Article No : a12_169

Gas Production, 1. Introduction

HEINZ HILLER, Lurgi, Frankfurt am Main, Germany
RAINER REIMERT, (formerly Lurgi) Engler-Bunte-Institut der Universit€at Karlsruhe,
Karlsruhe, Germany
HANS-MARTIN ST€oNNER, Lurgi, Frankfurt am Main, Germany

1. Types of Gases; General Overview of 4. Characteristics of the Basic Processes . . . . . 416

Production Methods and Characteristics . . . 403 5. Product Gas Treatment . . . . . . . . . . . . . . . . 418
1.1. Water Gas and Producer Gas . . . . . . . . . . . 403 5.1. Purification Processes . . . . . . . . . . . . . . . . . 418
1.2. Synthesis Gas and Reduction Gas . . . . . . . . 404 5.2. Conditioning . . . . . . . . . . . . . . . . . . . . . . . . 419
1.3. Town Gas and Medium-Btu Gas . . . . . . . . . 408 5.3. Byproducts. . . . . . . . . . . . . . . . . . . . . . . . . . 420
1.4. Biogas and Landfill Gas . . . . . . . . . . . . . . . 409 6. Acknowledgement . . . . . . . . . . . . . . . . . . . . 421
1.5. Rich Gas and Substitute Natural Gas (SNG) 409 References . . . . . . . . . . . . . . . . . . . . . . . . . . 421
2. Raw Materials for Gasification . . . . . . . . . . 410
3. Physicochemical Basis for Gas Production . 412

1. Types of Gases; General Overview Biogas and landfill gas (! Methane) are
produced during biological degradation of organ-
of Production Methods and ic matter. They may be collected and purified
Characteristics either to be used further (renewable energy) or to
prevent air pollution.
Gases for industrial or heating uses can be clas-
sified in various ways. The most appropriate 1.1. Water Gas and Producer Gas
classification appears by calorific (heating) value
ranges, in kJ/m3 (STP): The terms water gas and producer gas were first
used in solid fuel gasification technology. Both
types of gas were very important from the 1920s
Water and producer gas 4600 – 12 500 to the 1940s. They were the basis for producing
Synthesis and reduction gas ca. 12 500
Town gas and medium-Btu gas 16 700 – 20 000 synthesis gas, town gas, and fuel gas. The tech-
Biogas and landfill gas 18 000 – 29 000 nology is of only minor importance today because
High-Btu gas and substitute natural gas (SNG) 25 000 – 37 000 the raw material basis has shifted largely from
solid fuels to liquid and gaseous fuels, and high-
performance processes have been developed for
A distinction has deliberately been made be-
coal-based synthesis gas, town gas, and grid gas.
tween water gas and synthesis gas, although
water gas was formerly used in large quantities Production of Water Gas. Water gas is
for synthesis as well. However, the so-called usually produced in an alternating operation,
water gases are based on very specific raw ma- i.e., by alternately hot blowing a fuel layer with
terials and belong to a different generation of air and gasifying it with steam. Among its various
production methods compared to ynthesis gases modifications, the production of so-called blue
produced in modern plants. Reduction gas refers water gas from coke was the most common
to gases used in iron production. method, yielding gas with high hydrogen and
Synthesis gas is the basis for most of the carbon monoxide contents which was suitable
hydrogen (! Hydrogen) produced, and it is also for use as synthesis gas. By addition of higher
used as a fuel gas, e.g., in gas turbines (see ! Gas hydrocarbons, the calorific value of water gas
Production, 5. Examples of Complex Gas Pro- could be increased (carbureting) so it could be
duction Plants, Chap. 3.). used as town gas.

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a12_169.pub3
404 Gas Production, 1. Introduction Vol. 16

Although most water gas plants were based on A typical analysis of a producer gas, in percent by
coke, plants also operated with anthracite and volume, is
noncaking highly volatile types of coal (coal
water gas or double gas). Coal with a high volatile Carbon dioxide 5.5 Hydrogen 10.5
matter content gives gases with higher calorific Carbon monoxide 29.0 Nitrogen 55.0
values because gasification gas is supplemented
by a considerable amount of devolatilization gas. The higher heating values (HHV) for water gas
In the water gas process with its cyclic mode based on coke and for producer gas are 10 500 –
of operation, coke has two functions: (1) it reacts 12 500 kJ/m3 (STP) and 4600 – 6700 kJ/m3
with blowing air during warm-up and with steam (STP), respectively.
during gasification, and (2) serves as a heat The nitrogen content of water gas, amounting
regenerator. to ca. 5 vol %, does not originate from coke or
Because of the expensive raw material (coke), coal for the most part, but is due to the fact that air
complicated batch operation, and relatively low remains in the coke pores on transition from the
output per gasifier (6000 – 9000 m3 (STP)/h), blowing to the gasification period. This nitrogen
this method of producing synthesis and town content can be lowered by discarding a small
gases has been replaced by more up-to-date fraction of the gas produced at the beginning of
processes. The gas production of synthesis gas the gasification period.
plants based on either natural gas (in tubular
reformers; see ! Gas Production, 2. Processes,
Chap. 1.) or heavy oil (by partial oxidation; see 1.2. Synthesis Gas and Reduction Gas
! Gas Production, 2. Processes, Chap. 2.), and
of modern coal gasification plants (see ! Gas The gas production method used depends on the
Production, 2. Processes, Chap. 3.) is ten times raw materials. The raw materials are mainly natu-
higher than that of water gas plants. ral gas, naphtha, heavy vacuum residue, and coal
(see ! Gas Production, 2. Processes). In addition,
Production of Producer Gas. Producer gas unconventional fuels such as solid or liquid waste
is obtained by supplying a gasification agent materials or biomass gain interest. However, in the
consisting of air and steam continuously, rather recent decades most of the world production of
than cyclically, to a gas producer of the same synthesis gas was based on natural gas and sulfur-
general design as a water gas producer. This gas rich heavy vacuum residues. Because of more
has a lower calorific value than water gas because stringent environmental protection requirements,
it contains atmospheric nitrogen. Producer gas these residues may no longer be burned in boiler
was obtained from a variety of rotary grate gas plants in many countries, so their market value is
producers from the 1920s to the 1940s. Because often low. Countries that do not have these two
of its high nitrogen content, which cannot be raw materials, particularly countries in which no
eliminated at economically justifiable cost, this natural gas is available, often use naphtha. De-
gas is not suitable for use as synthesis gas; it was pending on certain boundary conditions such as
employed almost exclusively as fuel gas and as the relationship between oil and coal prices, as
an additive to town gases in municipal works. well as local factors and strategic considerations,
In addition to coke, noncaking coals were also plants based on coal will continue to be built.
used as feedstocks, and a few plants were also
built for the gasification of caking bituminous Production of Synthesis Gas. Because syn-
coals under atmospheric conditions and under thesis gas is processed under elevated pressure, a
pressure (Lurgi pressure gasification). trend toward operating gas production plants at
increasingly high pressure could be observed.
Nature of Water Gas and Producer Gas. Gas production at higher pressure reduces the
The following is a typical analysis of a water gas, cost of compressing synthesis gas to the required
in percent by volume: synthesis pressure.
Carbon dioxide 5 Hydrogen 50
Carbon monoxide 40 Nitrogen 5 Natural Gas as Raw Material (! Gas Pro-
duction, 2. Processes, Chap. 1.). Synthesis
Vol. 16 Gas Production, 1. Introduction 405

gases are produced from natural gas mainly in from naphtha is carried out almost exclusively
tubular reformers. If the atural gas contains vir- catalytically and at elevated pressure.
tually no nitrogen, a temperature of 750 – Externally heated tubular reformers contain-
800
C is sufficient for gas suitable in ammonia ing special catalysts are used to produce hydro-
synthesis. Residual unreacted methane is re- gen-rich gases (e.g., ammonia synthesis). Two
formed in a secondary reformer (catalytic partial processes stand out from the others: they differ in
oxidation with air) with simultaneous adjustment the types of tubular reformers recommended and,
of its nitrogen content. primarily, in the type of nickel catalyst used.
For normal methanol synthesis, reforming is Topsøe uses a nickel catalyst without alkali; ICI
performed in one step in a tubular reactor at employs one with a definite alkali content.
850 – 900
C in order to leave as little methane In future naphtha might replace methanol as a
as possible in the synthesis gas. raw material for hydrogen produced on board of
For large methanol synthesis plants, Lurgi has vehicles driven by fuel cells. Due to the much
introduced a two-step combination that gives smaller size of such production units as com-
better results. In the primary tubular reformer, pared with plants in the petrochemical industry
lower temperature (ca. 800
C) but higher pres- and due to restrictions by volume and by utilities
sure (2.5 – 4.0 MPa instead of 1.5 – 2.5 MPa) (e.g., steam and water), the production scheme
are applied. The secondary reformer operates and above all the reactors and heat exchangers for
with a fixed catalyst bed as in the case of ammo- naphtha reforming in vehicles look rather
nia synthesis gas, but pure oxygen is used for different.
partial oxidation. Apart from single-stage tubular reforming,
More recently, Lurgi developed another two- two-stage processes have also proved successful
step gas production scheme. It is based on cata- for the production of gases rich in carbon
lytic autothermal reforming with an adiabatic monoxide, such as those required for methanol
prereformer and has economical advantages for and oxo synthesis. An example of a two-stage
very large methanol plants (! Gas Production, process is the Recatro process, developed by
5. Examples of Complex Gas Production Plants, BASF – Lurgi. Here, naphtha is converted
Chap. 1.). with relatively little steam in an initial low-
The various tubular reformer designs differ temperature adiabatic stage over a special nickel
primarily in the method of firing the catalyst- catalyst to produce a rich gas containing ca.
containing tubes (from the side or top, terraced, 60 – 65 vol % methane plus hydrogen and
or from the bottom). Subsequent developments carbon dioxide. This gas is supplied together
of combined reforming resulted in the integration with the remaining steam to a conventional
of the primary and the secondary reforming step tubular reformer to be reformed to carbon
in one apparatus using the thermal energy of the monoxide-rich synthesis gas in the presence of
effluent of the autothermal process for heating a conventional catalyst. The two-stage opera-
the steam reformer part (M.W. Kellogg, Uhde). tion makes carbon dioxide recycling unneces-
Exxon tested the simultaneous reforming and sary in many cases or reduces it considerably.
partial oxidation of natural gas in a reactor with A few plants using partial oxidation with
fluidized catalyst. Apart from tubular reformer (Lurgi) or without (Shell, Texaco) catalysts have
technology with or without a secondary reformer, been built.
partial oxidation (in one step) is still used
sporadically for reforming natural gas. This can Heavy Fuel or Residual Oil as Raw Material
be performed either noncatalytically (Shell, (! Gas Production, 2. Processes, Chap. 1.).
Texaco) or catalytically (Lurgi). The latter is For the production of synthesis and reduction
used especially when low ratios of hydrogen to gases from heavy and residual oils, two processes
carbon monoxide are required. are accepted worldwide: the Shell and the Texaco
process, both operating under elevated pressure
Naphtha as Raw Material (! Gas Produc- and noncatalytic. The Texaco process was origi-
tion, 2. Processes, Chap. 1.). The purity of nally designed for partial oxidation of natural
naphtha allows the use of catalysts. Therefore, gas; the Shell process, developed later, was
the production of synthesis and reduction gases tailored from the beginning to gasification of
406 Gas Production, 1. Introduction Vol. 16

heavy oil. The differences between the two pro- latter two processes has a high carbon monoxide
cesses are virtually negligible and involve only content, requiring considerable conversion
details of equipment design. measures for certain syntheses. The gasification
processes applied to coal are also suitable for
Coal as Raw Material (! Gas Production, 2. petrol coke if they can cope with its low reactivity
Processes, Chap. 3.). Processes employing coal and they are also applied when biomass or waste
that are used in practice operate on a noncatalytic materials are used as fuels.
basis. Various processes operating under elevat-
ed pressure are available: Lurgi, BGL (British Production of Reduction Gas. In principle,
Gas/Lurgi), HTW (High Temperature Winkler), reduction gas production is very similar to that of
U-Gas, Texaco, Shell and Prenflo. The Kop- synthesis gas. However, iron ore is usually re-
pers – Totzek process and the original Winkler duced under atmospheric conditions, so reduc-
process operate at atmospheric pressure. Coal tion gas can be produced at atmospheric or
gasification plants for the production of synthesis slightly increased pressure. Reduction gases used
gas built since the 1950s are based essentially on for the production of sponge iron by various
the Koppers or Lurgi processes. direct reduction processes (! Iron, Section
In view of the distribution of fossil fuels in the 2.6.) must meet certain requirements. Generally,
world – almost ten times as much coal exists as the proportion of oxidizing components such as
petroleum and natural gas, and it is distributed steam and carbon dioxide in the gas mixture
relatively uniformly – and the sharp increase in produced should be as low as possible, always
oil prices in the 1970s, efforts have been made in < 10 %. This goal can be achieved by cooling the
many countries to develop new coal gasification gases produced from coal, oil, naphtha, or natural
processes tailored to the requirements of partic- gas and removing carbon dioxide. However,
ular countries and their coal deposits. because reduction gases in the shaft furnaces of
In most processes, the heat required for gasi- steel works are needed at high temperature, more
fication is provided by partial oxidation with pure cost-effective solutions are being sought and
oxygen. These processes are based essentially on used. In the Midrex process natural gas is con-
the following three process arrangements: verted at ca. 1000
C in the tubular reformer,
without the addition of steam, thereby producing
1. moving bed, only hydrogen and carbon monoxide; the con-
2. one or more fluidized beds, and version is such that the reformed gases can be
3. entrained-flow systems in which coal dust and used directly in the shaft furnace.
the gasification agent are conveyed co- As the recovery of byproducts from coke oven
currently. raw gas (benzene, phenol) loses economical
attractiveness, reduction gas is considered to be
Combinations of these three process arrange- produced from coke oven raw gas by catalytic
ments are being investigated, as are processes partial oxidation.
applying high-temperature melts.
The overall arrangement of various coal gas- Composition and Aftertreatment. Synthe-
ification plants, including downstream units, is sis gas requirements depend on the intended
determined essentially by the composition of the application.
raw gases. The gases produced at increased
pressure by the Lurgi and by the BGL gasification Ammonia synthesis units now generally op-
processes contain methane, which can be con- erate between 13.0 and 22.0 MPa and require gas
verted to carbon monoxide and hydrogen for with a hydrogen: nitrogen ratio of 3: 1. Impurities
downstream ammonia or methanol synthesis, or are limited in modern processes to < 1 ppm for
can be removed before entering the high-pressure sulfur and 2 – 10 ppm for oxygen-containing
compressor. The Koppers – Totzek, the Texaco, components such as oxygen itself, carbon diox-
as well as the other entrained-flow processes ide, and water. With a view to the economy of
yield a gas without methane, but with a higher synthesis (i.e., the purge gas quantities to be
specific oxygen consumption. As in all high- branched off), the methane content of synthesis
temperature gasification processes, gas from the gas must not exceed 0.5 – 0.8 vol %.
Vol. 16 Gas Production, 1. Introduction 407

This means that the reformer and gasification each of them arbitrarily is 2.0. A higher carbon
gases produced from various raw materials must monoxide content is required for fuel methanol
be conditioned appropriately. If the methane synthesis (Lurgi Octamix and others), in which a
content is originally considerably high it can be mixture of methanol and higher alcohols is pro-
lowered by secondary reforming with oxygen or duced as an additive to motor fuel. For high-
air. Because all reformed gases contain carbon pressure methanol synthesis (35.0 MPa), which
monoxide, they have to be converted, irrespec- is still used in a few cases, the presence of
tive of the raw materials from which they are methane adds an economic burden (as in ammo-
produced; this is done by catalytically reacting nia synthesis). It is less important in low-pressure
carbon monoxide with steam to form hydrogen (5.0 – 10.0 MPa) methanol synthesis (ICI, Lur-
and carbon dioxide (shift conversion). Depend- gi) because compression costs for this gas com-
ing on its residual content after shift conversion, ponent are practically negligible because of the
either the carbon monoxide concentration must lower compression ratio required. The content of
be lowered (to the ppm range) in a methanation sulfur compounds in the gas used for low-pres-
stage or it must be removed at low temperatures sure methanol synthesis, which is based on a
by a liquid nitrogen wash. Hydrogen sulfide, special copper-containing catalyst, must be ex-
organic sulfur compounds, and carbon dioxide tremely low. The amount of hydrogen sulfide and
have to be removed by appropriate washing organic sulfur compounds in the synthesis gas
procedures. produced from raw materials with relatively high
Similar conditioning and purification process- sulfur content can be lowered to ca. 0.1 ppm by
es have to be applied for the production of special processes (Rectisol for coal and oil gasi-
hydrogen for fuel cells (! Fuel Cells). fication gases; hydrogenation of the organic sul-
fur compounds in the presence of Comox and
Methanol is generated from carbon monox- Nimox catalysts, and subsequent adsorption pri-
ide as well as from carbon dioxide: or to the reforming of naphtha and natural gas in
the tubular reformer).
2 H2 þCO CH3 OH
Purities applicable in methanol synthesis are
also required for oxo synthesis. However, be-
3 H2 þCO2 CH3 OHþH2 O
cause the latter often requires a hydrogen: carbon
monoxide ratio of ca. 1: 1, the carbon: hydrogen
The preferred reaction path goes via carbon ratio of the feedstock may require that carbon
monoxide, some carbon dioxide is required for dioxide be recycled or fed to the gasification unit.
kinetic reasons. The ratio ðcH2  cCO2 Þ= For iron ore reduction gas, the sulfur content
ðcCO þ cCO2 Þ should generally be between 2.0 must be reduced to a few parts per million.
and 2.2. The theoretical value derived from Table 1 shows typical analysis data for raw
adding both reaction equations after pondering gases from various starting materials.

Table 1. Typical raw gas analyses

Content, vol %

Feedstocks and processes H2 CO CH4 C2þ N2þ Ar CO2 H2S þ COS

Coal
Lurgi pressure gasification 43 12 11.5 1 0.3 32 0.2
BGL 28 57 7.1 0.4 4.2 3 0.3
Koppers – Totzek 30 55 0.1 1.4 13.2 0.3
Texaco 37 41.3 0.1 0.6 20.7 0.3
Oil gasification
Shell – Texaco 46 47 0.5 0.6 5.5 0.4
Naphtha
Tubular reformer 67 19 3 11
Recatro (BASF – Lurgi) 66 22 4 8
Natural gas
Tubular reformer 73 16 4 7
408 Gas Production, 1. Introduction Vol. 16

1.3. Town Gas and Medium-Btu Gas tightened toward the end of the 1950s and begin-
ning of the 1960s, plant operators turned to
Because natural gas (! Natural Gas) has become processes using lighter hydrocarbons and contin-
the preferred fuel gas for households and industry, uous operation. The development of special
the production of town and medium-Btu gas from catalysts (ICI, Topsøe) permitted gas production
coal and liquid fuels is of minor importance today. from readily available liquid feedstocks (such as
High-temperature coking – formerly general lighter hydrocarbons and naphtha having a boil-
practice in town gas works – has disappeared ing end point up to 200
C) to be carried out in
almost completely (! Coal Pyrolysis). The externally heated tubular reformers. Apart from
following is a brief outline of gasification pro- its higher efficiency, this mode of operation had
cesses for the production of town gas. an additional advantage because the gases pro-
duced were available at increased pressure, thus
Basis of Production. When charcoal was reducing the expenditure for their distribution in
replaced in the last century by coke from bitumi- pressure gas systems. The methane content of the
nous coal to smelt iron in blast furnaces, large gases could be increased by keeping reaction
quantities of degasification gas were produced by temperatures in the tubular reformer low, so that
the carbonization of caking coals. Initially, these after a cold carbureting stage with propane –
gases were largely flared; later on, they were butane, standard town gas could be produced.
distributed through piping systems supplying gas Cold carbureting was often not applicable
particularly to the municipalities in the neigh- because either propane – butane was not avail-
borhood of steelworks. The gas grids were large able at a reasonable price, or certain standards
enough to provide sufficient gas from the coke with respect to dew-point were not met, there-
ovens even at times of peak demand; on Sundays fore, modified processes aiming at increased
and holidays, the gas was flared in the coking production of methane from naphtha (BASF/
plants. Lurgi, British Gas, Japan Gasoline Corp.) were
With the increasing demand for grid gas, developed. Because methane content increases
utilization of the gas system improved, so that with decreasing temperature according to ther-
towns had to build their own gas production modynamic equilibrium, appropriate catalysts
facilities to meet peak requirements. These facili- had to be developed. In these processes, a so-
ties were based mainly on water gas, which in called rich gas having a methane content of ca.
some cases was carbureted. 65 vol % is produced from naphtha and steam by
Both solid and liquid or gaseous fuels were a slightly exothermic reaction in a shaft reactor at
used as raw materials for town gas production. 400 – 490
C. Because the calorific value and
Liquid hydrocarbons such as fuel oil and, later specific gravity of this gas are too high, compared
on, naphtha were preferred, but coal was also with pertinent standards for town gas, part of
used. it must be reformed in a downstream tubular
Plants using fuel oil are based mainly on a reformer using commercial catalysts and then
cyclic process arrangement and became very remixed with the residual methane-rich gas.
successful since the 1950s. Some of them use Another method of obtaining a leaner gas is to
straight thermal processes without catalysts, but add nitrogen or air. Many European cities built
most employ a catalyst bed. During a blowing plants of this type with town gas capacities up to
phase, a bed of catalytic or noncatalytic material 1  106 m3 (STP)/d.
is heated by the combustion of fuel oil with air. Plants that converted propane – butane to
After switching to the gasification period, fuel oil town gas via externally heated tubular reformers
is passed over the hot bed along with steam. The were built particularly for small capacities. Part
ONIA GEGI and SEGAS processes and the of the propane – butane was added to increase
Koppers Cowper process have become widely the calorific value of the reformed gas after
known [1]. carbon monoxide shift conversion. A few plants
The disadvantages of these cyclic processes produced town gas by reforming natural gas in
are their relatively low output and difficulties externally heated tubular reformers for transi-
caused by excessive wear of the switchover tional periods. This was done mainly when the
mechanism. In addition, as environmental laws consumers’ existing piping systems and burners
Vol. 16 Gas Production, 1. Introduction 409

were to be used, even if a loss in efficiency had to Depending on the nature of landfill waste, the
be accepted in converting natural gas to town gas. gas may also contain considerable amounts of
Oil gasification by partial oxidation (Shell, halocarbons.
Texaco, Lurgi; see ! Gas Production, 2. Pro-
cesses, Section 2.2.2.) has not become important
in town gas production because of the high 1.5. Rich Gas and Substitute Natural
investment cost of such plants. The gases pro-
Gas (SNG)
duced, consisting essentially of hydrogen and
carbon monoxide must be carbureted to comply
Basis of Production. As a result of the
with standards.
doubts concerning gas supplies and their avail-
Along with the development of gas production
ability to the industrial nations in the 1970s
processes, downstream gas conditioning and gas
efforts were made to produce synthetic natural
cleaning units were adapted as well. Carbon
gas from the plentiful coal supplies. These efforts
monoxide shift conversion plants often reduced
were feasible where natural gas accounted for a
the carbon monoxide content to < 3 vol %,
high percentage of primary energy and cheap
sometimes even to < 1 vol %, to eliminate the
domestic coal was available. Thus, a plant was
danger of poisoning.
built in North Dakota (United States) which
The composition of town and grid gas is given
has gone into operation in 1984, producing ca.
in (! Gas Production, 6. Analysis and Quality
3.9  106 m3 (STP)/d of SNG from lignite. In
Control). Group A in these tables corresponds to
this plant, lignite is gasified in Lurgi pressure
town gas; Group B, to grid gas; and the first gas
gasifiers, and the methane content required is
family, to town and grid gases combined.
adjusted by reacting carbon monoxide and
hydrogen from the raw gas in a methanation
1.4. Biogas and Landfill Gas stage downstream of the gas cleaning unit. In
(! Methane) addition, the Lurgi gasification process has
been developed further to produce SNG more
Biogas is the gaseous reaction product from economically by increasing gasification pressure
anaerobic digestion of wastewater having a high to 10.0 MPa (Ruhr 100, see ! Gas Production,
BOD value or of sludge from wastewater treat- 2. Processes, Section 3.4.). Here, more than
ment plants. It is used solely as fuel for combus- 50 vol % of methane recoverable from coal is
tion engines to meet the power requirements of produced in the gasification stage proper.
the treatment plant. Heavy vacuum residues can also be used as
feedstock for SNG production. However, as in
Landfill gas is produced by the degradation coal-based plants, capital investment is relatively
of organic matter in the waste disposed of in high. The discovery of huge new natural gas
landfills under anaerobic conditions. Because resources in some areas of the world during the
access to oxygen is not strictly controllable, aer- past few years has made the production of SNG
obic degradation may occur simultaneously, pro- less attractive.
ducing water and carbon dioxide. Landfill gas is
recovered via pipelines buried in the landfill. For Composition. Rich gases have a higher cal-
existing landfills, wells are drilled and lined with orific value than grid gas, with gross calorific
tubes to allow the gases to be extracted. Landfill values from about 25 000 kJ/m3 (STP) upward.
gas is used mostly as fuel gas for cogeneration and A rich gas produced from naphtha (British Gas or
in combustion engines after suitable purification. BASF – Lurgi process) has the following typical
Composition. Biogas is composed of 60 – analysis, in percent by volume:
70 vol % methane and 30 – 40 vol % carbon
dioxide, depending on the feed and digester Carbon dioxide 21.6 Hydrogen 12.5
temperature (mesophilic – thermophilic). Carbon monoxide 0.3 Methane 65.6
Landfill gas is composed of 50 – 55 vol %
methane, 41 – 45 vol % carbon dioxide, and Substitute natural gas should differ as little
1 – 4 vol % nitrogen. as possible from natural gas. It must be condi-
410 Gas Production, 1. Introduction Vol. 16

tioned so that it can be substituted for natural gas. nents were then used for synthesis gas
This depends on the following parameters: high- production.
er heating value, density, and Wobbe index (see
! Gas Production, 6. Analysis and Quality Con- Liquid Fuels. In most cases, various frac-
trol, Section 3.1.3.). tions of crude oil are used for gasification. Only
In addition the specified content of impuri- in very rare cases is unrefined crude oil used
ties, particularly sulfur, must not be exceeded. directly for gasification because neither its
Typical SNG produced in a coal gasification economic nor its technical considerations are
plant in North Dakota has the following analy- optimum.
sis, in percent by volume (unless otherwise
stipulated): Liquefied petroleum gas (LPG, a propane –
butane mixture; ! Liquefied Petroleum Gas) is
Methane 96.3 Nitrogen þ argon 1.1
used for the production of town gas, particularly
Carbon monoxide 0.02 Carbon dioxide 1.2 in smaller capacity plants, and for peak shaving.
Hydrogen 1.38 Hydrogen sulfide 4 ppm It is virtually sulfur-free and can be processed
without significant problems. Light naphtha is
utilized for larger town gas plants and for the
production of synthesis gas. Generally, fractions
2. Raw Materials for Gasification boiling at 40 – 110
C are used, but full-range
straight-run naphtha with a boiling end point of
Gaseous Fuels. Natural gas as raw material 150 – 200
C may also be employed. Depending
is of paramount importance for gasification or on its origin, this naphtha has a sulfur content
reforming (the term reforming is used more between 30 and 300 ppm. Naphtha must be
commonly for gases) in externally heated tubular completely desulfurized because almost all con-
reformers to yield synthesis gas for various ap- ventional processes for the production of town or
plications. Plants also reform natural gas by synthesis gas include a reaction stage involving
partial oxidation. The composition of natural catalysts that are very sensitive to sulfur
gases is not important for the technology to be poisoning.
applied, as long as their inerts content is negligi- In some cases, LPG and naphtha have also
ble. However, if the nitrogen content rises above been converted to town and synthesis gas by
5 – 10 vol %, this may have consequences for partial oxidation (thermally or catalytically) with
the design of ammonia synthesis gas plants op- oxygen or oxygen-enriched air. For catalytic
erated on the tubular reformer principle. partial oxidation, desulfurization to 20 – 50 ppm
In certain new energy scenarios, natural gas is sufficient.
still plays an important role. Thus, the energy Synthesis gas is produced from high-boiling
required for natural gas reforming may be sup- residues by partial oxidation with oxygen. Origi-
plied – at least partially – by solar collectors or nally, the high-boiling fraction (initial boiling
high-temperature nuclear reactors. Liquid motor point above 350
C) from atmospheric distilla-
fuels can be synthesized from synthesis gas. In tion units of refineries (! Oil Refining) – the
this way, thermal energy, which is difficult to heavy fuel oil – was used for this purpose. To
store and utilize, is converted to energy carriers date even higher viscosity fractions from vacuum
better adapted to the requirements. distillation and conversion plants are being used
Coke oven gas (! Coal Pyrolysis) is of minor increasingly. Because of the more stringent
importance for producing synthesis gas because requirements imposed by environmental legisla-
special expenditures are necessary to remove tion, these heavy oils can no longer be burned
various impurities from the coke oven gas, and in boiler houses and are, therefore, cheap raw
compression costs are high. In older plants, coke materials for gasification, which also eliminates
oven gas was separated into its individual com- various pollutants in the residue such as sulfur
ponents by fractionated condensation and dis- and heavy metals. To be used in gasification
tillation at low temperature rather than being plants, the heavy oil must be suitable for pumping
reformed (the content of methane and higher and spraying. Therefore, the oils are preheated to
hydrocarbons is low anyway); these compo- attain the required viscosity.
Vol. 16 Gas Production, 1. Introduction 411

The ash content of the heavy oils and the Therefore, light hydrocarbons are desulfur-
composition of the ash affect the operating ized to < 0.1 ppm of sulfur upstream of plants
temperature of gasification plants and the service operated at low catalyst temperature (400 –
life of the refractory lining. Vanadium and nickel 700
C). The sulfur content may often be higher
in ash are particularly harmful. by one or two orders of magnitude in catalytic
Apart from petroleum fractions, other liquid processes operating above 850
C.
fuels may be used for gasification, although they
are not very important. These include: Solid Fuels. Various solid fuels are not all
equally suitable for gasification. In addition,
1. tars from bituminous coal and lignite for different gasification processes have different
gasification by partial oxidation; fuel requirements.
2. fractions from shale oil (! Oil Shale) Because endothermic gasification reactions
production, particularly heavy fractions, for should be as complete as possible, the suitability
gasification by partial oxidation; of solid fuels for gasification improves as
3. methanol for producing peak shaving gas in their reactivity increases. This reactivity can be
catalytic town gas plants; correlated with the oxygen content, which
4. hydrocarbon condensates from natural gas decreases with increasing carbonization (i.e.,
production for gasification by partial oxida- with increasing age of the fuel).
tion; and The classification and designation of various
5. waste from chemical plants (e.g., iso- types of coal are different in individual industrial
butyraldehyde). countries (! Coal, Chap. 4.). As a rule, however,
they depend on volatile matter, which almost
Purity Requirements for Liquid and always means classification by age of the coal.
Gaseous Fuels. Raw materials for gasification Additionally, the following properties of fuels
plants using catalysts must generally be very are essential for assessing their suitability for
pure. Therefore, in most cases, such plants are gasification:
equipped with special upstream purification
units. A certain tolerance regarding the content
Ash content Coal grain size
of impurities can be accepted in cyclic processes Water content Melting behavior of the ash
that regenerate catalysts in the respective Sulfur content Behavior of the coals on heating
cycles. However, continuous processes impor- Caking properties
tant to modern technology require exceptionally
pure fuels, especially with respect to sulfur Because coal gasification adds considerably
compounds. Catalysts used for these processes to the costs of upgraded energy (i.e., the gas), coal
thus permit the use only of gaseous fuels (natu- used for this purpose should be as cheap as
ral gas) and of liquid hydrocarbons up to a possible. Wherever possible, only coal that is
boiling end point of ca. 200
C. not suitable for other applications and, therefore,
Generally, the lower the operating tempera- has a low market price should be used. Coal
ture of the catalytic process, the lower is the produced by open-pit mining is of special interest
residual sulfur content that can be tolerated in for gasification.
the raw materials. How adverse an effect sulfur Almost all solid fuel such as wood, peat,
compounds in the gas have on the active sites of lignite, young and old bituminous coal, and coke,
catalysts can be derived from equilibrium con- including petrol coke, has been used for gasifi-
ditions governing the reaction of the metallic cation. In the future, more use should be made of
phase of the catalyst with the sulfur compounds. lignites and younger noncaking or caking bitu-
Most gasification catalysts contain nickel as an minous coal, as well as coal with a high ash
active substance. At constant partial pressure content (20 – 50 wt %) or sulfur-rich coal which
of sulfur compounds in the gas, nickel sulfide is rarely suitable for other applications.
formation increases with decreasing tempera- With regard to various types of petrol coke
ture; a sulfided catalyst no longer provides the (delayed, fluid, Lurgi – Ruhr gas (LR) coke, !
desired results regarding reaction direction (dan- Oil Shale, ), their high sulfur and heavy-
ger of carbon formation), speed, and selectivity. metal content (! Petroleum Coke, Section 3.2.)
412 Gas Production, 1. Introduction Vol. 16

Table 2. Comparison of capital cost and energy requirements for an drawn regarding the conversion of materials and
ammonia plant and a methanol plant with a capacity of 1000 t/d based
on gaseous, liquid, and solid fuel
heat of reaction.
Gasification of solid and liquid fuels involves
Natural Heavy heterogeneous reactions at the phase boundary of
gas oil Coal particles or droplets and homogeneous reactions
Ammonia plant in the gas phase. The latter include reactions of
Capital cost, % 100 170 225 components that devolatilize at operating
Energy requirements, % 100 115 135 temperature.
Methanol plant
Capital cost, % 90 150 200 The following principles form the basis for
Energy requirements, % 95 105 125 calculating gasification processes:

1. Material Balance. In establishing a material

renders combustion increasingly difficult in view balance, the total number of atoms of the
of pollution control measures. Petrol coke is, individual elements in the reactants is equal-
therefore, turning into a new potential raw material ized to that in the products, irrespective of
for gasification. the distribution of the elements between the
Gasification of wood has been revived be- individual components (principle of conser-
cause of increasing interest in renewable raw vation of mass).
materials. Emphasis is mainly on the production 2. Energy Balance. Energy balance is based
of clean fuel gas (low sulfur content of wood), but on the principle of conservation of energy.
synthesis gas production is also possible with Consequently, energy supplied to the system
modern fluidized-bed processes. (enthalpy of reactants and heat supplied) is
equal to energy removed from it (enthalpy of
Suitability of Fuels for Gasification. Con- products and heat removed). In determining
siderable differences exist in the complexity of enthalpy, formation and phase change ener-
gasification technology applied, depending on gies must be considered.
whether solid, liquid, or gaseous fuels are used. 3. Chemical Equilibrium. The equilibrium
A general rule is that capital cost and consumption composition of the gasification product is
figures are higher for solid than for liquid fuels, and determined by the temperature-dependent
for liquid higher than for gaseous fuels. Therefore, equilibrium constants of reactions going
in the production of particular gases, mere com- on in the system and by the operating
parison of specific energy prices of various fuels is pressure.
insufficient; individual costs for gasification must 4. Chemical Kinetics. Because equilibrium is
be considered as well (see Table 2). not attained when residence time is too short
To make end products competitive, the (for example, because the temperature is
specific energy price of coal must be lower than too low), the composition of the gasification
that of heavy oil, and the latter must be lower than product in this case is determined by the
that of natural gas. In principle, this also applies kinetics of the reactions. In addition, transport
to other solid and liquid fuels with regard to the phenomena, such as boundary layer or pore
complexity of the conversion plant based on diffusion, may have some influence.
these particular feedstocks.
Even if fuels of the same physical state are Practical calculation leads to nonlinear equa-
compared, great differences exist in the proper- tion systems in which the number of unknown
ties of individual substances, which also affect quantities is determined essentially by the num-
their suitability for gasification. ber of components in the raw gas. The solution
may be found iteratively or – if appropriate rou-
tines are used – simultaneously. Calculations are
3. Physicochemical Basis for Gas particularly complicated when chemical kinetics
Production must be considered.

Gasification can be described by overall chemi- Reaction Enthalpy of Gasification. Gasifi-

cal reactions, from which conclusions may be cation reactions can be described by many
Vol. 16 Gas Production, 1. Introduction 413

different equations. To calculate the reaction (homogeneous water gas reaction, shift con-
enthalpy of gasification, however, a limitation version)
to certain characteristic reaction groups is suffi-
cient. The reaction enthalpy of all other reactions Cn Hm þn H2 O n COþðm=2þnÞH2 ð8Þ
can be derived by combining these basic equa-
tions, and individual reactions have no influence For example,
on the total heat balance of a sequence of CH4 þH2 O COþ3 H2 DH ¼ þ206:28 kJ=mol ð8aÞ
reactions if the same feedstocks are turned into
the same products (Hess’s law). C2 H6 þ2 H2 O 2 COþ5 H2 DH ¼ þ347:50 kJ=mol ð8bÞ
The reaction groups characteristic of gasifica-
tion can be subdivided as follows (DH refers to C3 H8 þ3 H2 O 3 COþ7 H2 DH ¼ þ498:06 kJ=mol ð8cÞ
0
C and 0.1 MPa as reference state; DH is
negative for exothermic reactions and positive The enthalpy of the reaction of fuels with
for endothermic reactions): steam to produce carbon dioxideand hydrogen

1. Reactions with molecular oxygen (combus- Cn Hm þ2 n H2 O n CO2 þðm=2þ2 nÞH2 ð9Þ

tion)
can be determined by
Cþ1=2 O2 CO DH ¼ 110:62 kJ=mol ð1Þ
DHðEq: 9Þ ¼ DHðEq: 8Þþn DH ðEq:7Þ
COþ1=2 O2 CO2 DH ¼ 283:15 kJ=mol ð2Þ
because Equation 9 may be considered a com-
H2 þ1=2 O2 H2 O DH ¼ 242:00 kJ=mol ð3Þ bination of Equations (8) and (7).
3. Reactions with carbon dioxide
Cn Hm þðnþm=4Þ O2 n CO2 þm=2 H2 O ð4Þ
CþCO2 2 CO DH ¼ þ172:54 kJ=mol ð10Þ
For example,
CH4 þ2 O2 CO2 þ2 H2 O DH ¼ 802:86 kJ=mol ð4aÞ (Boudouard reaction)
Cn Hm þn CO2 2 n COþm=2 H2 ð11Þ
C2 H6 þ7=2 O2 2 CO2 þ3 H2 ODH ¼ 1428:8 kJ=mol
ð4bÞ For example,

CH4 þCO2 2 COþ2 H2 DH ¼ þ247:44 kJ=mol ð11aÞ

C3 H8 þ5 O2 3 CO2 þ4 H2 ODH ¼ 2045:4 kJ=mol
ð4cÞ
C2 H6 þ2 CO2 4 COþ3 H2 DH ¼ þ429:82 kJ=mol
The reaction enthalpy of combustion of other ð11bÞ
gaseous or liquid fuels is described in the
literature (e.g., [2–4]).For partial combus-
tion of gaseous or liquid fuels to carbon C3 H8 þ3 CO2 6 COþ4 H2 DH ¼ þ621:53 kJ=mol
monoxide and steam, ð11cÞ

Cn Hm þðn=2þm=4ÞO2 n COþm=2 H2 O ð5Þ Generally, the reaction enthalpies for hydro-

carbon gasification with carbon dioxide
the reaction enthalpy can be calculated from (Eq. 11) are obtained from the enthalpies of
the enthalpies of Equations (4) and (2) as Equations (8) and 7 as follows:
follows:
DHðEq: 11Þ ¼ DHðEq: 8Þn DH ðEq:7Þ
DHðEq: 5Þ ¼ DHðEq: 4Þn DH ðEq:2Þ
2. Reactions with steam 4. Hydrocarbon decomposition reactions (soot
formation) Hydrocarbon decomposition is de-
CþH2 O COþH2 DH ¼ þ131:38 kJ=mol ð6Þ
scribed by
COþH2 O CO2 þH2 DH ¼ 41:16 kJ=mol ð7Þ Cn Hm n Cþm=2 H2 ð12Þ
414 Gas Production, 1. Introduction Vol. 16

For example,
CH4 Cþ2 H2 DH ¼ þ74:91 kJ=mol ð12aÞ

C2 H6 2 Cþ3 H2 DH ¼ þ84:74 kJ=mol ð12bÞ

C3 H8 3 Cþ4 H2 DH ¼ þ103:92 kJ=mol ð12cÞ

may be considered the reverse of hydrocarbon

formation from its elements and is essential
for the gasification of hydrocarbons.The re-
action enthalpy can be calculated from the
combustion enthalpies of the reactants:
DHðEq: 12Þ ¼ DHðEq: 4Þn DHðEq: 1Þ Figure 1. Water gas equilibrium, Kp ¼ f (1000/T)
nDHðEq: 2Þm=2 DH ðEq:3Þ

In calculating the main gas components, side

reactions of sulfur compounds (H2S, COS, etc.) According to the laws of thermodynamics, the
and nitrogen compounds (NH3, HCN) are gener- equilibrium constant Kp of a reaction can be
ally neglected because they have no great effect calculated by means of the Gibbs free energy of
on the numerical distribution of the main gas the reaction or the free formation energies of the
components. If detailed information on the dis- reactants.
tribution of secondary components is required, Strictly speaking, the equilibrium constant Kp
further calculations can be made and the results in the above form applies only to ideal gases. At
used for the main gas components. increased pressure (total of ca. 1.0 MPa or more)
and near the boiling points of the liquids, the
Chemical Equilibrium. The gasification appropriate partial fugacities should be used
reactions represented by Equations 1 – 12 are instead of partial pressures. These fugacities
never complete in either of the two possible allow for the real behavior of individual gas
directions but tend to reach an equilibrium ex- components. However, in practice, partial pres-
pressed by the equilibrium constant Kp. For Equa- sures can be used for the calculation with suffi-
tion 8a, for example, this constant is given by cient accuracy in most cases.
In heterogeneous reactions, partial pressures
pCO p3H2 xCO x3H2 2 of the solids are not taken into account because
Kp ¼ ¼ P ¼ f ðTÞ
pCH4 pH2 O xCH4 xH2 O they are regarded as a function of temperature
where xi represents the mole fraction and pi the alone, which is included in the equilibrium
partial pressure of each of the four components, P constant Kp. However, the free formation ener-
the total pressure, and T the temperature. gy of the solids must be considered in a ther-
For Equation (7), the carbon monoxide shift modynamic calculation of the equilibrium
conversion (which in nearly any case has to be constants.
considered) the equilibrium constant is given by The three reactions described by Equations
(7), (8a) and (10) are almost always sufficient to
pCO2 pH2 xCO2 xH2
Kp ¼ ¼ ¼ f ðTÞ calculate the theoretical product gas composi-
pCO pH2 O xCO xH2 O
tion of various gasification processes. Table 3
In comparison to the steam reforming reaction shows the equilibrium constants of these three
8a the equilibrium composition of the shift con- reactions at different temperatures. In addition
version is not influenced by the total pressure, equilibrium constants for heterogeneous meth-
because simply spoken, the number of molecules ane decomposition (Eq. 12a) are given as an
on the right and on the left side of Equation 7 is example of hydrocarbon decomposition. This
identical. The temperature dependence of the equilibrium may also be derived from Equations
equilibrium constant (log Kp vs. 1/T) is shown (7), (8a), and (10). Additionally equilibrium
in Figure 1. constants for COS hydrogenation and
Vol. 16 Gas Production, 1. Introduction 415

Table 3. Temperature-dependent equilibrium constants of various reactions

Equation (7) (8a) (10) (12a) COS hydrogenation COS hydrolysis

Unit for Kp bar2 bar bar

Temperature,
C
100 12.4 4.39104
200 19.1 4.26103
300 38.5 6.13108 3.60107 4.36103 24.4 940
400 11.5 5.54105 8.55105 5.56102 28.0 323
500 4.82 9.16103 4.99103 3.76101 30.3 146
600 2.51 4.88101 1.16101 1.66 31.5 79.1
700 1.52 11.8 1.42 5.41 32.1 48.7
800 1.02 159 11.0 14.1 32.2 32.9
900 7.41101 1.38103 59.8 31.2 32.0 23.7
1000 5.71101 8.63103 249 60.6
1100 4.60101 4.12104 845
1200 3.84101 1.59105 2.43103
1300 3.30101 5.16105 6.08103
1400 2.91101 1.48106 1.36104
1500 2.61101 3.69106 2.79104

hydrolysis are included (see ! Gas Production, from the ASPEN program [5] which uses in this
3. Gas Treating, Chap. 3). case the correlations cited in [6]. Minor differ-
ences with respect to other literature data may
COSþH2 H2 SþCOCOSþH2 O H2 SþCO2
occur.)
A general assessment of tendencies in
The temperature dependence of the equilibri- gasification reactions is facilitated by the Le
um constants can be calculated with an equation Ch^atelier – Braun principle that a system in
of the following type equilibrium tries to evade a change forced upon
log K p ¼ AþB=TþC logTþDTþET 2 it. For example, in Equation (8a), an increase in
total pressure results in increased methane
where T is the absolute temperature in Kelvin. formation because the number of gaseous
For the various equilibria used in this article molecules on the right side of Equation (8a) is
the values of the constants A – E are given in higher than that on the left. A pressure increase
Table 4. (The data of Tables 3 and 4 were taken in reactions proceeding without a change in the
Table 4. Values of coefficients for calculating the equilibrium con- number of molecules, such as the homogeneous
stants of various reactions as a function of absolute temperature water gas reaction (Eq. 7) has almost no effect.
Equation (7) (8a)
Reaction Sequence for Various Gasifica-
A 8.000980 18.98177 tion Processes. No statements can be made on
B 2456.620 9520.569 the basis of thermodynamics regarding the chro-
C 1.984098 10.91012
D 0.3329441103 0.319556102
nological sequence of gasification reactions.
E 0.563315107 0.3631894106 Calculations must include reaction kinetics.
Equation (10) (12a)
Frequently, however, the required data are not
available. Approximation methods must then be
A 2.220419 21.61666 used to calculate product gas composition. A
B 8709.775 2875.50
C 2.495100 9.505546 common method involves use of Kp values
D 0.6399432103 0.3694027102 which, according to experience, reflect the actual
E 0.5280003107 0.5233708106 final state but pertain to a temperature other than
Equation COS hydrogenation COS hydrolysis that prevailing at the end of the reactor.
A 5.956145 4.485945
Some processes employ catalysts to acceler-
B 566.2154 1568.825 ate the reaction and enhance reaction kinetics in
C 1.309130 1.681947 order to approach equilibrium. Selective cata-
D 0.5766548104 0.7452208103 lysts promote desirable reactions at the expense
E 0.1222679107 0.1160356106
of undesirable ones (e.g., carbon formation
416 Gas Production, 1. Introduction Vol. 16

according to Boudouard). Generally, reaction tion pressure. Carbon monoxide and hydrogen
rate increases as temperature increases. Gasifi- are also produced by direct endothermic carbon
cation, therefore, approaches equilibrium more gasification with steam (Eq. 6). In entrained-
easily at higher than at lower temperature. flow gasification processes, the reaction se-
quence described is mostly overlapping. The
Tubular Reactor Reforming. When reform- mode of reaction essentially determines the
ing hydrocarbons, especially methane, in exter- temperature profile in a gas producer.
nally heated tubular reactors, conversion of the The composition of gasification gas is deter-
hydrocarbons with steam to yield carbon oxides mined by a more or less accurate adjustment of
and hydrogen (according to Eqs. 8 and 9) must be the simultaneous equilibrium among the shift
considered basic reactions. The composition of conversion reaction (Eq. 7), the methane
the product gas is determined by the simulta- reforming reaction (Eq. 8a), and the Boudouard
neous equilibrium between Equations (7) reaction (Eq. 10).
and (8a).
Because soot formation should be suppressed,
the Boudouard reaction (Eq. 10) and hydrocar- 4. Characteristics of the Basic
bon decomposition (Eq. 12 and, especially, 12a) Processes
are essential for an assessment of the reaction
system. In most cases, the aim is to produce gases with
high hydrogen and carbon monoxide content.
Rich-Gas Process. When naphtha is re- This applies to all synthesis gases and also to
formed catalytically with steam in a shaft reactor town gas. Depending on the particular require-
to yield gases with a high methane content, the ments, the carbon monoxide content may be
endothermic gasification reactions (Eqs. 8 and 9) reduced with steam to yield hydrogen and carbon
must be considered as starting reactions, whose dioxide. To produce such gases from various
products are then transformed in an exothermic solid, liquid, and gaseous fuels, heat must be
methanation reaction described by Equation (8). supplied to support the endothermic reactions.
The final condition of the reforming process is Thus, different processes can be classified ac-
determined by Equations (7) and (8a). cording to the type of heat supply.
On the other hand, processes for producing
Oil Gasification. In oil gasification with gases with high methane content, such as rich gas
oxygen and steam, partial combustion of hydro- and SNG, in principle require no external heat
carbons (Eq. 4), as well as steam and carbon supply because methane formation is exother-
dioxide gasification of carbon (Eqs. 8 and 11), mic. Therefore, the process characteristics of this
must be considered to proceed more or less group are different.
simultaneously. Product gas composition is Trends in the past decades have shifted from
determined by the final state of the simultaneous processes operated under atmospheric condi-
equilibrium among the reactions described in tions to those operated at elevated pressure.
Equations (7), (8a), and (10). This has resulted in economic advantages
because the subsequent chemical syntheses
Coal Gasification. The first step in a coal [ammonia, methanol, oxo (! Oxo Synthesis)
gasification reaction (e.g., with oxygen and and Fischer –Tropsch synthesis (! Coal Lique-
steam in countercurrent mode of operation) is faction)] operate at more or less elevated pressure,
exothermic combustion of carbon to carbon which removes the cost of compressing the high-
dioxide, according to Equations (1) and (2). The volume synthesis gas. Moreover, plants operating
carbon dioxide formed then reacts with hot under pressure can be designed for higher capaci-
carbon to yield carbon monoxide in an endo- ty due to their smaller gas volume, which again
thermic reaction (Eq. 6). This in turn reacts with means savings in capital costs.
steam to produce either hydrogen and carbon An essential criterion is whether catalysts are
dioxide (according to Eq. 7) or methane and used. With catalysts, a better approximation to
carbon dioxide (by the reverse of Eq. 11a). The reaction equilibria is attained and undesired
latter occurs particularly at increased gasifica- byproducts are mostly avoided. However,
Vol. 16 Gas Production, 1. Introduction 417

catalysts can thus far be used successfully only the catalyst would have to be very cheap so that it
for gaseous feeds and for distillate liquid feeds. could be disposed of along with the ash, or it
would have to be recovered by a very complex
Cyclic Processes. Cyclic processes use heat procedure.
carriers consisting of refractory brick lining (in Processes applying baths of molten slag,
regenerators, air heaters, etc.) or beds of ceramic iron, or salts as heat carriers and reaction
material, which may be appropriately impregnat- promoters have been used and are still being
ed to impart catalytic properties to them. Regen- developed. A characteristic of autothermal pro-
erative heating is provided by hot flue gases from cesses is that the oxygen added to generate heat
the combustion of liquid or gaseous fuels. During is chemically bound in the product gas, so the
gasification, the heat carrier transfers its heat to ratio of hydrogen to carbon monoxide in the
the raw material to be converted. The process is product is lower than in other processes. This
suitable for liquid and gaseous feedstocks. Any type of process is applied to solid, liquid, and
carbon black deposited during the reforming gaseous fuels.
period can be burned off after the system is
switched back to heating. The process is not Processes Involving Externally Heated
suitable for operation at elevated pressure. Walls. Processes using externally heated walls
include tubular reforming, which is used widely
Processes using circulating heat carriers today. To keep the tube stresses resulting from
are similar to cyclic gasification except for being elevated pressure and temperature to a minimum,
continuous processes circulating the heat carrier all tubular reformers employ a catalyst filling
in a closed loop. This carrier is heated by hot flue in the tubes, which allows lower reaction
gases and then fed to a reaction section in which temperature.
its heat is used for gasification. In addition to Modern materials permit tubes to be designed
sensible heat, some heat carriers used in the past for wall temperatures of ca. 900
C (in special
also produced heat through reaction with gas cases even 1000
C at atmospheric pressure) and
components (producing CaCO3 from burned pressures up to 4.0 MPa. All gaseous hydrocar-
lime and CO2). Any carbon formed in the process bons (with low unsaturated hydrocarbon content)
can be burned off in the heating zone. The and distillate liquid fuels are suitable feedstocks.
process is generally suitable for gaseous, liquid, When liquid hydrocarbons are used, demands
and solid fuels. The circulating heat carrier may on the catalysts are extremely high. Virtually
consist of granular catalytic or noncatalytic so- ash-free fuels are used almost exclusively to heat
lids, or of liquids (such as slag baths) and circu- the tubes because ash constituents (salts, metals)
lating gas. Although system design does not would damage tube walls.
altogether exclude elevated operating pressure, Reactors with externally heated walls are also
the necessary design and operating conditions used in gas production from solid feedstocks.
would be difficult to meet. This process technology offers the opportunity
to employ nonfossil energy (heat from nuclear
Autothermal Processes. Autothermal pro- reactors, solar energy) for gasification.
cesses produce the heat required for gasification
through partial combustion of the fuel to be Rich-Gas Processes. Because no external
converted in the reactor. Oxygen or air – if nitro- heat supply is required for rich-gas processes,
gen in the air is not a ballast in the product gas – is the equipment and process loops can be chosen
added for this purpose. The process may operate freely. In most systems, a catalyst is applied
with or without catalysts. If catalysts are used, the because methane formation is favored by lower
temperature can be kept lower because a closer temperature. Apart from the unfavorable equi-
approach to equilibrium is ensured. However, the librium position, the risk of carbon deposits
catalytic process cannot be used to gasify heavy resulting from the Boudouard reaction is higher
and residual oils because most of these oils at increased temperature, and other byproducts
contain ash particles that contaminate the cata- are formed as well. All the processes operate at
lyst. Also, because of the ash content, catalysts elevated pressure because this promotes methane
for coal gasification are not applied, so far. Either formation.
418 Gas Production, 1. Introduction Vol. 16

Because catalysts are highly sensitive with . Oxygen (coal gasification, oil gasification)
respect to attrition, reactors are normally of the . Cyanic compounds (coal gasification, oil
fixed- rather than the fluidized- or entrained-bed gasification)
type. Raw materials must be virtually free of all . Nitrogen oxides (coal gasification, oil
substances that may poison catalysts, particularly gasification)
sulfur compounds. . Carbon dioxide (all gasification processes)
. Hydrogen sulfide, carbonyl sulfide, organic
sulfur
5. Product Gas Treatment . compounds (all noncatalytic gasification
processes)
Each gasification plant requires gas treatment . Ammonia (all gasification processes)
facilities to purify product gases and also, in
many cases, to condition them. Whereas the gas Other gas components, even if they occur only
purification system eliminates the components in trace amounts, require specific measures to
that would affect downstream processing or uti- prevent long-range damage or malfunction of the
lization of these gases, the purpose of a condi- plant. This is particularly true for the gasification
tioning system is to adjust gas components to the of coal and heavy oils. Such components may
appropriate ratio. The ratio of hydrogen to carbon include volatile metal compounds and high mo-
monoxide, especially, must be matched to the lecular mass organic compounds.
requirements of downstream synthesis or reduc-
tion units and other gas consumers.
The task of gas purification and conditioning is 5.1. Purification Processes
most complex downstream of plants gasifying
solid fuels. Capital investment in these purifica- Because of the large number of impurities, along
tion units can be much higher than that required with their widely varying content and combina-
for the gasification plant itself. Treatment of gases tions, a variety of gas purification processes are
produced through gasification of high molecular available to meet the requirements of down-
mass liquid hydrocarbons (heavy oils, vacuum stream processing (synthesis, in particular) and
residues) is also rather expensive. Generally, the of industrial and municipal consumers (town
smaller the molecules from which a gas is pro- gas). Ammonia synthesis, for instance, tolerates
duced, the lower is the capital investment required only ca. 5 ppm (mL/m3) of oxygen compounds
in treatment facilities. The costs of gas purifica- (e.g., O2, CO, CO2, and H2O), and the sulfur
tion are also strongly dependent on the amount content must be < 1 ppm (mL/m3).
and type of impurities in the feedstock, particu- Methanol synthesis, on the other hand, requires
larly its content of sulfur and trace elements. a sulfur content of < 0.1 ppm (mL/ m3) and the
Whereas most catalytic gasification process- stoichiometric ratio ðcH2  cCO2 Þ=ðcCO þ cCO2 Þ
es have some purification facilities (removing must be adjusted to ca. 2 (see ! Gas Production,
sulfur, lead, chlorine) upstream of the gasifica- 5. Examples of Complex Gas Production Plants,
tion stage, the impurities in noncatalytic Section 1.2.). To achieve this ratio, the gas must
processes should be removed only from the contain a certain amount of carbon monoxide – a
product gas. factor that influences the selection of gasifica-
tion and purification processes and also raises
Impurities in the Gasification Gas. De- the question of whether an additional process
pending on the type and composition of feed- stage is required to convert carbon monoxide
stock and the type of gasification process used, a into hydrogen and carbon dioxide. Carbon di-
gas purification plant must handle the following oxide need not be removed completely so the
impurities: general plant design can be simplified consi-
derably.
. Dust (coal gasification) Reduction gases for direct reduction of iron
. Carbonization products, tar, gas liquor (coal ore may contain sulfur on the order of 7 ppm
gasification) (mL/m3), but the content of water and carbon
. Carbon (Heavy-oil gasification) dioxide should not exceed 5 vol %.
Vol. 16 Gas Production, 1. Introduction 419

If several gas purification plants are combined selection of appropriate solvents is determined to
for optimum effect, perhaps including gas con- a large extent by their specific solubility coeffi-
ditioning facilities as well, possible interaction cients for the desired gases and by their
should be checked carefully. Interactions could selectivity.
occur because of solvents contained in the gas, Chemical absorption systems (! Absorp-
depending on their vapor pressure, different tion, 1. Fundamentals, Section 1.5.) can be used
operating behavior, etc. If fuel gas is produced at elevated or atmospheric pressure. They are
for a combined power cycle (see ! Gas Produc- particularly suitable whenever the absolute quan-
tion, 5. Examples of Complex Gas Production tity of impurities to be removed is small. Con-
Plants, Chap. 3.), the gas purification plant must ventional processes differ mainly in the degree of
meet the load change requirements of such purity that can be achieved and the amount of
plants. energy (normally steam) required for regenera-
Gas purification processes may be classified tion. Numerous processes also use some combi-
as follows: nation of physical and chemical absorption
principles.
Adsorption. Adsorption describes the re-
tention of impurities by solids, either through Special Wash Processes. Special applica-
physical deposition or through chemical reaction tions include the removal of solids entrained with
(chemisorption) (! Adsorption, see also ! Gas gases in the form of dust or carbon black, dust-
Production, 3. Gas Treating, Chap. 6.). Whenev- laden tar, and high molecular mass or unsaturated
er solids have to be reused (e.g., for economic hydrocarbons that tend to form gums.
reasons), batchwise operation is necessary be-
cause the laden solids must be regenerated.
Sulfur compounds are eliminated by using 5.2. Conditioning
beds of iron hydroxide and zinc oxide (especially
for desulfurizing gaseous and liquid feedstocks For nearly all applications, gasification gases not
for catalytic gasification). Activated carbon is only must be purified but also conditioned to
favored in special cases for cleaning gases con- obtain the optimum proportions of desirable gas
taining high molecular mass organic sulfur components (! gas Production, 3. Gas Treating,
compounds. Chap. 2., ! gas Production, 3. Gas Treating,
Molecular sieves (! Adsorption; ! Zeo- Chap. 3., ! gas Production, 3. Gas Treating,
lites) have been developed for selective removal Chap. 4.).
of particular gases. They can be used not only for
carbon dioxide, sulfur compounds, and steam, Carbon Monoxide Shift Conversion.
but also for diatomic gases. Prominent among gas conditioning processes is
Gas purification systems based on the adsorp- catalytic carbon monoxide shift conversion,
tion (and chemisorption) principle are preferred which is based on water gas equilibrium (Eq. 7).
when small quantities of impurities must be By this process, the hydrogen content of a gas can
eliminated or small gas throughputs must be be increased as desired at the expense of its
purified. carbon monoxide content. This is important not
only for ammonia synthesis but also for town and
Absorption. A general distinction is made grid gas production. The process permits the gas
between physical and chemical absorption pro- to be adjusted to the standard density and Wobbe
cesses. Physical processes (! Absorption, 1. index, and also enables nontoxic, low-carbon
Fundamentals, Section 1.4., see also ! Gas monoxide town gas to be produced, in conformi-
Production, 3. Gas Treating, Chap. 5.) are par- ty with current regulations.
ticularly suitable for high pressure, high impurity Carbon monoxide shift conversion requires
content, and large gas throughput. The processes the addition of steam, which can be done in one of
available differ in solvents used, mode of plant several ways. Steam at the appropriate pressure
operation, operating temperature, method of en- may be added directly to the gas to be converted.
ergy recovery, and potential for recovering sev- If steam is not available in sufficient quantities
eral components more or less separately. The and under economically justifiable conditions, a
420 Gas Production, 1. Introduction Vol. 16

so-called saturator cooler loop is often used. With adsorption (PSA) (! Adsorption) or membrane
this arrangement, gas entering the conversion processes (! Membranes and Membrane Sepa-
section is humidified by circulating hot water, ration Processes) can be used. The PSA principle
and unreacted steam in the gas leaving this stage is based on the fact that the adsorption capacity of
is recondensed and recycled to the saturator. molecular sieves (! Zeolites) differs for differ-
A distinction is also made between high- and ent gases. Generally, heavier or polar gas com-
low-temperature conversion, the latter being ponents are adsorbed preferentially. When a gas
provided downstream of the former to reduce mixture is passed over a molecular sieve bed, the
the residual carbon monoxide content of the gas component least amenable to adsorption (e.g.,
to a minimum (e.g., for ammonia synthesis). H2) remains in the gas whereas other components
Shift conversion catalysts for sulfur-free gases are adsorbed.
are based on iron (high temperature shift) or Gas separation by membranes is based on the
copper (low temperature shift). They are differences in permeation coefficients of differ-
supplied as oxides and reduced during operation. ent gas components. Permeation denotes the
For gases containing sulfur compounds the shift sequence of absorption (solution) of the compo-
catalysts are based on cobalt and molybdenum. nent in the membrane material, diffusion through
They are active only as sulfides. the membrane, and desorption. The permeation
rate of a species increases with its solubility and
Methanation. Another gas conditioning its diffusion coefficient in the membrane materi-
method is methanation, the conversion of carbon al. Membranes may consist of ceramic or metal-
monoxide, carbon dioxide, and hydrogen to lic materials, organic liquids, or polymers.
methane according to Equations (8a) and (9). Both processes, PSA and membrane separa-
A methanation stage is included in many ammo- tion, can be used to advantage for gases at
nia synthesis plants to ensure a high degree of elevated pressure.
purity of the synthesis gas. Similarly, a metha- To remove traces of higher hydrocarbons
nation step is indispensable if a high-methane gas (e.g., compressor lubricants) from gases, beds
for SNG production is to be obtained. of activated carbon are used. For recovery of low-
boiling compounds, as well as purification from
Other Processes. The following processes traces of higher boiling compounds, cryogenic
may also be regarded as gas conditioning. processes (! Cryogenic Technology) can be
If the calorific value of town gas, grid gas, or applied. These employ primarily liquid methane
SNG is insufficient, the gasification gas may be or nitrogen to absorb higher boiling gases such as
carbureted by adding C3 and C4 hydrocarbons or, carbon monoxide.
less frequently, small quantities of high molecu-
lar mass hydrocarbons. On the other hand, too
high a calorific value can be reduced by adding 5.3. Byproducts
nitrogen, air, or oxygen.
For certain syntheses, gases must be dried. Some gasification processes yield byproducts
Drying is also necessary in pipelines, to protect along with the desired gas (see also ! Gas
the piping from corrosion where a risk of water Production, 4. Handling of Byproducts). A com-
condensation in the presence of carbon dioxide parison of different gasification processes should,
exists. In addition, the formation of gas hydrates therefore, always consider such byproducts and
is avoided. assess their importance. Environmental protec-
Unlike town gas produced in the past from tion, too, plays an important role because it im-
coke oven batteries, the town gas obtained today poses stringent conditions on pollutant discharge.
through gasification no longer contains any chem- Many gasification plant feedstocks contain
ical compounds that produce a manifest odor. sulfur, and sulfur often constitutes the main
Therefore, such gases are now odorized artificial- byproduct. Whether this is best recovered in the
ly so that leaks occurring in the piping or at the form of elemental sulfur or sulfuric acid is worth
consumer’s facilities can be detected easily. considering.
To recover particular components from a gas Other coal gasification processes have coke as
stream (e.g., H2 from purge gas), pressure-swing a byproduct.
Vol. 16 Gas Production, 1. Introduction 421

Gasification involving coal carbonization pro- cooling water, or be discharged to receiving

cesses can produce a large number of byproducts water via chemical or biological effluent treat-
such as tar, oil, gasoline, phenols, cresols, am- ment plants.
monia, and organic acids. Certain liquid bypro-
ducts may even contain solids whose elimination
would result in additional costs. Because of this,
processes have been developed to recycle certain
6. Acknowledgement
liquid fractions to the gasification plant if their
The topic Gas Production was coordinated by
market value is low.
GERHARD HOCHGESAND.
Heavy-oil gasification plants yield carbon as
a byproduct. Attempts to use it for special
industrial applications have been successful, but
demand for the specific qualities of carbon is References
limited. Therefore, processes are being devel-
oped to recycle most of this carbon to the 1 E. Michel, GWF Gas Wasserfach 95 (1954) 598 – 603.
gasification stage. These and processes where 2 H. Zeise: Thermodynamik vol. III/1, Leipzig 1954.
3 R. C. Weast: Handbook of Chemistry and Physics, CRC
carbon is burnt in conventional power stations at
Press, Cleveland, Ohio.
little extra cost are of major interest. 4 Nat. Ber. Stand: Selected Values of Chemical Thermody-
Gas liquor is a product of almost all gasifica- namic Properties, Washington 1952/53.
tion processes. Depending on its composition 5 L. B. Evans et al., Comput. Chem. Eng. 3 (1979) 319 – 327.
and on plant requirements, this gas liquor can 6 R. C. Reid, J. M. Prausnitz, B. E. Poling: The Properties of
either be treated for use as boiler feed water or Gases and Liquids, McGraw-Hill, New York 1987.