water;
stability under reservoir conditions;
no reaction with sulfur;
high solvent power for sulfur;
very low vapor pressure; and
noncorrosiveness.
Spindle oil and mixtures of spindle oil with
special aromatic coal tar fractions, which have a
very high solvent power for sulfur, are the most
common solvents for this purpose. These oils
simultaneously serve as carriers for corrosion
inhibitors.
Figure 6. Schematic of a typical sour gas well completion
a) Well head; b) Anchor casing; c) Cement; d) Intermedi-
ate casing; e) Injection annulus; f) Tubing; g) Production
packer; h) Liner; i) Perforations
Sulfur-laden oils can be regenerated, for ex-
ample, by extraction with amine solutions that
also contain hydrogen sulde. After removal of
sulfur by formation of polysuldes these solu-
tions can be regenerated as already mentioned.
Phase separation may be hindered by formation
of emulsions of the oil with the simultaneously
separated water, making specic measures nec-
essary.
Typical concentric piping for sour gas pro-
duction is shown in Figure 6, in which the sol-
vent is pumped into the well through the outer
concentric pipe and returns to the well head with
the gas production stream. A sour gas well with
solvent injection and the necessary regeneration
plant is depicted schematically in Figure 7 (see
next page).
2.3.2. Removal of Mercury
Natural gas from predominantly Rotliegen-
den reservoirs often contains mercury in va-
por and/or aerosol form [27]. Natural gas elds
containing mercury are known in Algeria, In-
donesia, The Netherlands, and the Federal Re-
public of Germany. Mercury has not resulted
in any problems in production from sour gas
elds. To avoid health hazards during treatment
and use, the mercury content is lowered in sep-
arate mercury-removal plants from 5 mg/m3 to
< 10 g/m3 .
A considerable portion of the mercury has
often already been removed by low-temperature
separation (LTS) in the dehydration unit at the
well. Mercury levels of < 5 g/m3 are attained
in downstream chemisorption xed-bed reactors
with, for example, sulfur-impregnated activated
carbon. Condensable components, such as water
or hydrocarbons, reduce the loading ability for
mercury or even deactivate the adsorbent. The
reactors are not regenerated; rather, the laden
adsorbent is fed to an external treatment plant.
Regenerative amalgamation processes are cur-
rently being tested.
Mercury is also collected from the liquid hy-
drocarbon stream by phase separation. Further
treatment with solid adsorbents reduces the mer-
cury content from 300 to 20 ng/g.

Figure 7. Flow diagram of a sulfur solvent inhibitor system
a) Lean oil storage; b) Sour gas well; c) Free water knockout; d) Liquid control valves; e) Flow control valve; f) Cooler; g) Sep-
arator; h) Stripper; i) Liquid storage; j) Phase separation; k) Extraction unit; l) Phase separator; m) Ethylamine polysulde;
n) Ethylamine regeneration; o) Ethylamine storage
2.3.3. Dehydration
In most cases, natural gas is dehydrated close to
the gas wells for safety reasons. The formation
of gas hydrates in high-pressure gas pipelines
can thus be avoided and problems arising from
liquids in the transportation system minimized.
In general, a water dew point of 8 C at the
pipeline pressure is adequate. In particular, in
the presence of carbon dioxide, hydrogen sul-
de, and chlorides, corrosion can be minimized
by decreasing the water content. In some gas
elds, dehydration is not employed; production
is maintained by the use of specic corrosion-
resistant materials together with corrosion in-
hibitors and thermally insulated equipment.
Cryogenic Dehydration. To decrease the
higher hydrocarbon content in addition to main-
taining a specic water dew point, cryogenic de-
Natural Gas 13
hydration of natural gas is often employed (see
Fig. 8). The wet gas is cooled until the compo-
nents to be removed precipitate by condensation
or formation of hydrates. Methanol, glycol, or a
parafn solvent is often also injected. The reduc-
tion in temperature can be achieved by Joule
Thomson expansion. This route is employed par-
ticularly in the rst phase of production in high-
pressure wells. When the production pressure is
close to that of the transportation system, exter-
nal cryogenic units are used.
Dehydration by Absorption Processes
[28]. Standardized dehydration plants using
glycol absorption are employed most widely.
Triethylene glycol (TEG) is used in preference
to other glycols (mono- and diethylene glycols)
because of its high absorption capacity for water
vapor, its low vapor pressure (small losses from
14 Natural Gas

Figure 8. Dehydration with a hydrate inhibitor and cooling at a high-pressure well

a) High pressure separator (free water knockout); b) Heater; c) Air cooler; d) Separator; e) Joule Thomson valve; f) Gas gas
heat exchanger; g) External cooling system for low-pressure wells

Figure 9. Glycol dehydration

a) Well head; b) Corrosion inhibitor sulfur solvent injection pump; c) High-pressure separator (free water knockout); d) Heater;
e) Flow control valve; f) Air cooler; g) Separator; h) Glycol absorber; i) Demister; j) Glycol gas heat exchanger; k) Glycol
pump; l) Glycol reboiler; m) High-concentration stripper; n) Glycol storage tank; o) Glycol stripper; p) Water solvent stripper;
q) Glycol lter; r) Produced liquids storage tank; s) Flare

evaporation), and its high thermal stability. This
type of dehydration plant is shown in Figure 9.
In the absorber (h), glycol and gas are brought
in contact countercurrently. Plant pressures of
2 10 MPa are typical.
In the approximately pressureless regenera-
tion step, water-laden glycol is heated to 200 C.
The energy requirement is reduced by extensive
heat exchange between laden and regenerated
glycol in a coiled tube in the storage vessel and
in the top of the regeneration column. Both di-
rect gas-red regenerators and those with steam
or electric heating are used. The residual water
content (ca. 1 %) in the glycol after thermal re-
generation can be reduced still further by strip-
ping with dry gas or applying a vacuum. The
stripping medium, often sweet gas, is passed
through the storage vessel to be heated in the
spiral tube before the desorption of the water
vapor in the distillation section is increased. A

residual water content in the glycol of < 0.3 %
can be achieved [29]. The dew points attainable
for natural gas in equilibrium with a triethylene
glycol water mixture are given in Figure 10 as
a function of contact temperature. The plants
are self- controlled; the dehydration process is
maintained by indirect control of the glycol cir-
culation rate, the regeneration temperature, and
the stripping gas rate [30].
Figure 10. Attainable dew points of natural gas as a func-
tion of the (gas) contact temperature with triethylene gly-
col water solutions
Enrichment of hydrocarbons in the glycol can
be limited by the use of oil skimmers. Degrada-
tion products resulting from entry of oxygen,
thermal decomposition, or inux of acids from
bore hole treatment render glycol corrosive. Cor-
rosion control is usually carried out by the addi-
tion of inhibitors that increase the pH. The gly-
col is usually ltered through activated charcoal.
The service life of glycol can be several years
[31].
Further measures are necessary for dehy-
dration of sour gas, as shown by the deshed
lines in Figure 5. At the usual plant pressure of
10.0 MPa, glycol absorbs considerable amounts
of hydrogen sulde, in addition to water va-
por. The former is released during regenera-
tion of the glycol, thereby leading to corrosion
and emission problems. High-pressure strippers
Natural Gas 15
are therefore installed. At a pressure slightly
above that of the glycol absorber, hydrogen sul-
de is removed from glycol by stripping with
heated sweet gas. The sweet gas often orig-
inates from neighboring elds or plants. The
strip gas, enriched with hydrogen sulde (repre-
senting < 2 % of the dehydration unit capacity),
is recycled to the absorber. Glycol dehydration
units are constructed of normal carbon steel.
In the nal phase of gas production from a
well, considerable amounts of salt-containing
formation water are coproduced. During ash-
ing and transportation of these laden liquids,
gases are released, including hydrogen sulde
and benzene toluene xylene (BTX). Emis-
sions can be minimized and risks reduced by ad-
ditional stripping or by recompression of these
ash gases.
Adsorptive Dehydration. In adsorptive de-
hydration the gas is brought in contact with
molecular sieves, silica gel, or Sorbead (i.e.,
Na2 O- containing SiO2 ). Plants with only two
adsorbers, working alternately, are possible.
Dew points < 70 C are attainable with ad-
sorption plants. This is particularly necessary for
cryogenic plants and liquid natural gas (LNG)
plants, where traces of water and carbon diox-
ide can lead to blockage by ice formation.
For regeneration, ca. 5 % purge gas is drawn
from the main gas ow and fed through the laden
adsorber at plant pressure and 200 330 C
(Fig. 11, see next page). Removed water vapor
from purging of the xed bed is condensed so
that the purge gas, which is at plant pressure,
can be recycled. Regeneration by depressuriza-
tion is seldom employed in natural gas treating.
Under the normal requirements of natural gas
treating dehydration units of this type are eco-
nomically less attractive than glycol and cryo-
genic dehydration plants described above. How-
ever, they are nevertheless employed when, in
addition to simply removing water, adjustment
to a specic hydrocarbon dew point is required,
removal of hydrogen sulde or carbon dioxide
is necessary, or an extremely low dew point is
required.
The adsorbent lifetime depends mainly on the
amount of impurities (e.g., salt, inhibitors, sulfur
compounds, and waxy hydrocarbons) that orig-
inate from well production. Conversion of sul-
fur compounds to hydrogen sulde or carbonyl
16 Natural Gas

Figure 11. Hydrocarbon removal with adsorption and regeneration under pressure
a) c) Adsorbers; d) Heater; e) Cooler; f) Chiller; g) Separator; h) Phase separator

sulde in the adsorber has been observed. Ad- The vapor pressure curve of pure methane is also
sorption plants are often used in offshore elds shown.
to minimize the need for scrubbing solvents.

2.3.4. Removal of Hydrocarbons

Recovery of hydrocarbons is mainly done for

economic reasons. However, removal may also
be necessary to avoid uncontrolled appearance
of hydrocarbon condensates in long-distance
pipelines and low-pressure distribution systems
in cities [32, 33]. Such condensates in pipelines
may produce liquid slugs, especially during
varying loads, which lead to errors in down-
stream measuring and controlling devices. In ad-
dition, plastic pipelines or plastic components
in meters are adversely affected. Furthermore,
condensates impair leak detecting by use of
odorants. Therefore, in addition to a water dew Figure 12. Phase diagram for natural gas containing higher
point, a hydrocarbon dew point is often spec- hydrocarbons and for pure methane
ied. Thus, condensation of hydrocarbons is a) Dew point curve; b) Boiling point curve; c) Critical point;
avoided at ground temperature and typical pres- d) Cricondentherm point
sure ranges of the transportation system (10
0 MPa) [34]. The required hydrocarbon dew point cannot
Higher hydrocarbons strongly inuence the be attained with cryogenic processes. Industri-
dew point curves of natural gas and also de- ally, adsorption plants with activated charcoal
termine the conditions under which retrograde or Sorbead are used, in which the higher hy-
condensation can occur (see Section 1.2). As an drocarbons are removed and recovered preferen-
example, the dew point lines of an untreated and tially at elevated regeneration temperatures and
a treated natural gas are shown in Figure 12. short cycle times (see Fig. 11). Presence of wa-
 Natural Gas 17

ter causes problems and is usually removed rst

in upstream dehydration plants [32].

2.4. Removal of Carbon Dioxide and

Sulfur Components

Removal of the sour gas components hydrogen

sulde and carbon dioxide is one of the most
common aims of natural gas treating. Further-
more, other sulfur compounds (e.g., COS or mer-
captans) are frequently present and must also be
removed. The quality demands on puried gas
and the anticipated type of processing or further
use of the separated components are quite varied. Figure 13. Physical scrubbing with regeneration by depres-
As a result, a choice of many different processes surization and stripping
is available [35]. a) Absorber; b) Solvent recovery; c) Stripper; d) Recompres-
sor

2.4.1. Absorption Processes Important processes include the following:

The method with the broadest application is gas
scrubbing. Here, the sour gas components are re-
versibly bound to a solvent by chemical or phys-
ical absorption. In the regeneration step the com-
ponents are desorbed unchanged and the solvent
is recycled to the scrubber.
2.4.1.1. Physical Absorption Process [3537]
If selective removal of sulfur compounds is re-
quired for natural gases with a high content
of sour components, physical absorption pro-
cesses are preferred. In physical absorption,
carbon dioxide and hydrogen sulde are only
physically dissolved in the solvent. The pro-
cess is reversible: during regeneration under
strongly reduced pressure, absorbed gaseous
components are released unchanged from the
solvent ( Absorption, Chap. 4.1.) (Fig. 13).
(1) the Purisol process, which operates with
N-methylpyrrolidone (NMP); (2) the Selexol
process, in which the solvent is a mixture of
poly(ethylene glycol dimethyl ether)s; (3) the
Sepasolv process, with poly(ethylene glycol
methyl isopropyl ether); (4) the Fluor solvent
process, with propylene carbonate; and (5) the
cold methanol process (Rectisol). With the ex-
ception of the Rectisol process (which operates
at 10 to 30 C), all operate at ambient tem-
perature and employ high-boiling organic sol-
vents (Table 6). The absorption properties for
carbon dioxide are similar; the selectivity of
NMP for hydrogen sulde is higher, which is
often desirable.
Physical scrubbing agents are usually anhy-
drous; thus both dehydration and removal of car-
bon dioxide and/or hydrogen sulde can be car-
ried out in a single step; the separate dehydra-
tion step usually required in chemical absorption
process is superuous. At a water content of ca.

Table 6. Characteristic properties of physical solvents

Property Purisol Selexol Propylene carbonate Sepasolv Rectisol

Vapor pressure (25 C), Pa 53.2 0.097 11.3 0.049 13 000
Solubility of CO2 (25 C), m3 /m3 3.54 3.6 3.38 3.38 13.43
Solubility relative to CO2
CH4 0.072 0.067 0.038 0.066 0.051
C3+ 1.07 1.02 0.51 2.35
COS 2.72 2.33 1.88 2.54 3.92
H2 S 10.2 8.53 3.29 6.86 7.06

at 25 C.
18 Natural Gas
3 5 % in the scrubbing agent (e.g., Selexol),
itis also possible to regenerate without a strip
gas compressor; the stripping agent is then the
water vapor present.
To reduce losses and prevent condensation of
the scrubbing agent in the pipeline, small post-
treatment units are often installed (e.g., with gly-
col). Washers, activated carbon adsorbers, or re-
frigeration systems, are also possible. Because
of the good solubility of higher hydrocarbons
in these physical solvents, these processes also
allow the recovery of LPG.
Amount of Scrubbing Agent. The circulat-
ing amount of scrubbing agent required is almost
independent of the concentration of the compo-
nents to be removed but does depend on pressure
and raw gas throughput. Loading of the physical
scrubbing agent increases with the partial pres-
sure of the components to be removed: Thus,
physical absorption is used advantageously at
higher concentration of these components and
higher process pressure. A large amount of coab-
sorbed methane can be released in the rst de-
pressurization step by ashing (usually multi-
stage ashing) and can be fed protably into in-
ternal fuel-gas systems.
A high selectivity for hydrogen sulde com-
pared to carbon dioxide leads to process streams
with high hydrogen sulde concentration, which
can be used in the Claus process. A certain resid-
ual amount of carbon dioxide in the treated gas
may be desirable to adjust its caloric value to
required specications. To match quality spec-
ications, physical scrubbing processes can be
operated with variable selectivity by adjusting
circulation of the solvent and temperature.
Physical scrubbing processes are noncorro-
sive, and regular carbon steel is generally used
as construction material. Complete removal of
carbonyl sulde from the crude gas requires so-
phisticated equipment.
2.4.1.2. Chemical Absorption Processes [35,
3840]
Alkanolamine scrubbing, known since 1930,
is currently one of the most frequently used
processes ( Gas Production). Aqueous so-
lutions of monoethanolamine (MEA), dietha-
nolamine (DEA), diisopropylamine (DIPA), di-
glycolamine (DGA), and methyldiethanolamine
(MDEA), in particular, are used as absorbents.
The choice of solvent is determined by different
factors.
Monoethanolamine allows a high nal pu-
rity but requires a considerable amount of en-
ergy for regeneration, and absorption of carbon-
yl sulde leads to degradation products that must
be eliminated in a reclaimer (see Section 2.8).
Selective removal of hydrogen sulde is not
possible. Diglycolamine, like MEA a primary
amine, is suitable for the complete absorption
of both hydrogen sulde and carbon dioxide
and can also be used for scrubbing of carbonyl
sulde and mercaptans. The secondary amines
DEA and DIPA show a lower heat of reaction
for absorption desorption of sour gas compo-
nents; as a result, they require less regeneration
steam than MEA. At higher carbon dioxide lev-
els, various degradation compounds are formed
that cannot be regenerated, and require use of
a reclaimer (see Section 2.8). A certain selec-
tivity for hydrogen sulde is possible, particu-
larly with DIPA, because its reaction with carbon
dioxide is slower. Tertiary amines such as MDEA
have considerably better selectivity for hydro-
gen sulde. The heat of reaction with MDEA
is lower, degradation products are not formed
with carbonyl sulde and carbon dioxide, and
only a few corrosion problems arise. If gases
at low pressure are puried, the normal pipeline
specication for hydrogen sulde is not attained.
Comparative data for characterization of various
alkanolamines are presented in Table 7.
Table 7. Comparison of chemical solvents
Absorbent Heat of Relative CO2 Capacity
reaction, kJ/kg absorption, %
H2 S CO2 H2 S CO2
MEA 1905 1920 100 0.07 0.50
DEA 1190 1510 40 0.09 0.32
DIPA 1140 2180 20
MDEA 1050 1420 10 0.10 0.12
Moles of sour gas per mole of amine for
solutions with 1.3 mol of amine per kilogram
water.
Addition of corrosion inhibitors and special
chemically active components leads to advanced
processes that allow higher alkanolamine con-
centration and higher loading, for example, or

better selectivity for hydrogen sulde and, there-
fore, lower circulation rates. A lower corrosion
tendency and a reduction of energy required
for regeneration can thereby be obtained. Ex-
amples are the Amine Guard, Econamine, ac-
tivated MDEA (BASF), Gas/Spec, and Ucarsol
processes [41, 42]. Selectivity can be increased,
and further savings in energy can be obtained by
the use of sterically hindered amines (Flexsorb,
Ucarsol Innovator Solvent 111). The energy con-
sumption for the hydrogen sulde/carbon diox-
ide or carbon dioxide scrubbing system is also
lower with these amines [43, 44].
Activated and inhibited potassium carbonate
solution (Beneld, Catacarb) is widely applied
for purication of natural gas ( Gas Produc-
tion) [45]. The process can in principle be used
to remove carbon dioxide, hydrogen sulde, car-
bonyl sulde, and carbon disulde. However, it
is used mostly in treating gases with high car-
bon dioxide content. The steam requirement for
regeneration can also be reduced by addition of
hindered amines.
2.4.1.3. Physical Chemical Absorption
Processes
The advantages of chemical absorption (e.g., re-
moval of COS, low coabsorption of methane) are
combined with those of physically effective or-
ganic solvents (e.g., high loading at high partial
Figure 14. Schematic of physical-chemical scrubbing with hot regeneration
a) Absorber; b) Air cooler; c) Regenerator; d) Air condenser; e) Intermediate ash stage with reabsorber; f) Reboiler; g) Phase
separator; h) Expansion turbine
Natural Gas 19
pressure). As amines, DIPA and MDEA are pref-
erentially employed. The physical absorbents
are high-boiling solvents (e.g., Sulfolan or Se-
lexol). In addition, 5 30 % water is present. The
Sulnol process has found widespread use [46,
47] and has proved useful in the United States,
Canada, and the Federal Republic of Germany
for simultaneous removal of hydrogen sulde,
carbon dioxide and organic sulfur compounds.
However, the coabsorption of hydrocarbons is
also increased by a physical solvent, so that
an intermediate ash step with reabsorber for
the recovery of sulfur-free fuel gas (shown as a
dashed line in Fig. 14) is indispensable. Selec-
tive hydrogen sulde scrubbing can be attained
with this process by proper choice of the amine.
Other physicalchemical absorption pro-
cesses include Selening, Flexsorb PS [44], and
Amisol. With the Amisol process a mixture of
methanol and alkanolamines or aliphatic alkyl-
amines is used [48]. Like in all chemical scrub-
bing processes, the gas is saturated with water
vapor in the absorption step, making a down-
stream dehydration unit necessary.
Selection Criteria for Absorption Pro-
cesses [35, 38, 40, 49]. Selection of the best
suited process is essentially determined by the
pressure and composition of the raw natural gas,
the trace components, and the desired quality
of marketable natural gas and separated sour
gas components. Investment and operating costs
20 Natural Gas
are also important. The design of the absorber
and the amount of solvent required are deter-
mined by the absorption behavior of the least
soluble compound to be removed. Of the invest-
ment cost, 50 70 % are directly related to the
required amount of scrubbing agent in circula-
tion. In contrast, operating costs are determined
to about 70 % by the energy requirements for
regeneration and recirculation of the scrubbing
agent. In view of the many parameters to be con-
sidered, a simple selection of a process by means
of a diagram or a table is not possible. Only a
few factors can be mentioned here.
Raw Gas Composition. Physical absorbents
are generally not used for the purication of nat-
ural gas that contains higher hydrocarbons. The
solubility of butane, for example, in most sol-
vents is similar to that of hydrogen sulde. Se-
lective removal of the latter, therefore, is not pos-
sible. Hydrocarbon solubility in aqueous chemi-
cal scrubbing agents is low. Unfortunately, some
chemical absorbents react with gas components
(e.g., COS, CO2 , and CS2 ) to form corrosive
products, whereas physical solvents remain un-
changed.
Gas Throughput. Physical scrubbing sys-
tems are in general more complex and, there-
fore, require higher investment. For this reason,
chemical scrubbers are often more economical
for small gas streams if no side reactions with
the chemical absorbent occur. For large plants,
the low operating costs of physical absorption
processes outweigh the higher investment costs.
Pressure. In chemical absorption processes
the capacity of the solvent is determined by reac-
tion of the sour gas components with the active
solvent component; i.e., saturation is reached at
relatively low pressure. The circulation rate is
then proportional to the quantity of the compo-
nents to be removed and thus also to the total
pressure. For physical scrubbing agents, load-
ing increases with pressure, and the circulation
rate is inversely proportional to the total pres-
sure.
Claus Gas. In most cases, the sour gas re-
moved is fed to a Claus plant for recovery of
elemental sulfur ( Sulfur). For this purpose,
the gas should have as high a content of hydro-
gen sulde and as low a content of hydrocar-
bons as possible. If the gas to be puried con-
tains a high level of carbon dioxide in addition to
hydrogen sulde, a selective absorption process
is preferable. This requirement is better met by
physical than chemical processes. If strip gas is
used for regeneration, the hydrocarbon content
of the Claus gas should be lowered by interme-
diate ashing stages and recompression.
Sales Gas. When hydrogen sulde and car-
bon dioxide must be simultaneously and al-
most entirely removed, chemical or physical
chemical scrubbing processes can be attractive.
The presence of organic sulfur compounds ex-
cludes some solvents. If only partial removal of
carbon dioxide is required, selective amine ab-
sorption processes are used at low pressure, and
physical processes are preferred at high pres-
sure.
Special solvent properties such as vapor pres-
sure, viscosity, toxicity, heat of absorption
desorption, and corrosion behavior must be con-
sidered, along with foaming tendency, water-
absorbing capacity, pricing, and environmental
impact. The decomposition products that must
be disposed of can often be reduced by a reclaim
and recovery unit.
2.4.2. Liquid Oxidation Processes
The conventional absorptive removal and sepa-
rate processing of hydrogen sulde is often too
expensive, particularly when the gas stream to
be treated is relatively small, the hydrogen sul-
de content is low, or the pressure is low. In this
case selective liquid oxidation processes can be
used [50].
The following steps are generally involved in
this process:
Absorption of hydrogen sulde in alkaline solu-
tion
Oxidation of dissolved hydrogen sulde ions to
elemental sulfur with simultaneous reduction of
a chemical oxygen carrier or microoganisms
Reoxidation of the active component with air, in
special processes with the aid of bacteria
Separation of elemental sulfur by ltration, cen-
trifugation, otation, or sedimentation and, if
necessary, further purication.
 Natural Gas 21

The processes are differentiated from each cal oxidation. It requires a sulfate bleed stream
other only by the specic redox system em- [82, 83]
ployed. A ow sheet is shown in Figure 15. The
sour gas to be puried is brought in contact with
the absorption solution in a venturi scrubber or 2.4.3. Adsorption Processes
an absorption column. The liquid, which may
Adsorption processes for the removal of hydro-
now contain elemental sulfur in colloidal form,
gen sulde and carbon dioxide are used in natu-
is then treated with air to complete the formation
ral gas treatment predominantly when only small
of elemental sulfur and to reoxidize the reduced
amounts of acidic components must be removed
oxygen carrier which is then recycled to the ab-
[51, 52].
sorption step. The sulfur sludge is collected and
Activated charcoal and zeolitic molecular
treated further.
sieves are used as adsorbents. Zeolites, in par-
The following processes are used:
ticular, are suitable for selective separations be-
1) Stretford, Sulfolin, Unisulf Vanadates are em- cause of their ordered crystal lattice with ex-
ployed for oxidation of the absorbed hydrogen tremely uniform pore size and their high adsorp-
sulde. Organic oxygen carriers (e.g., anthraqui- tive capacity. Typical equilibrium loading curves
nonedisulfonic acids) are required to reoxidize are shown in Figure 16.
the vanadium compounds. Optimized formula-
tions suppress side reactions (e.g., formation of
sulfate and thiosulfate) and lower the consump-
tion of chemicals.
2) Takahax, Hiperion For these processes, naph-
thoquinonesulfonates or chelates are used as ox-
idizing agents. Some environmental problems
associated with the use of vanadates can thus
be avoided. In both groups of processes, hydro-
gen sulde is absorbed very selectively; they are
also suitable for gases with a high carbon dioxide
content.
3) Lo-Cat, SulFerox, Sulnt, Bio-SR After ab- Figure 16. Loading of molecular sieve 5A
sorption in a solution of NaHCO3 Na2 CO3 ,
hydrogen sulde is oxidized with iron(III) ami-
Adsorption processes ( Adsorption) are
nopolycarboxylic acid chelates. The resulting
generally run continuously in such a way that the
iron(II) chelates are reoxidized with air. Differ-
raw gas to be puried passes through at least one
ences in composition of the solutions employed
adsorber, while the other adsorber(s) undergo a
in individual processes inuence the absorption
regeneration cycle. Regeneration can be carried
capacity for hydrogen sulde, the side reactions,
out by temperature swing, pressure swing, inert
the selectivity of absorption in the presence of
gas stripping, or a combination of these.
carbon dioxide, and the ease of removal of sul-
fur particles. The Bio-SR process works at pH 2
and without chelates. Iron(II) sulfate is oxidized 2.4.3.1. Adsorption of Carbon Dioxide
by Thiobacillus Ferroxidans[81]
Molecular sieves are used widely for the pu-
4) Sulfa-Check In this batchwise process, hydro- rication of natural gas when itis used as feed-
gen sulde is oxidized to elemental sulfur with a stock for a cryogenic plant for production of liq-
nitrite solution. The solution used and the sulfur- ueed gas. In these plants, even low levels of
containing sludge must be disposed of. carbon dioxide cause problems because the gas
5) Thiopaq Thiopaq is a biological process for freezes in the low-temperature unit and can lead
SO2 reduction, employing absorption in caustic to blockage. The simultaneous removal of traces
solution and a sulfur formation step by biologi- of water by molecular sieves is also an advan-
tage here. A gas quality of < 50 ppm of carbon
22 Natural Gas
dioxide and 1 ppm of water can be attained in
this way.
The main elements of an adsorption plant
with three towers based on the temperature
swing process are shown in Figure 11. The rst
tower (a) is in the adsorption stage for purica-
tion of the raw gas; the second (b) is cooled with
the treated gas which, after being heated, regen-
erates the adsorbent in the third tower (c). Af-
ter completion of this adsorption regeneration
cycle the function of the three identical towers
is changed by automatically controlled valves.
The regeneration gas, which is enriched in car-
bon dioxide, can be used for heating. In large
plants, however, the volume of regeneration gas
may become so large that absorptive workup and
recirculation should be considered.
2.4.3.2. Adsorption of Hydrogen Sulde
Various adsorptive processes are available for
the removal of hydrogen sulde; these are dif-
ferentiated by the type of binding to the adsor-
bent and the method of regeneration. Activated
charcoal, iron oxide, and zinc oxide are generally
used only for the removal of smaller amounts of
hydrogen sulde because of the limited regen-
eration capability of these adsorbents [53].
Molecular sieves display a high afnity for
sulfur compounds. These materials can be se-
lected to permit simultaneous dehydration and
desulfurization without removal of carbon diox-
ide from the gas. Plants are in service which can
purify gas containing 10 6000 ppm of hydro-
gen sulde and 0.1 50 % carbon dioxide. The
valuable but hydrogen sulde-rich regeneration
gas is usually treated further [54] and reused.
With special molecular sieves, hydrogen sul-
de can be removed and, in the presence of car-
bon dioxide, converted to carbonyl sulde:
H2 S + CO2 COS + H2 O
For gas with low hydrogen sulde content the
permitted level of carbonyl sulde in marketable
natural gas can be exploited by this means. Re-
generation and further treatment of the hydro-
gen sulde-containing desorption gas are then
no longer necessary. A survey on adsorption pro-
cesses is given in Table 8.
Table 8. Adsorption processes
Basic process Examples Product
Adsorption adsorption from oxygen-free H2 S
gases on active carbon or rich gas
molecular sieves
Adsorption and chemical reaction with ZnO ZnS
chemical reaction
Adsorption and regeneration by extraction or
oxidation desorption
Chemical reaction reaction of H2 S with iron to S/Fe2 S3
and oxidation Fe2 S3 regeneration by
oxidation to Fe2 O3 and
elemental sulfur
Adsorption, catalysis oxidation of H2 S with O2 to S
elemental sulfur under
active carbon catalysis
2.5. Membrane Processes
Gas separation with membranes has developed
into an economically interesting process in the
last decade. Membranes can be used for almost
all aspects of natural gas treating. The following
are of particular interest:
Separation of carbon dioxide and methane
Removal of carbon dioxide and hydrogen sulde
Dehydration
Recovery of higher hydrocarbons [5557]
Poreless, dense polymer lms are used for
the separation of gas mixtures. Individual com-
ponents of the gas dissolve in the polymer and
move through it by diffusion. Material trans-
port can be described by the following steps:
absorption from the gas phase into the mem-
brane matrix, diffusion through the membrane,
and desorption out of the membrane into the gas
phase. The general rule is that a larger avail-
able membrane surface area, thinner effective
membrane separating layer, greater difference
in partial pressures, higher membrane-specic
ow rate of the components to be separated
( permeation coefcient), and better selectivity
for individual gases result in more complete sep-
aration of a mixture. A multitude of polymer
membranes are connected in a module to reach
as high a packing density as possible. Hollow
ber, spiral-wound, and envelope-type modules
have become generally accepted. The principle
of a two-step module plant for the treatment of
sour natural gas is shown in Figure 17.
The most widespread membrane processes
are those for the separation of carbon dioxide
from natural gas. An overview of the membrane
 Natural Gas 23

Figure 17. Two-stage membrane process

Table 9. Types of membranes and modules for carbon dioxide separation and dehydration [7680]

Type of membrane and polymer Type of module Company Selectivity Permeability of

aCO /CH , COa2 , H2 Ob
2 4
b
H
m3 (STP) m2 h1 bar1
2 O/CH4

CO2 Separation
Asymmetric cellulose acetate spiral-wound Separex 25 30a 0.25 0.4a
Asymmetric cellulose triacetate hollow ber Cynara, Dow 25 30a 0.25 0.4a
Asymmetric cellulose acetate spiral-wound Grace 25 30a 0.25 0.4a
Composite polysulfone/silicone (PRISM) hollow ber Permea, 17 24a 0.1a
Monsanto
Polyaramide hollow ber Medal (Du
Pont/Air Liquide)
Asymmetric polyimide (6 FDA/DMB [79]) at sheet (spiral-wound) Grace 19a 0.4a
H2 O Separation
Polysulfone, polyphenylene oxide hollow ber Permea
(PRISM CACTUS)
Composite polyetherimideethylcellulose ether at sheet (envelope type) GKSS 500b 35b
Asymmetric cellulose acetate spiral-wound Grace 300b 3.2b

and module types used in this area is given in
Table 9.
A large number of membrane plants are in
service in the United States. They are used to re-
duce the carbon dioxide, hydrogen sulde, and
water content of natural gas directly at the well.
Membrane separators are simple to operate and
require no electrical energy, coolant, or chem-
icals. They function without moving parts and
can be operated with a minimum of supervi-
sion and maintenance. The permeate containing
the separated components can, depending on its
composition, be used as low- caloric fuel gas
employed in the recovery of sulfur, ared, or
vented directly to the atmosphere.
The service life of membranes, the pressure
difference required, and the loss of gas to the
permeate must all be taken into consideration
for process selection.
2.6. Cryogenic Natural Gas Separation
Cryogenic processes are always employed when
very low-boiling components are to be sepa-
rated because none of the processes thus far de-
scribed is suitable. Examples are reduction of
the nitrogen content in natural gas and recovery
of helium. In these processes, distillation steps
are combined in which the considerably differ-
ent boiling ranges of the primary components
methane, nitrogen, and helium can be employed
for separation (see Noble Gases).
24 Natural Gas
2.7. Recovery of Sulfur
2.7.1. Claus Process
Sulfur is recovered directly in elemental form
from treated natural gas only by liquid oxidation
processes (see Section 2.4.2). With all other ab-
sorption and adsorption processes, the regenera-
tion gas stream, containing mainly carbon diox-
ide and hydrogen sulde is processed further,
predominantly by the Claus process. This pro-
cess route to liquid sulfur is used widely in the
natural gas industry [58].
High conversion rates of hydrogen sulde are
mandated worldwide by clean air regulations.
Furthermore, the recovery of sulfur is also of
economic interest. Liquid sulfur is stored and
transported easily, and solid sulfur can be mar-
keted in the form of slates, prills, and pills.
In the Claus process, hydrogen sulde con-
version occurs in a thermal and a catalytic step.
The Claus reaction is based on the exothermic
overall reaction
2 H2 S + O2 2 S + 2 H2 O (1)
The rst exothermic reaction step (Eq. 2) takes
place in the combustion chamber at ca. 900
1100 C:
2 H2 S + 3 O2 2 SO2 + 2 H2 O (2) (2)
Subsequently, sulfur dioxide reacts with addi-
tional hydrogen sulde to form elemental sulfur
(Eq. 3). This reaction occurs in the presence of
catalyst in several consecutive steps at a stepwise
reduction of temperature from 350 to 190 C.
2 H2 S + 2 SO2 4 S + 2 H2 O (3) (3)
Cooling of the process gas from the combustion
chamber occurs in the waste-heat boiler, which is
combined with a brick-lined combustion cham-
ber. For each tonne of sulfur produced, more than
2 t of steam is coproduced. Condensers are ar-
ranged between individual stages, in which the
evaporation of water is used to cool the reaction
gases as much as possible; the aim is to attain as
high a degree of separation of elemental sulfur
as possible.
Prior to the catalytic reaction, reheating of the
gas occurs to the activation temperature of the
catalyst (ca. 180 220 C). Inactivation caused
by condensation of sulfur must be excluded. In
larger plants, both gas gas heat exchangers and
in-line burners are used. The latter must be run
exactly and substoichiometrically because the
Claus reaction is very sensitive to disturbances
and catalysts are deactivated by reaction with
oxygen. Attainable yields depend on the hydro-
gen sulde content of the gas and the number
of catalytic steps. The choice of catalyst and
the heater separator concept are also impor-
tant. The pressure is predetermined: it is approxi-
mately the atmospheric regeneration pressure of
the upstream gas scrubbing units. The pressure
drop in sulfur recovery plants is 20 50 kPa.
In the combustion chamber and the waste-
heat boiler, 50 70 % of the hydrogen sulde is
converted to elemental sulfur. The combustion
chamber conditions and the construction of the
burnerboth multijet burners and single burners
have been built for plants generating sulfur at up
to 1500 t/dinuence the course of combustion
and the formation of compounds that inuence
the process. Signicant amounts of carbonyl sul-
de, carbon disulde, carbon monoxide, hydro-
gen, and sulfur trioxide are formed [59, 60].
Catalysts for the Claus process are generally
based on aluminum oxide, which may also con-
tain other metal oxides. Traces of sulfur triox-
ide, which may be formed by reaction of sulfur
dioxide and traces of oxygen during start-up
shut-down, lead to rapid deactivation of the cata-
lyst by formation of aluminum sulfate. Catalysts
based on titanium dioxide are also available that
are not sensitive to oxygen and hydrolyze more
than 90 % of the COS CS2 formed in the com-
bustion chamber, which would otherwise require
additional measures in downstream off-gas pu-
rication plants [61, 62].
To achieve a high degree of sulfur recovery
in a Claus plant, an exact amount of combustion
air is required. This amount cannot be calculated
precisely in advance because side reactions, such
as the formation of hydrogen, carbon monoxide,
carbon disulde, and carbonyl sulde, also have
some effect on the optimal air quantity.
Continuously operating analytical devices for
determination of hydrogen sulde and sulfur
dioxide concentration have been established. A
sulfur recovery degree of 94 96 % can be at-
tained with two catalytic reaction stages; with
three reactors, > 97 % recovery can be achieved.

2.7.2. Tail-Gas Cleanup Processes
The sulfur recoveries attainable in Claus plants
often do not meet the emission standards in force
(exceptions are very small plants). Usually, vari-
ous standards are set, depending on plant capac-
ity. Mandated sulfur recoveries for plants in the
Canadian province of Alberta are shown in Fig-
ure 18. Specic emission limits based on both
the plant capacity and the hydrogen sulde con-
tent of the sour gas are applied in the United
States. In the Federal Republic of Germany a
recovery of at least 99.5 % is demanded for all
plants with a capacity of > 50 t/d [6365].
Figure 18. Sulfur recovery requirements for Alberta sour
gas plants (August 1988)
Posttreatment of Claus tail gases is therefore
generally required. A series of tail-gas purica-
tion processes is available which also produce el-
emental sulfur. The most important industrially
applied tail-gas treating processes are described
below [41].
Processes Utilizing the Claus Reaction. In
the rst group the formation of sulfur according
to the Claus reaction from hydrogen sulde and
sulfur dioxide is performed in an additional cat-
alytic step. This step is operated at a temperature
below the sulfur dew point, thereby shifting the
equilibrium in the direction of sulfur formation.
In the so-called dry-bed processes the reaction
and precipitation of sulfur occur over aluminum
oxide catalysts. When the maximum sulfur load
is reached the catalyst is regenerated with hot hy-
drogen sulde-containing recycle gas, and then
tail gas is passed to an already desorbed and
cooled reactor. Sulfur recoveries of 98 99 %
can be reached in this way. Established processes
include the following: Sulfreen, CBA, MCRC,
and Maxisulf.
In the IFP Clauspool process the reaction is
carried out in a high-boiling solvent that con-
Natural Gas 25
tains a catalyst; the sulfur formed is drawn off
as a liquid. Yields correspond to those of the dry
processes.
Sulfur recoveries of 99 % can also be attained
with the Superclaus 99 process, rst introduced
commercially in 1989. A conventional Claus
plant is run with a substoichiometric amount
of air, so that practically no sulfur dioxide ap-
pears in the tail gas. Unreacted hydrogen sulde
is converted to sulfur by reaction with air in a
downstream reactor using a special iron chro-
mium catalyst with a small specic surface area
[66, 67].
Processes with Catalytic Conversion to
Hydrogen Sulde. In the second group, all
sulfur-containing components in the Claus tail
gas are catalytically converted to hydrogen sul-
de. Further treatment takes place after cooling
and condensation of a large part of the water va-
por [68]. The following treating processes exist:
1) Absorption processes with regeneration. The
hydrogen sulde removed is returned to
the Claus plant. The Scot, Sulften, and
BSRMDEA processes ( Sulfur) are re-
presentatives of this group. To reduce en-
ergy consumption, absorbents are being de-
veloped which show better selectivity for
hydrogen sulde and lower energy require-
ments for regeneration (Flexsorb, Ucarsol).
2) Liquid oxidation processes by which ab-
sorbed hydrogen sulde is converted in so-
lution directly to elemental sulfur (Stret-
ford, Sulfolin, and Unisulf process, see Sec-
tion 2.4.2). Sulfur of lower quality is pro-
duced than with the other methods.
3) Catalytic processes in which hydrogen sul-
de is converted to sulfur in the gas phase by
addition of air, oxygen, or sulfur dioxide. The
sulfur is recovered by condensation. Repre-
sentatives of this group are MODOP [69],
Selectox, and Ultra ( Sulfur).
All processes in this group can be designed
so that sulfur recoveries of 99.5 % are attain-
able. With absorption processes, a recovery of
> 99.7 % is possible.
Processes with Catalytic Oxidation to Sul-
fur Dioxide. This group encompasses processes
in which all sulfur-containing components are
26 Natural Gas
Table 10. Balance of a sour gas treating plant (nonselective chemical physical scrubbing)
Quantity Sour gas
600 000 m3 /h
H2 S 10 vol %
CO2 10 vol %
N2 5 vol %
CH4 balance
C2+ 0.2 vol %
Organic sulfur compounds 220 ppm
Elemental sulfur 1 g/m3
H2 O dew point, C saturated
a
Fuel gas for internal use.
b
Marketable product (highly pure liquid sulfur).
oxidized to sulfur dioxide. After cooling, sul-
fur dioxide is removed by absorption. The sulfur
dioxide-rich gas arising from regeneration of the
laden solvent is recycled to the Claus plant. The
Wellman Lord and Solinox processes, in which
a sulfur recovery of > 99.5 % can be achieved,
is commercially important.
2.7.3. Incineration
With only a few exceptions, the off-gas from
Claus plants or tail-gas cleanup plants must be
fed to an incinerator in which the residual sulfur-
containing components are oxidized to sulfur
dioxide. For thermal incinerations 600 800 C
is necessary, whereas catalytic plants require
only 300 350 C. All these processes lead to
an off-gas with < 10 mg/m3 of hydrogen sul-
de. If the off-gas to be treated contains other
sulfur compounds such as carbonyl sulde or
carbon disulde, then a value of 10 mg/m3 can
also be obtained in a thermal incineration plant,
provided the temperature is sufciently high. For
the catalytic process in this case, however, up to
80 mg/m3 of sulfur must be expected in the off-
gas. In principle, energy recovery by waste-heat
boilers or gas gas heat exchangers is possible
for both processes. Nevertheless, traces of sul-
fur trioxide can lead to condensation of sulfuric
acid in the heat exchanger. To avoid corrosion,
heat exchange must be limited which means that
less energy can be saved [70].
2.8. Example of an Integrated Plant
A ow diagram of an operating plant for the pu-
rication, dehydration, and conditioning of two
Pure gas Flash gas a Claus gas Sulfur b
473 200 m3 /h 4500 m3 /h 127 000 m3 /h 86.5 t/h
max. 5 mg/m3 ca. 10 ppm 47.2 vol %
ca. 100 ppm 4 vol % 47.2 vol %
6.3 vol % 3.7 vol % 0.1 vol %
balance balance 1.7 vol %
0.3 vol % 0.1 vol %
max. 5 mg/m3 400 ppm
8 C saturated saturated
different raw natural gases is shown in Figure 19
(see next page). The design capacity amounts to
a maximum of 14106 m3 /d for raw gas 1 and
5106 m3 /d for raw gas 2. Characteristic data
for the units processing raw gas are presented in
Table 10.
Production of sulfur is set at 2100 t/d. The
sour gases are predehydrated in the eld (see
Fig. 5) and are low in higher hydrocarbons.
Treatment is thereby reduced to the removal of
sulfur components and the adjustment of the
inert-gas content. This special plant design has
been chosen because of the following criteria
[71]:
The high degree of carbonyl sulde removal,
which is necessary for underground storage of
the pure gas, can be achieved with the chem-
ical physical Sulnol scrubbing process. The
latter is unselective but, depending on the ra-
tio of hydrogen sulde to carbon dioxide in the
crude gas, may provide a sufcient Claus gas
quality. The high energy consumption of sol-
vent regeneration is also taken into account.
The high-caloric pure gas can be stored in a
nearby underground storage, but, after addition
of nitrogen, can also be fed directly to the sales
pipeline as low-caloric gas. The gas must be de-
hydrated because a water-containing scrubbing
agent is used. The three-stage Claus plant attains
a sulfur recovery of 97.5 %; the total recovery
is increased to 99.8 % in a downstream tail-gas
cleanup plant using the Scot process. After de-
gassing, the sulfur produced is stored as a liquid
and transported by rail. Sometimes the sulfur is
solidied to prills or pellets outside the plant.
Steam generated in a Claus plant is used in the
reboiler for heating the Sulnol solvent. Expan-
sion turbines are employed for depressurization
of the rich Sulnol, which produce surplus elec-

Figure 19. Flow diagram of a natural gas treating plant in the Federal Republic of Germany
a) Sour gas manifold; b) Town gas manifold; c) Disposal well
Steam; Condensate
tricity. In many cases the energy recovered from
expansion, heat exchangers, and Claus waste-
heat boilers is sufcient for regeneration and
running the pumps. The total energy require-
ment of the sour gas treatment described here
is ca. 3 % of the feed gas. One of the greatest
consumers of energy is the tail gas purication
plant.
Degradation of the DIPA content of the sol-
vent to oxazolidone occurs because of the high
carbon dioxide content of crude gas. The ox-
azolidone is regenerated to reusable scrubbing
Natural Gas 27
agent in a secondary plant. In another secondary
plant a sulfur-dissolving agent, which prevents
sulfur plugging of the wells (see Section 2.3.1),
is regenerated for further use.
Lean raw gas 2, which contains a low level of
hydrogen sulde, is treated in a Purisol scrubber.
Carbon dioxide remaining in the raw gas helps
in adjusting the caloric value in the total pure
gas stream from the Sulnol unit. The ash gases
are so low in hydrogen sulde that they can be
burned in a boiler.
28 Natural Gas
Auxiliary Plants. Natural gas treating plants
are connected to the public energy distribution
network. Reliable auxiliary plants are required
to guarantee a high level of availability and in-
dependence.
Steam Generation. Waste heat from the
Claus process is used in the processing plant to
drive process pumps and turbine-driven gener-
ators, and to heat solvents. The high-pressure
steam generated is rst expanded in turbines.
The saturated low-pressure steam obtained can
be used reboiling of the solvent at constant tem-
perature. The reboiler steam pressure is 0.5
0.7 MPa and is adjusted to match the thermal
stability of the solvent. Waste-heat boilers in
the Claus plant operate at steam pressures of
1.6 4.0 MPa; the sulfur condensers at 0.1
0.6 MPa. By proper choice of driving equipment
and steam pressure, energy requirements can be
balanced so that only a little external energy is
needed. Small amounts of blow-down streams
must be continuously removed from boilers and
condensers to avoid corrosion. These streams
must be replenished by water from a treatment
plant and a boiler feedwater degassing plant.
Electrical Power. Large compressors, circu-
lating pumps, and blowers are often driven by
steam turbines to achieve a better control of their
speed. Frequently, the plants own power station
is only used for start-up and shutdown, whereby
both steam- and gas turbine-driven generators
are employed.
Inert Gas. Occasionally, puried natural gas
must be mixed with inert natural gas to meet
specied quality standards. When the admixing
of air is not possible because of limitations of
the oxygen content, inert gas plants are required.
Inert gases produced from both catalytically pu-
ried ue gases and air separation are used. The
dry gases are generally produced at low pressure
and brought to pipeline pressure (ca. 10 MPa) by
multistage compressors. Inert gases are also em-
ployed for safe start-up and shutdown of plants
and for regeneration of the Claus catalyst [72].
Tank Storage. Both higher hydrocarbons and
sulfur are stored in tanks as liquids. They are
transported further by road, rail, and frequently,
pipeline. With special thermal insulation, liq-
uid sulfur transportation through pipes of more
than 8 km in length is possible without additional
heating [73].
Wastewater. Natural gas treating plants pro-
duce little noxious wastewater. The boiler- and
cooling tower blow-down water is fed to public
sewage systems. Waste waters from piping and
equipment cleaning are collected and treated in a
reclaimer. Remaining residues are injected with
the salt-containing formation water in separate
disposal wells.
Gas Mixing. Different eld qualities are
mixed in the so-called raw gas manifold, so that
the absorbers can be charged with gas of con-
stant composition. Special separators minimize
the entrainment of liquids and impurities that
would damage the solvent or cause foaming.
Pipelines from the eld can be charged from the
manifold with pigs for cleaning purposes. Mix-
ing of different pure gases to adjust the Wobbe
index and the net caloric value is possible in
the pure gas manifold.
Reclaimer, Filter. Through side reactions,
chemical scrubbing solvents in particular be-
come enriched with degradation products, fre-
quently of unknown nature. These substances
are corrosive and may cause foam formation in
the absorbers. Solvent quality is stabilized by
removing a small side stream and addition of
fresh solvent. This side stream is processed in a
reclaimer, which is usually an auxiliary distil-
lation plant. Puried absorbent can be reused in
the process [74].
With physical scrubbing agents, removal of
undesired substances (e.g., hydrocarbons) is fre-
quently achieved by addition of water and phase
separation. Mechanical lters are used in a side
stream.
Special Construction Features. High partial
pressures of carbon dioxide and hydrogen sul-
de in a wet environment lead to serious cor-
rosion. In particular, the stress corrosion crack-
ing (SCC) caused by hydrogen sulde corrodes
high-strength steel from inside: atomic hydro-
gen can be formed by acid corrosion in connec-
tion with water, and can diffuse into the steel
because of its small size of the atom. The hydro-
gen atoms recombine in the area of microcracks
and local inhomogenities; the resulting pressure,
which can reach 105 MPa, leads to cracks and
blistering (hydrogen-induced cracking).
High-alloy hard steels are particularly sus-
ceptible; the necessary construction and testing
regulations must be adhered to. Consequently,
the carbon content of the steel is limited. Equip-

ment and pipeline welding joints must be an-
nealed. A hardness H RC of < 22 must be main-
tained. Excessive stresses ( particularly at plate
edges) and thickness changes which are caused
by the fabrication techniques must be avoided.
Specially designed forged nozzles based on -
nite element analysis are customary [75].
3. Liquefaction
The principal reason for liquefying natural gas is
a 600-fold reduction in volume that occurs with
the vapor-to-liquid phase change. In its naturally
occurring vapor state, natural gas is a bulky en-
ergy source, which is sometimes cumbersome to
handle. Storage of the vapor requires huge un-
derground caverns or large telescoping storage
tanks. Transporting natural gas from production
sources to points of consumption necessitates
large pipeline networks. Thus, only overland or
somewhat shorter undersea routes can be consid-
ered. Finally, natural gas at atmospheric pressure
is too bulky to be considered as a fuel for trans-
portation purposes; at the very least, it must be
compressed.
Liquefaction of natural gas serves to over-
come these obstacles, and permits transport over
larger distances and more diverse application of
liqueed natural gas (LNG) as an energy source.
For example, LNG produced in the Middle East
and throughout the Pacic Rim supplies ca. 10 %
of Japans primary energy consumption. Storage
of LNG near urban areas permits peak demands
for natural gas to be satised without building
additional pipelines that would be underutilized
most of the time.
Compressed natural gas is a feasible trans-
portation fuel for truck and bus eets. However,
more recent aircraft and railroad applications
[87] require the higher energy density of LNG
to be commercially viable.
3.1. Physical Properties of LNG
In the nomenclature of the energy industry, LNG
is on the light end of the liqueed gas spectrum
that also includes natural gas liquids (NGL, pri-
marily ethane with some propane) and liqueed
petroleum gas (LPG; Liqueed Petroleum
Gas, which consists mainly of propane with a
Natural Gas 29
signicant proportion of butane). Common to
each of these products is the lack of a standard
set of physical properties. Nevertheless, certain
characterizations of LNG are possible and use-
ful.
Because methane is its primary component,
the boiling point of LNG at atmospheric pressure
is ca. 160 C. Liqueed natural gas is odorless
and colorless. Trace contaminants, especially
mercury, can render LNG potentially corrosive
if they are not removed to sufciently low lev-
els during the prepurication (see Chap. 2) and
liquefaction processes. Liqueed natural gas is
a commercial product, so the need to avoid so-
lidication of trace contaminants is buttressed
by rigid specications for an environmentally
acceptable fuel. Therefore, contaminants such
as water vapor, carbon dioxide, and sulfur com-
pounds, which may be found in vapor-phase nat-
ural gas, generally do not exist in LNG. Simi-
larly, the relatively low boiling point of LNG
limits the maximum concentration of pentane
and heavier hydrocarbons that can exist in the
liquid phase.
3.2. History
Early attempts to commercialize LNG failed.
Barge transport between stockyards in Chicago,
Illinois and gas elds in Louisiana did not em-
ploy adequately designed storage [88]. Simi-
larly, a prototype peak-shaving storage tank in
Cleveland, Ohio failed in 1944 because of poor
material selection. The resultant spill from the
tank vaporized, traveled through an adjacent
sewer system, and caused a number of remote
casualties upon ignition. These early setbacks,
as well as the subsequent explosion of a poorly
designed LNG tank undergoing repair on Staten
Island, New York in 1973, did much to hinder the
commercialization of LNG in the United States.
Much of the early development centered around
Europe and North Africa.
The rst baseload LNG trade began in 1964
from Algeria to Canvey Island in England and
to Le Havre in France. Subsequent projects were
built in Libya and Algeria to supply LNG to Eu-
rope and its expanding pipeline grid. Japan be-
came a purchaser of LNG in 1969, with the re-
ceipt of its rst cargo from Kenai, Alaska. Since
that time, Japan has become the preeminent
30 Natural Gas
buyer of LNG in the world. Major production
facilities now also exist in Indonesia, Abu Dhabi
(United Arab Emirates), Brunei, Malaysia, and
Australia. Qatar started LNG shipments to the
Far East late in 1996 and will be a major LNG
exporter early in the next century.
Peak-shaving applications of LNG expanded
rapidly in the late 1960s and throughout the
1970s in both Europe and North America. This
growth mirrored the increased use of natural gas
in urban areas and, in particular, the preponder-
ant use of natural gas for heating. Virtually no
growth of the peak-shaving business occurred
in the 1980s because of a number of diverse
factors, ranging from energy conservation and
environmental siting restrictions to changes in
governmental regulations.
Experiments in LNG fueling of transporta-
tion vehicles have been carried out for more than
20 years. Several driving forces exist for this
work, including the environmental advantages
of natural gas combustion compared to conven-
tional fuels. However, no major infrastructure
for LNG fueling exists to support the conversion
of automobiles and trucks. Current development
for railroad and marine vessels is, therefore, fo-
cusing on closed-loop applications in which the
vehicle returns to the fueling station as part of its
normal routing. Fishing vessels may also prot
from the low temperature of LNG, which can
be used to refrigerate the sh that are caught.
Similarly, to best utilize LNG as a fuel for high-
performance aircraft, the leading edges of the
wings may have to be cooled with LNG to re-
duce skin-friction drag, while the LNG is being
vaporized for use in the aircrafts engines.
3.3. Production
Because of the high critical pressure of methane,
LNG must be produced commercially by refrig-
eration rather than pressurization. A number of
processes have been commercialized for LNG
production.
Common to all natural gas liquefaction pro-
cesses is the need to pretreat the gas feed for
removal of components that would either freeze
outthus restricting the ow of the processor
lead to pollution upon combustion of the revap-
orized LNG (see Chap. 2).
3.3.1. Baseload Liquefaction Processes
( Refrigeration Technology, Cryogenic
Technology)
Large-capacity or baseload liquefaction of nat-
ural gas is performed with emphasis on process
efciency. The scale of operations means that
production with lower installed power capacity
and lower fuel consumption is economically fa-
vored. Because the heat that must be removed
from natural gas to cool it to 160 C is even-
tually rejected to ambient air or water, rather
elaborate systems have resulted.
Cascade Refrigeration Processes. The ear-
liest liquefaction processes employed cas-
cades of single-component refrigerants in se-
ries ( Refrigeration Technology) (see Fig. 20).
Each refrigerant is established as a separate
closed-loop refrigerator that supplies refriger-
ation at discrete temperature levels. Typically,
propane, ethylene, and methane are used to pro-
vide a wide, balanced range of refrigeration. Af-
ter compression (a) three temperature levels for
each of the three refrigerants form a nine-stage
cascade. Each of these temperature levels corre-
sponds to a preset pressure letdown (d) for evap-
orating the refrigerant in heat exchange with the
natural gas feed and a separate refrigerant stream
that requires cooling (e). In this fashion, heat
is removed from the natural gas at successively
lower temperatures; i.e., the refrigerant is boiled
at successively lower pressure. Heat is rejected
to ambient air or water via the warmest refrig-
erant, generally propane, and compressor after-
coolers (b). The methane refrigerant loop is open
in that it is combined with the natural gas feed
and after the nal pressure letdown the liquid
methane forms part of the LNG product. Cas-
cade processes allowed use of single-component
refrigerants at a time when thermodynamic cor-
relations and thermophysical data bases were
not as well developed as they are at present. In
addition, the processes could be made very ef-
cient (i.e., the amount of irreversibility could
be reduced) by increasing both the number of
refrigerants employed and the number of boil-
ing stages for each refrigerant. This improve-
ment in efciency, however, had signicant cost
penalties. Each refrigerant requires its own com-
pressor, compressor driver, vessels, and heat ex-

Figure 20. Nine-stage cascade liquefaction process
a) Compressor; b) Condenser; c) Accumulator; d) Phase separator; e) Heat exchanger
changers, together with attendant piping, insula-
tion, and instrumentation. Each additional stage
of boiling adds to the number of heat exchang-
ers and vessels and to the number of sidestreams
entering the compressor.
All-Mixed-Refrigerant Processes. The
problems of complex layout, relatively high
capital cost, and limited train capacities inher-
ent in cascade processes were addressed by
the mixed-refrigerant processes that succeeded
them. As equipment and analytical capabilities
advanced, the refrigerants could be combined
in a single refrigeration loop (see Fig. 21). In
such processes, a single refrigerant mixture of
pentane, butane, propane, ethane, methane, and
nitrogen, for example, is constituted to match
the cooling curve of the natural gas to be liq-
ueed; i.e., the temperature enthalpy warming
curve of the mixed refrigerant closely tracks the
natural gas cooling curve in (g). This reduces
the irreversibility of the process. The same re-
frigerant is then condensed, a part against air
or water at (d) and the balance at lower tem-
perature in heat exchange against itself in (f).
In the latter case, incoming gaseous refrigerant
is cooled and condensed at elevated pressure in
Natural Gas 31
countercurrent ow against evaporating liquid
refrigerant fractions, each ashed (h) to a much
lower pressure and, hence, temperature. The all-
mixed-refrigerant process has performed well in
a number of plants and represents a simplica-
tion compared to the cascade process. However,
it is not thermodynamically efcient enough
to be economical in the face of rising energy
prices. To match the cooling curve of the natural
gas feed over the wide range from the tempera-
ture of cooling water or ambient air down to the
liquefaction temperature, compromises in the
mixed-refrigerant composition are necessary.
The wide range of boiling points for the refrig-
erant components also means that some of the
heavier components are compressed to higher
pressures than actually required for their con-
densation to ensure condensation of the lighter,
lower boiling components such as nitrogen and
methane. Such a recompression penalty cannot
be avoided without a certain degree of separation
of the refrigerant components such as occurs in
precooled mixed refrigerant processes.
Precooled Mixed-Refrigerant Processes.
In the early 1970s, a third generation of pro-
cesses, precooled mixed-refrigerant processes,
32 Natural Gas

Figure 21. All-mixed-refrigerant (MR) liquefaction process

a) First stage MR compressor; b) Cooler; c) Second stage MR compressor; d) Cooler; e) Phase separator; f ), g) Heat exchangers;
h) Joule Thomson valve; i) Product letdown valve; j) Driver

developed from direct combination of the other

two. The most widely used process employs two
separate refrigeration systems, a propane cas-
cade refrigerant loop in series with a mixed-
refrigerant cycle that incorporates propane,
ethane, methane, and nitrogen as components
[89] (Fig. 22 shows the cooling curves for this
process). The propane loop precools the natural
gas and serves as an intermediate refrigerant for
heat rejection from the mixed-refrigerant sec-
tion to cooling air or water. The propane section
can be fabricated from lower cost carbon steel,
whereas the lower temperature sections require
aluminum or nickel steels. Thus breaking the
cooling process at the propane stage is compati-
ble with economical material selection. Finally,
by reducing the range of cooling that must be
achieved by the mixed refrigerant, its composi-
tion can be optimized and energy losses due to
recompression signicantly reduced.
Additional process schemes have been devel-
oped that fall in the category of precooled mixed-
refrigerant processes. If ethane is added to the Figure 22. Cooling curve for a propane precooled mixed-
precooling refrigerant to form a dual mixed-re- refrigerant liquefaction process
a) Cooling curve of natural gas; b) Propane cascade; c) Mixed
frigerant process, then the precooling tempera- refrigerant (stage 1); d) Mixed refrigerant (stage 2)

ture can be lowered in accordance with the oper-
ating conditions of the loop and the proportion of
ethane added [90]. With this process the refrig-
eration duty can be shifted between the two re-
frigeration loops a capability that may be use-
ful in the face of changing feed gas conditions or
changing power availability. The latter can oc-
cur because of ambient temperature changes that
affect the power output of gas turbine drivers. A
binary precooling refrigerant is somewhat more
complicated to operate because simple pressure
control is no longer adequate, but it may be pre-
ferred in certain scenarios.
Another precooled process has been pro-
posed for plants that employ gas turbine drivers
in the mixed-refrigerant section. In this cong-
uration, waste heat from the gas turbines is used
to separate ammonia and water in an ammonia
absorption refrigerator [91]. This system could
provide precooling duty while eliminating the
need for costly compressors and drivers. Nei-
ther of these two systems has been employed in
an operating facility.
3.3.2. Peak-Shaving Liquefaction Processes
Peaking-shaving LNG plants differ from
baseload facilities in several signicant aspects
that affect plant design. Peak-shaving plants
are much smaller, operate only seasonally, and
are often located near the point at which the
pressure in gas trunk lines is decreased and
the lines branch into lower pressure local gas
distribution systems. The design emphasis for
peak shavers is thus on capital cost minimiza-
tion rather than high thermodynamic efciency.
All-mixed-refrigerant liquefaction cycles have
therefore been employed in a large proportion
of peak-shaving facilities. If a local distribution
pipeline is available at a pressure substantially
below that of the main gas trunk line, expander
processes can be utilized to take advantage of the
pressure difference as shown in Figure 23. Sev-
eral variations exist, but the principle of these
plants is to expand the inlet gas nearly isentrop-
ically through a turbine, thus rapidly lowering
the temperature and partially liquefying the gas.
The liquid is sent to storage, and the residual
gas is compressed in a compressor mechanically
linked to, and driven by, the expander. This gas
Natural Gas 33
is then sent to the lower pressure pipeline for
distribution outside the plant.
Figure 23. Schematic of an expander liquefaction process
a) Turbine expander; b) Separator; c) Compressor
3.4. Storage
Storage tanks for LNG are an important part of
both baseload and peak-shaving LNG facilities.
In addition, they constitute the major portion of
the investment in import receiving terminals. Be-
cause of the high cost of these units and their im-
portance in the overall safety of LNG facilities, a
great deal of attention has focused on LNG tank
design.
One of the earliest efforts in tank design was
directed at proper material selection. The Cleve-
land, Ohio tank failure in 1944 was attributable
to the use of 3.5 % nickel steel which became
embrittled at LNG temperature. Subsequent to
this, large-scale programs have proved the suit-
ability of 9 % nickel steel, stainless steels, and
certain aluminum alloys (5000 series) for LNG
tank fabrication. Designs with the latter have
been somewhat limited in size, because the coef-
cient of thermal expansion for aluminum is ap-
proximately double that for steel; in large tanks,
such thermal movement during cooldown could
result in tank failure.
Tank designs have also evolved as more so-
phisticated safety analysis has been applied to
LNG installations [92]. Early designs featured
an internal cryogenic liquid tank enclosed by an
outer tank that contained the insulation system
for the inner one. In some designs the outer tank
contained gaseous nitrogen and was, in turn,
connected to a variable-volume or bladder tank,
which compensated for changes in the nitrogen
volume due to changes in ambient temperature
while avoiding pressurization or depressuriza-
tion of the outer tank. In other designs, the roof
34 Natural Gas
Figure 24. Simplied cross-sectional drawing of single-integrity LNG storage tank
a) Suspended deck; b) Outer tank; c) Sidewall insulation; d) Inner tank; e) Load-bearing insulation; f) Foundations; g) Dike
of the inner tank was not gastight but merely
supported insulation, and the outer tank served
as a natural gas holder (see Fig. 24). In both de-
signs, the outer tanks were fabricated of carbon
steel and surrounded by a low dike to contain
any LNG spills.
Analytical studies indicated that the prime
safety risk with an LNG spill is the formation
of a large product vapor cloud that can drift, ig-
nite, and cause widespread damage. Subsequent
designs incorporated outer tank materials less
prone to failure at cryogenic temperatures and
taller dikes built closer to the tanks. These mea-
sures lead to less free surface for any LNG spill
from a tank failure and therefore a lower feed
rate to the ensuing vapor cloud.
Additional studies reviewed the consequence
of an external impact, such as a crashing aircraft,
leading to tank failure and the effect of a catas-
trophic inner tank failure on outer tank contain-
ment. These studies all focused on the need for
much more secure outer containment. Resultant
tank designs have double-integrity tankage; i.e.,
a liquid spill from a failure of the inner tank
is contained by a second concentric tank that
is structurally independent of the rst [93]. The
outer tanks have been built of reinforced con-
crete with a stainless steel liner. Finally, full-
height earthen berms have been built to protect
the tankage from external damage and to con-
tain the postulated asymmetric loading on the
outer tank resulting from catastrophic failure of
the inner tank. Where the site is too small to per-
mit full development of earthen berms, inground
storage or additional reinforced concrete outer
containment is employed.
3.5. Transportation
3.5.1. Peak Shaving
Peak-shaving LNG facilities typically vaporize
LNG from storage and send it out via a local
distribution network. In some installations, how-
ever, LNG is merely stored and vaporized for
send-out. These satellite facilities receive LNG
from other production sites, which is transported
in over-the-road trailers. The trailers are similar
to those employed in transporting liquid nitro-
gen and oxygen, and consist of an inner cryo-
genic vessel and an outer protective vessel of
noncryogenic material. The space between ves-
sels is typically lled with expanded perlite insu-
lation and evacuated to subatmospheric pressure
to further decrease heat in-leak.
3.5.2. Baseload
Baseload LNG facilities are linked to their cor-
responding receiving terminals by eets of large
oceangoing tankers. Modern tankers typically
can hold 125 000 m3 of LNG. Each tanker em-
ploys one of several containment systems, which
can be divided into three principal types. One de-
sign employs free-standing spherical tanks sup-
ported on cylindrical skirts (see Fig. 25, next
page). Each tank is insulated and located bet-
ween bulkheads in a separate section of the ship.
These compartments are blanketed with inert ni-
trogen gas, which is sampled periodically to de-
tect any LNG leakage.
A second family of designs is the membrane
tank. In ships using this type, the insulation and
a secondary barrier are applied to the hull of

Figure 25. Spherical ship tank
a) Weather cover; b) Tank; c) Insulation; d) Support skirt;
e) Thermal break; f) Inner hull; g) Ballast tank; h) Outer hull
Figure 26. Membrane ship tank
a) Membrane liner; b) Insulation; c) Inner hull; d) Ballast
tank; e) Outer hull
the ship (Fig. 26). The insulation also transmits
the load from the LNG cargo to the hull and
its structure. A metallic membrane containment
barrier is then installed over the surface of the
insulation. The membrane may consist of Invar
(highly alloyed steel with an extremely low co-
efcient of thermal expansion) or of a wafe
structure (made of nickel steel), where the cross
section of the wafe allows two-dimensional
thermal movement while maintaining intimate
contact with the load-bearing insulation. Mem-
brane tanks are also compartmentalized and en-
able more efcient storage use of the hull vol-
ume. This manifests itself in a attop deck and a
lower center of gravity, whereas spherical tanks
extend up through the deck and require domed
covers.
Natural Gas 35
A third type of LNG tanker employs free-
standing prismatic tanks. This design seeks
to combine efcient use of hull space with
the structural independence of a self-supporting
structure. A number of earlier ships were built
with this design type, but it is relatively expen-
sive and, with the exception of two smaller ships
for the Alaska Japan trade, is not employed in
newer tankers.
3.6. Safety Aspects
Liqueed natural gas may be viewed as a cre-
ation of the modern era, and as such, it has been
subjected to more thorough scrutiny than tradi-
tional fuels such as gasoline and fuel oil. The
hazards associated with LNG are that it is a low-
temperature uid, is ammable, and can create
vapor clouds dense enough to cause asphyxia-
tion. Because none of these is a problem when
LNG is contained in properly designed storage
tanks or piping and equipment, safety studies
have generally focused on LNG spills. In LNG
facilities, extensive safety systems exist to de-
tect gas leaks, to detect and counter res, and to
detect smoke. Spill prevention and containment
are implicit in the design of plant facilities, par-
ticularly of storage tanks because they contain
the greatest quantity of LNG.
If an LNG spill is ignited soon after it oc-
curs, a pool re results. This re is certainly a
problem, but it is contained in a facility staffed
and equipped to deal with such emergencies. A
greater concern is that the same spill may be
given sufcient time to evaporate and form a va-
por cloud that can travel for some distance before
ignition. A number of variables such as the na-
ture of the surface underneath the spill, the wind
velocity, and the presence of obstructions to the
cloud act to shape and direct it [94]. Mechani-
cally, the cloud is formed as LNG boils from the
surface of the spill [95]. The evolving vapors are
much colder than air and initially form a dense,
low-lying cloud. As the cloud mixes with air and
is warmed by its surroundings, it begins to rise.
Wind serves to add a horizontal component to
the clouds motion. As air mixes with the natural
gas, the mixture becomes ammable (i.e., local
compositions are between the lower and upper
ammability limits of LNG). The ammability
limits vary with LNG composition, particularly
36 Natural Gas
the proportion of propane. This cloud is then po-
tentially hazardous to areas beyond the battery
limits of the LNG facility.
A number of large-scale tests have demon-
strated certain characteristics of LNG vapor
cloud res. These res are deagrationsrapid
combustions in which the ame front that moves
through the cloud is preceded by a weak, decou-
pled shock wave [96]. An accompanying radia-
tion hazard exists, but not the pressure damage
of a shock wave that occurs when mixtures of
other hydrocarbons and air are detonated.
4. Transmission, Storage, and
Distribution
More than 50 % of world gas reserves are lo-
cated in remote areas. For example, part of the
gas used in Western Europe is produced in the
Figure 27. European natural gas transmission system
harsh permafrost environment of Siberia or in
the North Sea.
In most cases, producers ship the gas from the
elds to the borders of the countries in which it is
used. Importers buy the gas at these points under
long-term contracts and resell the fuel to local
utilities as well as to industrial users and power
stations connected directly to the transmission
system. Residential and commercial consumers
are normally served by the local distribution
companies. The European natural gas transmis-
sion system is shown in Figure 27.
Natural gas is used chiey for heating. There-
fore, gas demand varies substantially between
winter and summer, weekdays and week-ends,
or day and night. The ratio between summer
and winter loads in Europe is between 1 : 5 and
1 : 10. Production, transmission, storage, and
distribution facilities must be designed and sized
to handle these load variations.

Of the gas traded across international borders,
75 % is shipped by pipelines, and 25 % is carried
by LNG tankers.
Gas eld development and the construction
of transportation systems from distant areas of
production to gas-importing nations are highly
capital-intensive projects. Thus, the load factors
at which gas is imported are nearly always very
high. For load equalization, gas is stored in un-
derground storage facilities during the off-peak
season and produced from storage during pe-
riods of peak demand in winter. Pipeline pres-
surization (line packing) in the transmission and
distribution systems themselves, as well as peak-
shaving installations, also help to handle load
variations.
4.1. Transportation
4.1.1. Pipeline Transmission
Transportation of large gas volumes is best
achieved by large-diameter pipelines operating
at high pressure. Currently, the pipeline diam-
eter may be up to 1400 mm and working pres-
sure up to 8 MPa. Such pipelines carry gas at a
ow rate of 2106 m3 /h (STP) over a distance of
ca. 1000 km. This capacity is insufcient, how-
ever, to ship gas from distant elds to markets.
Compressor stations must therefore be built to
increase the pressure of the gas. Gas compres-
sors are normally driven by turbines or engines
fueled by their own pipeline gas for reliability
and lower cost. The number of compressors re-
quired for a given carrying capacity depends on
the distance over which the gas must be shipped
and on the compression ratio, which is given by
po
= (1)
pi
where po is the maximum compressor outlet
pressure (bar) and pi the minimum compressor
inlet pressure (bar).
As the compression ratio increases, the num-
ber of compressors needed to operate a gas trans-
mission line decreases. Hence, transmission en-
gineers must seek to optimize capital outlay and
follow-up operating expenses for pipelines and
compressor stations.
For large-diameter pipelines, the optimum
compression ratio is generally relatively low; it
Natural Gas 37
is between = 1.25 and = 1.4 [97]. Offshore
pipelines are currently built with diameters up
to 1000 mm. Pipelines from the North Sea to
continental Europe are 1000-mm-diameter lines
that are laid at a water depth of 150 m; Italy and
North Africa are connected by 500-mm lines that
cross 600-m-deep water. The very high working
pressures at which offshore lines can be oper-
ated partly make up for the loss in capacity due
to the smaller diameters. If necessary, pipeline
bundles are laid [98].
Offshore compressor stations are extremely
costly structures because they must be built on
platforms. For this reason, the optimum com-
pression ratio of offshore pipelines is higher than
that of onshore pipelines. Depending on ow, it
may be as high as = 4.
4.1.2. LNG Transportation
Although the energy input required for lique-
faction of natural gas is substantial (see Sec-
tion 3.3), the volume advantage makes lique-
faction economically viable. Cryogenic LNG is
shipped by LNG tankers at atmospheric pres-
sure. The cargo tanks are insulated to minimize
evaporation. Nevertheless, the boil-off rate is
between 0.2 and 0.25 % of the cargo per day.
The gas that evaporates is used to fuel the ships
engine. Reliquefaction is presently not viable.
Figure 28. Cost of LNG transportation and cost of pipeline
transmission as a function of transportation distance
a) Offshore pipeline (900-mm diameter); b) LNG transporta-
tion with liquefaction onshore (125 800 m3 ); c) Onshore
pipeline (1000-mm diameter)
The transportation of LNG is often the only
way of bringing gas from distant gas-producing
countries to market outlets. Any cost compar-
ison between LNG transportation and pipeline
38 Natural Gas

transmission must, of course, be geared to the l

p21 p22 = 4.64011015 f Q2
n T K (3)
circumstances of the project. Generally speak- d5 n
ing, an LNG chain is the only answer if pipeline where Qn is the hourly ow rate under normal
transmission is not feasible for technical or other conditions (m3 /h); p1 the absolute pressure at the
reasons or if the distance is sufciently long. The pipeline inlet (bar); and p2 the absolute pressure
cost of LNG transportation is lower than that at pipeline outlet (bar).
of offshore pipeline transmission even for dis- Equation (3) may be rewritten using the fol-
tances of several hundred kilometers, whereas lowing terms
onshore transmission is nearly always less ex-
pensive than LNG transportation unless the dis- p21 p22 = K cQ2n (4)
tance is extremely long [97, 99101]. A compar-
ison of costs of LNG transportation and pipeline where
transmission is given in Figure 28 (see previous
l
page). c= 4.64011015 f 5
n T
d


c bar2 h2 m6 (5)

4.1.3. Gas Transmission Pipeline Design

According to Nikuradse, the pipe friction
Pipelines for gas transmission must be designed factor f for turbulent ow and rough-surface
so that, under peak load conditions, gas is al- pipes is given by [102].
lowed to ow from the point of delivery at the
inlet of the system to the outlet of the system 1
f =  2 (6)
at a pressure between the maximum and min- d
2log k +1.14
imum allowable operating pressure. Generally,
pipeline capacity is somewhat lower in summer According to the Colebrook equation, the fol-
than in winter because of the following reason: lowing applies to the friction factor in the tran-
The atmospheric temperature increases soil tem- sition regime between a hydraulically smooth
perature and hence gas temperatures, and power and a hydraulically rough pipe surface:
output from the compressor engine decreases be-  
1 2.52 k
cause of the higher temperature of the intake air. = 2log + (7)
f Re f 3.71d
According to Darcy and Weisbach, the pres-
sure drop in a gas transmission pipeline is given where k is the surface roughness factor.
by the following equation: The limit between hydraulic roughness and
the transition regime is given by
16 l T
p21 p22 = f
n qn2 pn K (2)  2
2 d5 Tn 200 d
fl = (8)
Re k
where p1 and p2 are absolute pressures (Pa); pn
is the normal pressure, 1.01325105 Pa; p21 p22 where the Reynolds number Re can be calculated
represents the pressure drop (Pa2 ); T is the ab- by using the following equation:
solute temperature (K); T n the normal tempera-
ture, 273.15 K;
n the gas density under normal Q2n
n
Re= 353.678 (9)
conditions (kg/m3 ); f the pipe friction factor; qn d
the ow rate under normal conditions (m3 /s); l where is the dynamic viscosity of the uid
the length of the pipeline (m); d the diameter of (106 P a s).
the pipeline (m); K the gas ow deviation coef- If the pipe friction factor is f l , then the ow
cient; and subscript 1 denotes the pipeline inlet is in the transition regime.
and subscript 2 the pipeline outlet. For the design of new lined large-diameter
Equation (2) is usually transformed into the pipelines, the pipe roughness factor k (in mm) is
following equation in which the pressure is ex- used in ow calculations:
pressed in bar and the ow rate in cubic meters
per hour: Hydraulically rough regime (Nikuradse)
0.012 mm
 Natural Gas 39

Transition regime (Colebrook) 0.006 Looping of Pipeline Sections. The increase

0.008 mm in capacity due to the installation of compressor
stations increases the system cost in steps [104].
The gas ow deviation factor K describing
For this reason, additional compressor horse-
the real-gas behavior of natural gases is another
power is not a cost-efcient method of increas-
important term in ow equations. For most nat-
ing capacity for all additional capacity require-
ural gases, K may be approximated by
ments. Alternatively, pipeline sections may be
looped to obtain exactly the additional capacity
K = K (pm ,Tm )
that is needed. The increase in capacity achieved
2 p31 p32
pm = (10) by a loop line of the same diameter as the main
3 p21 p22 line is given by the following formula (if no gas
is taken off between the inlet and the outlet of
the pipeline system):

4.1.4. Increase in Capacity QL 1

If the capacity of an existing pipeline must be
increased, (1) new compressor stations can be
installed or (2) pipeline sections can be looped.
Installation of New Compressor Stations.
The increase in capacity that can be achieved by
the installation of compressor stations is given
by
Qn
= n + 1100 %
Q0
where Qn is the capacity of the system with com-
pressor stations (m3 /h); Q0 is the carrying capac-
ity without compressor stations (m3 /h) and n is
the number of compressor stations.
To maximize the increase in carrying capac-
ity achieved by the installation of compressor
stations, the compressor station sites must be op-
timized. The optimum site depends on whether
ow is constant throughout the pipeline system
or varies because of offtakes between the inlet
and the outlet of the system (see Table 11) [103].
=  100 % (12)
Q0 1 34 LL
1
where QL is the capacity after addition of a loop
line of length L 1 (m3 /h); Q0 is the capacity with-
out looping (m3 /h); L is the length of pipeline
between inlet and outlet (m); and L 1 the length
of the loop line (m). The length of the loop line
required to provide a specied additional capac-
ity depends critically on whether or not gas is
tapped from the pipeline system between the in-
let and the outlet points [103].
(11)
The increase in capacity as a function of loop
line length is plotted in Figure 29. If a loop line
of the same diameter is assumed, 75 % of the
main line must be looped to increase capacity
by 50 % if all gas ows from the inlet to the out-
let of the transmission system. If gas is taken
off regularly between the inlet and the outlet (as
in the case of a regional line), only 40 % of the
original pipeline has to be looped.

Table 11. Optimum compressor station sites

Number of Site, % of total length

compressor Pipeline Pipeline Maximal

stations without with transport
offtake offtake capacity, %

0 100
1 50 21 141
2 33 / 67 13 / 31 173
3 25 / 50 / 75 9 / 21 / 38 200
4 20 / 40 / 60 / 80 7 / 16 / 26 / 42 224 Figure 29. Increase in carrying capacity as a function of loop
length
a) Pipeline without offtake; b) Pipeline with offtake
40 Natural Gas
4.1.5. Transient Flow in Gas Transmission
Systems
Flow rate and pressure in pipelines are a function
not only of distance but also of time. Therefore,
line packing effects play an important role. Sim-
ulation of transient ow, of course, produce dif-
ferent results than steady-state simulation. In a
typical gas system, for instance, an hour of peak
demand is usually preceded by a phase of low
demand. As pressure increases when demand is
low, a large gas volume is packed in the line
when the demand peaks. During the period of
peak load offtakes, the pressure in the line de-
creases because of the pressure drop resulting
from the higher gas ow velocity through the
line. Part of the gas packed in the line is there-
fore discharged from the system, covering peak
demand.
Figure 30. Transient ow in gas transmission systems
A) Constant ow rate at pipeline inlet; B) Constant pressure
at pipeline inlet
Figure 30 shows the ows through a pipeline
system into which gas is delivered at location
1 and from which gas is taken off at location
2 at different load factors. If the ow rate at the
pipeline inlet (location 1) is constant (Fig. 30 A),
inlet and outlet pressures will vary considerably
and line packing will contribute substantially to
covering peak load demand. As gas is normally
delivered into a pipeline system at a continuous
rate, the line will be repacked during periods of
low demand, for example, during the night. If
delivery into the pipeline system is at constant
pressure (Fig. 30 B), the delivery rate will vary.
However, the response at the point where gas is
delivered into a pipeline system is always de-
layed with respect to the system behavior at the
point where gas is taken off from the system; for
this reason, delivery into the system and delivery
from the system never coincide exactly.
4.2. Storage
Gas storage facilities are integrated into the
pipeline system to match the high load factor at
which gas is produced and delivered by suppliers
to the pattern of end-user demand, which varies
between winter and summer, over the week, and
from hour to hour.
4.2.1. Determination of Storage
Requirements
Gas demand is inuenced by many different
physical and economic parameters. Because
substantial quantities of gas are used for space
heating, ambient temperature is the most crit-
ical one. Typical average daily deliveries Qdi
in Northwestern Europe as a function of tem-
perature are shown in Figure 31. Gas demand
increases as a linear function of temperature de-
crease and is constant above a certain limit tem-
perature. The correlation is represented by the
following equation:
Qdi = Qdg + m (tl ti ) (13)
where Qdi is the daily gas demand at the daily
average temperature t i (kW h/d); Qdg the daily
baseload gas demand (kW h/d); t l the limit tem-
perature for space heating ( C); t i the average

temperature on a given day ( C); and m the in-
crease in deliveries per C decrease in temper-
ature (kW h d1 C1 ). This equation allows
sufciently accurate predictions of daily gas off-
takes [98].
Figure 31. Daily average delivery as a function of tempera-
ture
10 m (slope) = increase in delivery per degree temperature
decrease
Transmission, storage, and distribution facil-
ities must, of course, be sized for the design day
peak load on the system, determined by Equa-
tion (13). The ratio between system capacity
specied for peak load conditions and capac-
ity utilization is a crucial commercial and eco-
nomic factor. Utilization time or system load is
expressed differently in various countries.
In Central Europe, the concept of utilization
time expressed in annual utilization hours or
annual utilization days is frequently employed.
Utilization time is given by equations (14) and
(15):
Utilizationhoursperyear =
Annualgasvolume
(14)
Peakhourly volume
Utilizationdaysperyear =
Annualgasvolume
(15)
Peakdaily volume
Natural Gas 41
In the United States and the United Kingdom,
the load factor expresses the same relationship.
It correlates with the quantities given in Equa-
tions (14) and (15) as follows:
Annualvolume
Loadfactor =
8760 Peakhourly ow rate
Annualutilizationhours
Loadfactor = (16)
8760
Irrespective of the actual load of the system,
transmission, storage, and distribution facilities
must be designed for adequate gas supplies re-
gardless of ambient temperature or other condi-
tions. With regard to storage facilities, gas deliv-
eries from storage must at all times be sufcient
to satisfy any demand in excess of gas supplies
from gas elds into the transmission system. The
volume of gas that is stored must be adequate to
maintain this delivery throughout the period for
which demand exceeds eld supply. The neces-
sary storage capacity is thus determined by the
difference between the eld supply load pattern
and the demand load pattern, as well as by ambi-
ent temperature during the period in which sup-
ply is lower than demand. The volume of gas
needed to satisfy peak demand must be stored
from excess eld supplies during off-peak peri-
ods. A typical daily load curve for a period of
one year (for Northwestern Europe) is shown in
Figure 32.
Figure 32. Daily load curve showing gas delivered from
storage and gas added to storage
42 Natural Gas
4.2.2. Storage Systems
Different systems are used by the gas industry to
store gas during off-peak periods and to deliver
gas from storage for peaking service. Various
storage systems serve different peaking needs
(see Table 12). The storage of gas in low-pres-
sure containers has decreased substantially in
importance because the quantity of gas stored in
such a facility is insufcient.
Table 12. Suitability of various storage systems for different peak
needs
Peaks
Daily Weekly SeasonalSystem operator
Low-pressure local distribution
container companies
High-pressure
container
Line packing limited regional transmission
companies
Cavern, elds limited supraregional
transmission
companies
Storage pipe arrays or spherical gas tanks
in which gas is stored at high pressure provide
peaking service for diurnal swings and short
peaks within a week. Spherical gas tanks op-
erate between 0.6 and 1.6 MPa and can have a
diameter as large as 30 m. Pipes used for storage
may hold gas at a pressure up to 8 MPa.
Line packing in high-pressure gas transmis-
sion pipelines is a method of handling diurnal
peaks. For line packing, the pipeline must have
a large diameter and must be designed for high
working pressure. Line packing is feasible only
if at least temporary spare capacity is available
in the system. Normally, the transmission sys-
tem design engineer plans a line packing ca-
pacity approximately eight times the difference
between the hourly delivery rate and the peak
hourly sendout into the system. This capacity
corresponds to ca. 6 7 % of daily sendout.
Any demand peaks not provided for at the re-
gional or the local level must be handled at the
supraregional level. The quantities of gas that
must be stored for seasonal peak shaving are
substantial, and large underground storage fa-
cilities are practically the only system that will
hold sufciently large volumes of gas. Figure 33
shows the storage capacity that must be created
to handle seasonal space heating load peaks as
a function of supply load factor.
Figure 33. Storage capacity required for seasonal peak shav-
ing as a function of the supply pattern
Gas is stored below ground in appropriate
rock formations (see Fig. 34, next page). Suit-
able formations for underground storage of gas
include porous or ssured rock as well as cav-
erns mined in salt rock, for example. These
formations must be covered with impermeable
caprock to prevent gas from escaping.
The following types of underground storage
facility exist:
1) depleted gas elds, oil elds, and aquifer
storage facilities (porous rock storage);
2) salt cavern storage facilities; and
3) mined cavern storage facilities (only of mi-
nor importance).
Underground storage facilities hold both
working gas and cushion gas. Working gas is
the gas that may be produced from storage for
peak-shaving operations.
Cushion gas, sometimes referred to as base
gas, is the gas required to ensure sufcient reser-
voir pressure for recovery of the working gas. It
provides the pressure needed to cycle the normal
working storage volume.
Porous Rock Storage. Gas can be stored
below ground in rock pores. The rock should
have sufcient porosity and permeability, and
the storage horizon (which must be at sufcient
depth) should be covered by tight caprock and
be a structure that entraps gas injected into the
rock. Structures used for porous rock storage
include depleted oil and gas elds as well as
aquifer structures. Development of a gas stor-
age facility in a depleted gas eld does not pose
a major risk because data on rock properties and

Figure 34. Underground storage facilities for natural gas
information on the tightness of the caprock are
available. The working gas capacity, the maxi-
mum reservoir pressure, and the delivery rates as
a function of reservoir pressure are known from
production history. For the storage of gas in de-
pleted oil elds, gas oil separators are needed;
however, secondary oil production by gas injec-
tion often makes a depleted oil eld a commer-
cially attractive storage site [105].
In aquifer storage reservoirs, interstitial wa-
ter in the pores is displaced by the gas injected
at high pressure. Considerable geological and
reservoir engineering effort is required to decide
whether an aquifer structure is suitable for un-
derground storage of gas: i.e., the structure of the
potential storage horizon must be evaluated; the
thickness, porosity, and permeability of the stor-
age rock must be determined; and the thickness
of the caprock must be veried.
Salt Cavern Storage. Gas may also be stored
in caverns leached into salt rock. Unlike the vol-
ume of a natural storage rock reservoir, the vol-
ume of these cylinder-shaped caverns can be
controlled within certain limitations. The diam-
Natural Gas 43
eter of such a cavern may be as large as 80 m and
its height 400 m. The cavern volume can reach
500 000 m3 .
The capacity of cavern storage facilities can
be adapted to increased storage needs by adding
further caverns in a given formation as required.
The cushion gas volume required for operation
of a storage cavern is much lower than the base
gas volume in a porous rock reservoir and may
amount to only 20 % of total capacity. Storage
caverns allow the production and injection of gas
at very high rates that are limited chiey by the
capacity of the above-ground installations.
In salt storage caverns, convergence can oc-
cur because cavern leaching operations and pres-
sure cycling after commissioning produce strain
in the rock. As a result, salt ows into the cavern,
reducing its volume. Within limits, convergence
may be controlled by retaining a minimum quan-
tity of gas in the cavern [102,105107].
4.2.3. Optimized Storage Planning
As the load curve in Figure 32 shows, storage
facilities produce gas for only relatively short
44 Natural Gas
Figure 35. Optimum production of gas from porous rock storage and salt cavern storage for peak shaving
periods of time. Depending on supply and de-
mand load patterns, gas withdrawal is required
for peak shaving on 80 150 days per year. If the
ambient temperature rises, the withdrawal phase
may be interrupted on days in which demand is
lower than supply thereby allowing more gas to
be injected into a partially depleted storage fa-
cility.
With porous rock storage facilities, pro-
duction rates are limited by the resistance of
the rock to gas ow to the wells. Depending
on depth, reservoir pressure, and permeability,
wells may produce gas at rates between 1000 and
70 000 m3 /h (STP). At salt cavern storage sites,
the withdrawal rate is limited only by pressure
loss in the tubing and the design of above-ground
facilities. Storage caverns today are normally de-
signed for production rates of up to 250 000 m3 /h
(STP). However, because gas cools rapidly dur-
ing depressurization, production at such a high
rate is feasible only for a relatively short dura-
tion up to 60 h in a limited number of production
phases during the year. Similar restrictions do
not exist for porous rock storage facilities, which
normally hold substantially larger quantities of
working gas that is produced at lower rates. The
working gas volume at a salt cavity storage site,
on the other hand, may be increased by leaching
an appropriate number of caverns.
Transmission system operators optimize their
peak-shaving operations by employing both
porous rock and salt cavern storage facilities.
The peaking service baseload is provided by the
production of gas from porous rock facilities
at relatively constant load, whereas caverns are
used in periods of maximum demand. The op-
timum employment of storage caverns and stor-
age reservoirs depends, of course, on supply and
demand load patterns (see Fig. 35).
4.3. Distribution
Distribution systems take gas from regional sup-
ply centers and transport it to residential, com-
mercial, and industrial users. These systems
consist of high-pressure, medium-pressure, and
low-pressure grids. Distribution systems tend to
be operated at low load factors because they
serve a market in which demand varies consid-
erably. If most gas is used for heating, the grid
is designed for peak load on a winter day.
Distribution grids have grown in most ar-
eas over the years because gasworks were built
in many cities long before natural gas became
available. For this reason, distribution grids con-
sist of mains of different diameters and different
materials laid in different years.
Old distribution lines often operate at 2
8 kPa, whereas new distribution mains are fre-
quently designed for a working pressure of
100 kPa. Low-pressure distribution grids are
normally tied into medium-pressure or high-
pressure distribution systems from which they
receive gas at special supply stations.
Since local distribution networks consist of
mains cross-connected at numerous points, com-
puters are required to predict ow in distribu-
 Natural Gas 45

tion lines. Early models and methods for solving pressures are often necessary to serve rural areas
these nonlinear patterns were proposed by Cross because 100-kPa distribution lines can transport
in 1936 and Mac Illroy in 1949 [108]. Substan- gas over much longer distances.
tial computing time is required for such a non-
linear model, which originally consisted of very
few nodes in view of the limited performance of
early computers. As data-processing technology
progressed during the 1950s, network analysis
techniques become more widely used. They are
now state of the art and are employed as a matter
of course in distribution system design. Modern
software models all the details of distribution
systems.
Many of the input data required for network
analysis can be determined only by statistical
methods and eld tests. For example, statistics
are necessary to predict system loads controlled
by the demand of numerous gas users whose me-
ters are usually read only once each year. Pipe
roughness, which is crucial for the hydraulic be-
havior of the grid, must be measured in many
cases because pipe properties depend on the year
in which the distribution line was constructed.
Distribution networks must also be designed
to handle peak loads that can be 10 or 15 times
higher than the baseload. To optimize the eco- Figure 36. Pipeline diameter as a function of working pres-
nomics of gas distribution, distribution system sure for constant pipeline capacity (in relation to pipeline
capacity is regularly adapted to growing de- diameter for 2.5-kPa working pressure)
mand. Methods of increasing capacity include
the following:
1) replacement of mains or laying of new lines;
5. Economic Aspects
2) increasing distribution system pressure often Natural gas is the worlds third most important
to a maximum of 10 kPa in old systems and energy source, behind oil and coal, covering ca.
installation of service regulators to lower the 23 % of the 1995 world energy demand.
pressure to 2 kPa at which most appliances
are operated; or Reserves. Proven world gas reserves at the
3) installation of new medium-pressure or high- end of 1995 totaled about 150 1012 m3 (V st i.e.,
pressure system stations to feed gas into the standard cubic meter of natural gas at 15 C and
low-pressure grid. 101.3 kPa with a net caloric value of 35.2 MJ
New governor stations to interconnect ring or 9.776 kW h) (equivalent to 51711018 J or
mains and distribution lines constitute a particu- 134109 t of oil), corresponding to ca. 95 % of
larly effective method of increasing distribution proven oil reserves [111]. A geographical break-
grid capacity [109, 110]. Local distribution com- down is shown in Table 13. These reserves equal
panies normally combine all three methods to about 55 years of current annual gross produc-
optimize the economics of gas distribution. The tion.
new distribution lines that are increasingly being In addition, ca. 2221012 m3 (V st ) (equiv-
built to develop service in rural regions are de- alent to ca. 77701018 J or 200109 t of oil
signed mainly for a pressure of 100 kPa, because [112]) has been identied as probable gas re-
the higher distribution pressure substantially re- serves. Including this gure, the total 1995 gas
duces pipeline diameter for the same pipeline inventory equals approximately 135 years of
capacity (see Fig. 36). In fact, high distribution current annual gross production.
46 Natural Gas

Table 13. Worlds proven natural gas reserves as of January 1,

mer Soviet Union and Eastern Europe as well as
1996 [111] North America both produce and consume ca.
30 % of the worlds annual natural gas availabil-
Area 1012 m3 (V st ) 1018 J %
ity.
North America 6.5 222 4.3
Latin America 8.0 277 5.4
Western Europe 6.3 220 4.3
International Trade. Although marginal
Former Soviet Union, compared to total consumption, a sizable trade
Eastern Europe 59.2 2037 39.3 over national borders has developed since 1960.
Africa 10.0 346 6.7
Initial international deliveries were mainly
Middle East 45.3 1558\011 30.1
Asia, Oceania 14.8\011 512 9.9 to neighboring countries through pipelines,
Total 150.2 5171 100.0 whereas shipments of LNG developed in the
1970s. Table 15 summarizes the natural gas vol-
ume traded internationally in 1995. Of the total
Production. The worlds 1995 gross gas of 395109 m3 (V st ) (equivalent to 131018 J
production amounted to 2.75 1012 m3 (V st ) or 352106 t of oil) traded, approximately
(95.15 1018 J or 2.4109 t of oil), of which 92109 m3 (V st ) or 23 % was received in the
about 80 % was marketed. The rest covers rein- form of LNG.
jection, aring, losses, etc. The total 1995 mar-
keted volume of 2.211012 m3 (V st ), broken Pricing. Except for a minor amount used
down into major geographic zones, is shown in as chemical feedstock, natural gas is primar-
Table 14. ily employed as clean heating fuel in indus-
Table 14. World natural gas in 1995 [109 m3 (V ST )] [111] try, power plants, commercial installations, and
households. To maintain its competitiveness ver-
Area Marketed Consumption sus alternative energies, natural gas prices for
production
the nal consumer are generally determined by
North America 689 686 prices of competitive fuels such as light heat-
Latin America 101 103 ing oil, heavy fuel oil, coal, LPG, or electricity,
Western Europe 241 350
Former Soviet Union, with due consideration of the inherent environ-
Eastern Europe 734 657 mental, handling and nancial advantages of gas
Africa 84 46 utilization.
Middle East 145 145
Asia, Oceania 213 1220
Since gas transportation costs signicantly
Total 2207 2207 exceed those of oil or other fuels, gas netbacks at
the wellhead are generally lower than those for
crude oil. To compensate for the heavy front-
Consumption. Consumption patterns in var- end investment in production, purication, and
ious regions of the world generally follow pro- transportation facilities, a large share of inter-
duction proles, as shown in Table 14. The For- nationally traded natural gas is normally sold
Table 15. International gas trade in 1995 [109 m3 (V ST )]

Supplies from Imports to

Japan Germany United States France Italy United Kingdom Belgium Others Total

Former Soviet Union 32 13 14 58 117

Canada 79 79
Netherlands 25 6 4 5 1 41
Norway 11 7 2 3 5 28
Algeria 1 8 17 4 8 38
Indonesia 23 10 33
Malaysia 11 2 13
Brunei 7 1 8
United Arab Emirates 5 5
United States 2 2 4
Others 9 1 19 29
Total 57 69 80 34 35 2 12 106 395

by producers under long-term contracts of up
to 35 years duration, which oblige sellers to
make predetermined annual quantities available,
whereas buyers are obliged to offtake certain
minimum quantities per year (take-or-pay obli-
gation: usually 80 % of availability). Prices of
such long-term gas deliveries are generally tied
to ofcial international crude or fuel oil quota-
tions.
6. Testing and Analysis
Natural gas analysis can be divided into two ar-
eas: chemical analysis of the composition, and
determination of the physical properties. Chem-
ical analysis methods for natural gas are sum-
marized in [113, 114]. Instructions for both the
chemical analysis and determination of physical
properties for natural gases are given in [114].
For the analysis and quality control of gases,
see also Gas Production.
6.1. Analysis of Natural Gas
Composition
The most important method for chemical anal-
ysis of natural gas is gas chromatography [115
121]. Sampling must be carried out before the
gas can be analyzed.
Figure 38. Gas chromatograph
a) Carrier gas; b) Regulating valve; c) Manometer; d) Chart recorder; e) Air thermostat; f) Separating column; g) Thermal
conductivity detector; h) Flow meter; i) Three-way tap; j) Trap
Natural Gas 47
6.1.1. Sampling
Glass equipment is mainly used for sampling
because glass is not attacked by any component
of natural gas and does not affect the composi-
tion of the gas [122]. Vessels with two taps (see
Fig. 37) are used, which must be completely dry.
The gas to be analyzed is rst passed through
the sampling vessel to completely displace the
air from it. Both taps are then closed so that the
sample is contained in the vessel. The sample
should always be under slight overpressure, so
that no air is drawn into the vessel even if the
taps are not closed tightly.
Figure 37. Sampling vessel
6.1.2. Gas Chromatography
Gas chromatography has developed since 1952
and has replaced the Orsat method, previously
used for analysis of natural gas ( Gas Pro-
duction, Chap. 8.2.2.1.). Gas chromatography is
the preferred method for most gas analyses. The
analysis of natural gas by gas chromatography
has been standardized in ASTM D-1945. In gas
48 Natural Gas
Table 16. Standard reference mixtures for the chromatographic
analysis of natural gas

Component Lean gas, Rich gas,

mol % mol %

Methane 85.0 74.0

Ethane 6.0 10.0
Propane 4.0 7.0
n-Butane 2.0 3.0
Isobutane 2.0 3.0
n-Pentane 0.5 1.0
2,2 Dimethylpropane 0.5 1.0
Isopentane 0.5 1.0
Hexanes and higher
hydrocarbons 0.1 0.2
Nitrogen 4.0 0.5
Carbon dioxide 1.0 1.0
Helium 1.0 0.5
Hydrogen 3.0 0.5
Figure 39. Gas chromatogram of natural gas

chromatography, the gas to be analyzed is trans-
ported by a carrier gas stream (usually helium
or argon) through a separating column. Carbon
dioxide may also be used as carrier gas according
to the Janak ( Gas Production, Chap. 8.2.2.1.),
[123]. Figure 38 shows the setup for gas chro-
matography [118] and Figure 39 an example of a
gas chromatogram of natural gas [118]. The sep-
arating column is lled with a molecular sieve
or with Chromosorb.
Thermal conductivity detectors and ame
ionization detectors are most commonly used,
mass spectrometers may also be used for detec-
tion [117]. In some cases, two columns must be
used one for the separation of hydrocarbons,
the other (for a new sample) mainly for determi-
nation of nitrogen and oxygen. Standard refer-
ence mixtures are used for two gas qualities: lean
gas (i.e., gas containing few or no condensable
hydrocarbons and thus having a lower caloric
value) and rich gas (i.e., gas containing a higher
amount of condensable hydrocarbons and thus
having a higher caloric value) (see Table 16).
6.1.3. Analysis of Nonhydrocarbons
Natural gases can contain various gases apart
from hydrocarbons: nitrogen, carbon dioxide,
and noble gases can be determined during gas
chromatographic analysis of the hydrocarbons.
A gas chromatographic analysis method for non-
condensable gases in light hydrocarbons is given
in [124]. The content of water, sulfur com-
pounds, and mercury may also be determined.
Determination of Water. Water must be re-
moved from natural gas to prevent its condensa-
tion and to avoid the formation of gas hydrates
[125] (see Section 1.2). Low water content of
the order of milligrams per cubic meter can be
titrated according to the classical Karl Fischer
method, in which water reacts with iodine in an
alcoholic solution of sulfur dioxide and pyridine
[126]. The iodine can also be determined coulo-
metrically. Water can be determined gravimet-
rically by absorption using a desiccant such as
magnesium perchlorate. A variety of hygrome-
ters [127] measure, for example, the variation in
the conductivity of glycerol with water content.
Dew point measurements (see Section 6.2.4) in-
directly give the water content.
Determination of Sulfur Compounds. Nat-
ural gases can contain hydrogen sulde and oc-
casionally mercaptans (see Section 2.4). The to-
tal sulfur content can be determined by combus-
tion with excess air or oxygen. Either the sul-
fur dioxide formed can be determined, e.g., by
means of a coulometric titration, or the combus-
tion products can be absorbed in an oxidizing
solution and the sulfuric acid formed is deter-
mined.
Hydrogen sulde can be detected qualita-
tively using lead acetate producing a black col-
oration due to the formation of lead sulde.
In the ASTM standard test method a mea-
sured volume of gas is bubbled through two so-
lutions rst a neutral cadmium sulfate solution
and then a basic cadmium sulfate solution [128].
Hydrogen sulde is found in the neutral solution

and the mercaptans in the basic solution. Hydro-
gen sulde and mercaptans are then determined
iodometrically.
Determination of Trace Components.
Heavy metals, especially mercury (see Sec-
tion 2.3.2), are the most important trace compo-
nents. There are at present no standard determi-
nation methods; atomic absorption spectroscopy
(AAS) is usually used.
6.2. Determination of Physical
Properties
Natural gases are characterized and classied ac-
cording to their physical properties. The Wobbe
index (W ) (see Section 1.3.2) is the most impor-
tant characteristic for the classication of natu-
ral gases and they are divided into two groups:
group L (low Wobbe index) and group H (high
Wobbe index). The Wobbe index is calculated
according to
 
WS = HS / d MJ/m3 ,
where H S is the gross caloric value and d the
relative density (based on air). In addition to
the more commonly used superior Wobbe index
W S , the inferior Wobbe index W I can be calcu-
lated, whereby the inferior caloric value H I is
used instead of H S . The Wobbe indices indicate
gas quality for combustion.
Usually the Wobbe index is calculated from
H S and d. Automated calorimeters are available
for its direct determination (Wobbe recorders)
which use a gas stream that is adjusted
so that
the ow rate is proportional to1/ d. Important
physical properties of natural gas include the fol-
lowing:
Density
Caloric value
Molecular mass
Dew point
6.2.1. Density
Density can be measured with a gas density bal-
ance. The method is based on the different buoy-
ancy of a nitrogen-lled glass sphere suspended
Natural Gas 49
from a balance in various test gases [129]. The
gas to be measured and nitrogen should have
the same temperature and pressure. Instruments
of this type also allow continuous measurement
and recording of gas density in a gas stream.
A particularly reliable method is to weigh a
specic volume of gas in a glass ask (e.g., a
Chancel ask according to IP 59). Either the
density of the gas (mass per unit volume) or the
relative density d (the ratio of the density of the
gas to that of dry air) is determined. The den-
sity and relative density can also be calculated
from the composition determined by gas analy-
sis [130].
6.2.2. Caloric Value
The caloric value in MJ/m3 can be determined
in three ways: (1) directly by combustion of the
gas at constant pressure in a gas calorimeter, (2)
by stoichiometric combustion and measurement
of the gas : air ratio, and (3) by calculation from
the values obtained from gas analysis.
The principle of continuous recording gas
calorimeters is combustion of a controlled
stream of gas, followed by heat exchange bet-
ween the combustion gases and a liquid, whose
temperature increase is measured and recorded
[131]. This method is the most widely used. Dis-
continuous gas calorimeters involve combus-
tion of a specic amount of gas and the resulting
temperature increase is measured directly.
6.2.3. Molecular Mass
The molecular mass of natural gas is calcu-
lated as an average value from the concentrations
determined by gas analysis and the molecular
masses of the components (see Chap. 1).
6.2.4. Dew Point
In order to avoid condensation of water, the gas
temperature should not drop below the dew point
of the water contained in the gas. The dew point
can be determined directly by passing a constant
stream of gas over a polished metal mirror that is
slowly cooled. The dew point is the temperature
at which the rst signs of condensation appear on
50 Natural Gas
the mirror. These methods can be used for gases
under pressures of up to 10 MPa. Automated in-
struments using photocells are also employed
[132]. If the gas stream contains easily condens-
able hydrocarbons, then these must be washed
out by passing the gas through high-boiling liq-
uid parafn prior to determination.
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