Ullmanns 3 PDF

Article No : o02_o12
Ammonia, 3. Production Plants

MAX APPL, Dannstadt-Schauernheim, Germany
1. Complete Ammonia Production Plants . 227 1.2. Ammonia Plants based on Partial
1.1. Steam Reforming Ammonia Plants . . . . 228 Oxidation . . . . . . . . . . . . . . . . . . . . . . . . 243
1.1.1. The Basic Concept of Single-Train Plants. 228 1.2.1. Ammonia Plants Based on Heavy
1.1.2. Further Developments . . . . . . . . . . . . . . . 229 Hydrocarbons . . . . . . . . . . . . . . . . . . . . . 243
1.1.3. Minimum Energy Requirement for Steam 1.2.2. Ammonia Plants Using Coal as Feedstock 247
Reforming Processes . . . . . . . . . . . . . . . . 231 1.3. Waste-Heat Boilers for High-Pressure
1.1.4. Commercial Steam Reforming Ammonia Steam Generation . . . . . . . . . . . . . . . . . 248
Processes . . . . . . . . . . . . . . . . . . . . . . . . 234 1.4. Single-Train Capacity Limitations
1.1.4.1. Advanced Conventional Processes . . . . . . 234 Mega-Ammonia Plants. . . . . . . . . . . . . . 250
1.1.4.2. Processes with Reduced Primary Reformer 2. Modernization of Older Plants
Firing . . . . . . . . . . . . . . . . . . . . . . . . . . . 237 (Revamping) . . . . . . . . . . . . . . . . . . . . . 251
1.1.4.3. Processes without a Fired Primary Reformer 3. Material Considerations for Equipment
(Exchanger Reformer) . . . . . . . . . . . . . . . 240
Fabrication . . . . . . . . . . . . . . . . . . . . . . 252
1.1.4.4. Processes without a Secondary Reformer
References . . . . . . . . . . . . . . . . . . . . . . . 254
(Nitrogen from Air Separation) . . . . . . . . 243
1. Complete Ammonia Production costs of feedstock and energy, is decisive for the
production economics. An important develop-
Plants ment was the concept of single-train plants, first
The previous sections mainly considered the indi- introduced for steam reforming based production
vidual process steps involved in the production of by M.W. Kellogg in 1963 with a capacity of
ammonia and the progress made in recent years. 600 t/d. Before then maximum capacities had
The way in which the individual process steps mostly been about 400 t/d, with several parallel
involved in the production of ammonia are com- trains in the synthesis gas preparation stage and
bined with respect to mass and energy flow has a the synthesis loop. Today world-scale plants
major influence on efficiency and reliability. Apart have capacities of 1200 2000 t/d. The lowest
from the feedstock, many of the differences bet- capital cost and energy consumption result when
ween various commercial ammonia processes lie steam reforming of natural gas is used. In addi-
in the way in which the process elements are tion site requirements can influence the layout
integrated. Formerly the term ammonia technolo- considerably. In contrast to a stand-alone plant,
gy referred mostly to ammonia synthesis tech- ammonia production at a developed industrial
nology (catalyst, converters, and synthesis loop), site may import and/or export steam and power,
whereas today it is interpreted as the complete which affects the total energy consumption.
series of industrial operations leading from the With the exception of the Koppers Totzek
primary feedstock to the final product ammonia. coal gasification process, which operates at near
The major determinant for process configura- atmospheric pressure, all modern gasification
tion is the type of feedstock, which largely processes operate at elevated pressure. Steam
governs the mode of gas generation and purifi- reforming of light hydrocarbons at 30 40 bar
cation. The other important factor is the plant and partial oxidation of heavy hydrocarbons at
capacity, which, together with consumption and 40 90 bar are generally used.
2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.o02_o12
228 Ammonia, 3. Production Plants Vol. 3
1.1. Steam Reforming Ammonia the carbon dioxide removal system. Because
Plants considerable mechanical energy is needed to
drive compressors, pumps, and blowers, it was
1.1.1. The Basic Concept of Single-Train most appropriate to use steam turbine drives,
Plants since sufficient steam could be generated from
the waste-heat. As the level was high enough to
The innovative single-train concept, introduced raise high-pressure steam (100 bar) it was possi-
in 1963 by Kellogg, was a technical and an ble to use the process steam first to generate
economical breakthrough and triggered a tre- mechanical energy in the synthesis gas compres-
mendous increase in world ammonia capacity. sor turbine before extracting it at the pressure
No parallel lines, even for high capacity, and a level of the primary reformer. Table 1 lists all
highly efficient use of energy, with process steps significant energy sources and sinks within the
in surplus supplying those in deficit, were the process.
main features. Figure 1 shows a block flow dia- The earlier plants operated at deficit, and
gram and the gas temperature profile for a steam needed an auxiliary boiler, which was integrated
reforming ammonia plant [398]. in the flue gas duct. This situation was partially
High level surplus energy is available from the caused by inadequate waste-heat recovery and
flue gas of the reformer and the process gas low efficiency in some energy consumers. Typi-
streams of various sections, while heat is needed, cally, the furnace flue gas was discharged in the
for example, for the process steam for the re- stack at rather high temperature because there
forming reaction and in the solvent regenerator of was no air preheating and too much of the reac-
Figure 1. Block diagram and gas temperature profile for a steam reforming ammonia plant
Vol. 3 Ammonia, 3. Production Plants 229
Table 1. Main energy sources and sinks in the steam reforming The new plant concept had a triumphant
ammonia process
success story. By 1969, 30 new Kellogg large
Process section Origin Contribution single-train plants with capacities of 1000 t/d or
more were in operation, and other contractors
Reforming primary reforming duty demand
flue gas surplus were offering similar concepts.
process gas surplus The decrease in energy consumption com-
Shift conversion heat of reaction surplus pared to the older technology was dramatic, and
CO2 removal heat of solvent regeneration demand with the low gas prices at that time it is under-
Methanation heat of reaction surplus
Synthesis heat of reaction surplus standable that greater emphasis was placed on
Machinery drivers demand low investment cost, although there was a con-
Unavoidable loss stack and general demand siderable potential for further reducing the ener-
Balance auxiliary boiler or import deficit gy consumption.
export surplus
With the advent of the single-train steam
reforming plants, it became standard for licen-
sors and engineering contractors to express the
total net energy consumption per tonne of am-
tion heat in the synthesis loop was rejected to monia in terms of the lower heating value of the
the cooling media (water or air). In addition, feedstock used. The total net energy consump-
efficiency of the mechanical drivers was low and tion is the difference between all energy imports
the heat demand for regenerating the solvent (mainly feedstock) and all energy exports (most-
from the CO2 removal unit (at that time aqueous ly steam and/or electric power) expressed as
MEA) was high. Maximum use was made of lower heating value of the consumed feedstock,
direct steam turbine drive, not only for the major whereby electric power is converted with an
machines such as synthesis gas, process air, efficiency of 25 30 % and steam is accounted
and refrigeration, but even for relatively small for with its caloric value.
pumps and blowers. The outcome was a rather
complex steam system. Even after substitution
of the smaller turbines by electric motors, the 1.1.2. Further Developments
steam system in the modern plant is still a
complex system as shown in Figure 3. Ammonia The significant changes in energy prices from
plant steam systems are described in [3, 4, 369, 1973 onwards were a strong challenge to process
166169]. licensors, engineering contractors and plant own-
The first generation of the single-train steam ers to obtain better energy efficiency. The overall
reforming plants is discussed in [8, 164, 165, 184, energy consumption was reduced from around
185, 193, 200], and the required catalysts are 45 GJ per tonne NH3 for the first large single-
reviewed in [81, 83, 204]. A survey of the train units to less than 29 GJ per tonne NH3
development of the steam reforming concept (Table 2).
through 1972 can be found in [174]. Other re- Energy saving modifications are described in
ferences which cover the development of the [2, 119, 175183, 205, 206, 210, 223, 230, 235,
steam reforming before the introduction of the 342]. For catalyst improvements see [411]. Some
single-train concept (1940 to 1960) can be found of the most important improvements compared to
in [3 p. 276]. the first generation of plants are discussed below.
Table 2. Development of the net energy consumption of natural gas based steam reforming ammonia plants (real plant data) in GJ per tonne NH3
Year 1966 1973 1977 1980 1991

Plant A B C D E
Feed 23.90 23.32 23.48 23.36 22.65

Fuel, reformer 13.00 9.21 7.35 5.56 5.90
Fuel, auxiliary boiler 2.60 5.02 3.06 1.17
Export 0.55
Total 39.50 37.55 33.89 30.18 28.00
Feedstock Purification. In feedstock puri- a very low residual CO content and low byprod-
fication, mainly desulfurization, adsorption on uct formation. A new generation of HT shift
active carbon was replaced by catalytic hydro- catalysts largely avoids hydrocarbon formation
genation over cobalt molybdenum or nickel by Fischer Tropsch reaction at low vapor par-
molybdenum catalyst, followed by absorption of tial pressure, thus allowing lower steam to carbon
the H2S on ZnO pellets with formation of ZnS. ratio in the reforming section (see ! Ammonia,
By itself this measure has no direct influence on 2. Production Processes, Section 6.1.2).
the energy consumption but is a prerequisite for
other energy saving measures, especially in re- Carbon Dioxide Removal Section. In the
forming and shift conversion. carbon dioxide removal section the first genera-
tion of single-train plants often used MEA with a
Reforming Section. In the reforming sec- rather high demand of low-grade heat for solvent
tion energy savings were achieved by several, regeneration. With additives such as UCAR
often interrelated, measures, of which the most Amine Guard [87, 88], solvent circulation could
important are the following: be reduced, saving heat and mechanical energy.
Much greater reduction of energy consumption
. Reduction of the flue gas stack temperature to was achieved with new solvents and processes,
reduce heat losses to the atmosphere [82] for example BASF aMDEA or Benfield LoHeat.
. Avoiding excessive heat loss by better insula- Other hot potash systems (Giammarco Vetro-
tion of the reformer furnace coke, Catacarb) and physical solvents (Selexol)
. Introduction of combustion air preheating were introduced (! Ammonia, 2. Production
[223] Processes, Section 6.1.3).
. Preheating the reformer fuel
. Increased preheat temperatures for feed, pro- Final Make-Up Gas Purification was im-
cess steam and process air proved by removing the water and carbon diox-
. Increased operating pressure (made possible ide traces to a very low level by using molecular
by using improved alloys for the reformer sieves. Some concepts included cryogenic pro-
tubes and improved catalysts) cesses with the benefit of additional removal of
. Lowering of the steam to carbon ratio [237] methane and argon.
. Shifting some reformer duty from primary to
secondary reformer with the use of excess air Ammonia Synthesis Section. In the ammo-
[18, 19] or oxygen-enriched air [363] in the nia synthesis section conversion was increased by
secondary reformer, including the possibility improved converter designs (see ! Ammonia, 2.
of partially bypassing the primary reformer Production Processes, Section 6.3.2), larger cata-
[238, 241] lyst volumes, and to some extent with improved
. Installing a prereformer or rich-gas step is an- catalysts. The main advances in converter design
other possibility to reduce primary reformer duty were the use of indirect cooling instead of quench-
and stack temperature of the flue gas [1017], ing, which allowed the recovery of reaction heat
especially in LPG- and naphtha-based plants high pressure steam. Radial or cross-flow pattern
for the synthesis gas instead of axial flow was
A more recent development that breaks away introduced. All modern plants include installations
from the usual plant configuration is to replace for hydrogen recovery (cryogenic, membrane, or
the traditional fired primary reformer with an PSA technology; see ! Ammonia, 2. Production
exchanger reformer which uses the heat of the Processes, Section 6.3.5).
effluent of the secondary reformer [2027, 240,
241]. Also other applications have been reported Machinery. Developments in compressor
in which flue gas [240] heat from the fired and turbine manufacturing have led to higher
reformer is used to perform a part of the efficiencies.
reforming.
. Gas turbine drive for a compressor and/or an
Shift Conversion. Improved LT shift cata- electric generator combined with the use of the
lysts can operate at lower temperatures to achieve hot exhaust as combustion air for the primary
reformer or raising steam (combined cycle) ences, and the economic premises of the custom-
[9599, 244]. er. An evaluation of the individual merits of the
. Employing electric motors instead of conden- described measures in terms of investment and
sation turbines [245]. operational cost in a generalized form is not
. Application of liquid and gas expansion tur- possible and can be done only from case to case
bines can recover mechanical work (e.g., let- in real project studies.
down of the CO2-laden solvent, liquid ammo- To illustrate the forgoing discussion of the
nia, purge and fuel gas). concept of the single-train steam reforming plant,
Figure 2 presents a modern low-energy ammonia
Steam System and Waste-Heat Recovery plant with flow sheet and process streams (UHDE
were improved by the following measures: in- process).
creased pressure and superheating temperature of Figure 3 shows a simplified diagram of the
high-pressure steam; providing a part of the steam system. Even in such an advanced plant the
process steam by natural gas feed saturation quantity of steam generated from waste-heat is as
[19, 87, 170172]; inclusion of a steam super- much as 3.4 times the weight of ammonia
heater downstream of the secondary reformer produced.
[169, 173].
Process Control and Process Optimiza- 1.1.3. Minimum Energy Requirement for
tion. Progress in instrumentation and computer Steam Reforming Processes
technology has led to increased use of advanced
control systems and computerized plant optimi- The energy saving measures described in Sec-
zation. Advanced control systems [186192, tion 1.1.2 have considerably reduced the demand
338340] allow operating parameters to be kept side (e.g., CO2 removal, higher reforming pres-
constant in spite of variations in external factors sure, lower steam to carbon ratio, etc.). On the
such as feedstock composition or ambient or supply side, the available energy has been in-
cooling water temperatures. These systems may creased by greater heat recovery. The combined
be operated in open loop fashion (set values effects on both sides have pushed the energy
changed manually by the operator) or in closed balance into surplus. Because there is no longer
fashion (set points automatically adjusted to an auxiliary boiler which can be turned down to
optimum values by using a computer model with bring the energy situation into perfect balance,
input of operational and economic data). Also the overall savings usually could not be trans-
plant simulation [194197] is possible by using lated into further actual reduction of the gross
extensive computer models of complete plants. energy input to the plant (mainly natural gas). In
These models can simulate in real time the some cases this situation can be used advanta-
dynamic response to changes in operating para- geously. If the possibility exists to export a
meters, plant upsets, etc. Such systems are used substantial amount of steam, it can be economi-
for off-line optimization studies and for operator cally favorable (depending on feedstock price
training [198, 199]. and value assigned to the steam) to deliberately
The above list, by no means complete, is also a increase the steam export by using additional
survey of options for plant revamps (Chap. 10). fuel, because the net energy consumption of the
Quite a number of options can be found in papers plant is simultaneously reduced (Table 3).
presented at the AIChE Annual Symposium A reduction in gross energy demand, that is, a
Ammonia Plants and Related Facilities giving lower natural gas input to the plant, can only be
practical experience and presenting case stories achieved by reducing fuel consumption, because
[389]. the actual feedstock requirement is determined
Many of these elements are strongly interre- by the stoichiometry. So the only way is to
lated with each other and may affect different decrease the firing in the primary reformer, which
sections of the plant concept. It is thus a demand- means the extent of reaction there is reduced.
ing engineering task to arrive at an optimum plant This can be done by shifting some of the reform-
concept, which can only defined by the condi- ing duty to the secondary reformer with surplus
tions set by the feedstock price, the site influ- air or oxygen-enriched air, although this makes
Figure 2. Modern integrated single-train ammonia plant based on steam reforming of natural gas (Uhde process)
a) Sulfur removal; b) Primary reformer; c) Steam superheater; d) Secondary reformer; e) waste-heat boiler; f) Convection
section; g) Forced draft fan; h) Induced draft fan; i) Stack; k) HT and LT shift converters; l) Methanator; m) CO2 removal solvent
boiler; n) Process condensate separator; o) CO2 absorber; p) Synthesis gas compressor; q) Process air compressor; r) Ammonia
converter; s) High-pressure ammonia separator; t) Ammonia and hydrogen recovery from purge and flash gas
1 2 3 4 5 6 7 8 9
CH4, mol % 91.24 91.24 14.13 0.60 0.53 0.65 1.16 24.34 0.12
CnHm, mol % 5.80 5.80
CO2, mol % 1.94 1.94 10.11 7.38 18.14 0.01
CO, mol % 9.91 13.53 0.33 0.40
Ar, mol % 0.28 0.25 0.30 0.37 7.21 0.01
H2, mol % 65.52 54.57 59.85 73.08 73.54 21.72 0.03
N2, mol % 1.02 1.02 0.33 23.64 20.90 25.56 24.93 46.55 0.02
NH3, mol % 0.18 99.82
Drygas, kmol/h 1713.7 534.43 5296.4 8414.2 9520.7 7764.0 8041.4 319.9 3676.6
H2O, kmol/h 3520.6 4086.1 2979.6 22.8 13.3 0.2 0.9
Total, kg/h 30213 9422 121183 199555 199555 70084 71004 6496 62626
p, MPa 5.00 0.25 3.95 3.90 3.61 3.43 3.23 0.25 2.50
T, C 25 25 808 976 229 50 35 38 20
an additional step for the removal of surplus From a mere thermodynamic point of view, in
nitrogen necessary. A more radical step in this an ideal engine or fuel cell, heat and power should
direction is total elimination of the fired primary be obtainable from this reaction. Since real pro-
reformer by using exchanger reformers like the cesses show a high degree of irreversibility, a consi-
ICI GHR and the Kellogg KRES. derable amount of energy is necessary to produce
Based on pure methane, it is possible to ammonia from methane, air and water. The stoi-
formulate a stoichiometric equation for ammonia chometric quantity of methane derived from the
production by steam reforming: above reaction is 583 m3 per tonne of ammonia,
corresponding to 20.9 GJ per tonne NH3 (LHV),
which with some justification could be taken as
minimum value. If full recovery of the reaction heat
is assumed, then the minimum would be the lower
heating value of ammonia, which is 18.6 GJ per
tonne NH3. Table 4 compares the specific energy
Figure 3. Steam system of a modern steam reforming

a) Steam drum, 125 bar; b) NH3 loop; c) Turbine for syngas compressor; d) Turbine for process air compressor and alternator;
e) Surface condenser; f) Condensate treatment; g) BFW pump
requirement for ammonia production by steam The beneficial effect of energy export to the net
reforming with the theoretical minimum. energy consumption is discussed above. Gas
Comparison of energy consumption figures composition is also of some importance. Nitrogen
without precise knowledge of design and evalua- content is marginally beneficial: 10 mol % nitro-
tion criteria can be misleading. First of all the state gen leads to a saving of about 0.1 GJ per tonne
of the ammonia product should be noted. Relative NH3, whereas a content of 10 mol % carbon
to the delivery of liquid ammonia to battery limits dioxide would add 0.2 GJ per tonne NH3 to the
at ambient temperature, the production of 3 bar total consumption value [201 p. 263].
ammonia vapor at the same temperature would Energy requirements and energy saving pos-
save 0.6 GJ per tonne NH3, while delivery as sibilities are also discussed in [2, 119, 205, 206,
liquid at 33 C would need an extra 0.3 GJ per 210, 223, 230, 235, 342].
tonne NH3. The temperature of the available The energy consumption figures discussed so
cooling medium has a considerable influence. far represent a thermodynamic analysis based on
Increasing the cooling water temperature from the first law of thermodynamics. The combina-
20 to 30 C increases energy consumption by tion of the first and second laws of thermody-
0.7 GJ per tonne NH3 . A detailed energy balance, namics leads to the concept of ideal work, also
listing all imports and exports, together with the called exergy. This concept can also be used to
caloric conversion factors used for steam and evaluate the efficiency of ammonia plants. Ex-
power is needed for a fair comparison of plants. cellent studies using this approach are presented
Table 4. Specific energy requirement for ammonia production com-

Table 3. Increase of plant efficiency by steam export (GJ per tonne pared to the theoretical minimum
NH3)
GJ per tonne % theory
Plant Difference NH3 (LHV)
Classical Haber Bosch (coke) 80 90 (338 431)

A B
Reforming, 0.5 10 bar (1953 55) 47 53 225 254
Natural gas 27.1 32.6 5.5 Reforming, 30 35 bar (1965 75) 33 45 139 215
Electric power 1.1 1.1 Low energy concepts (1975 84) 29 33 139 158
Steam export 6.4 6.4 Modern concepts (since 1991) < 28 134
Total energy 28.2 27.3 0.9 Stoichiometric CH4 demand 20.9 100
Table 5. Energy analysis of a low energy ammonia plant (GJ per tonne processes and special engineering know-how to
NH3)
competent engineering companies possessing no
HHV LHV Exergy knowledge of their own in the ammonia field.
There are also several smaller companies with
Input
Natural gas consumption specific and sometimes proprietary know-how
Reformer feed 24.66 22.27 23.28 which specialize in revamps of existing plants or
Reformer fuel 7.49 6.78 7.08 small plant concepts.
Auxiliary boiler fuel 0.34 0.29 0.33 In the following, each of the commercially
Total consumption 32.49 29.34 30.69
Losses most important processes is discussed in some
Reforming 0,38 0,38 4,94 detail and a shorter description of economically
Steam generation 0.33 0.33 2.39 less important processes is given. The process
Shift, CO2 removal, methanation 1.30 1.30 0.67 configuration offered and finally constructed by a
Synthesis 1.70 1.70 1.55
Turbines and compressors 6.50 6.50 0.54 given contractor may vary considerably from
Others (including stack) 1.30 0.68 0.46 case to case, depending on economic and site
Total losses 11.51 10.89 10.55 conditions and the clients wishes. Thus plants
NH3 product 20.98 17,12 20.14 from the same contractor and vintage often differ
Efficiency, % 64,60 58,40 65,60
considerably. It is possible to categorize steam
reforming plants according to their configuration
in the reforming section:
in [202 p. 258], [203]. Table 5 [202] compares
the two methods. The analysis in Table 5 was 1. Advanced conventional processes with high
based on pure methane, cooling water at 30 C duty primary reforming and stoichiometric
(both with required pressure at battery limits), process air in the secondary reformer
steam/carbon ratio 2.5, synthesis at 140 bar in an 2. Processes with reduced primary reformer fir-
indirectly cooled radial converter. ing and surplus process air
Almost 70 % of the exergy loss in the process 3. Processes without a fired primary reformer
occurs in the reforming section and in steam (exchanger reformer)
generation. From conventional first law analysis 4. Processes without a secondary reformer using
it can be seen that almost all of the losses are nitrogen from an air separation plant
transferred to the cooling water. As the analysis
assumes water in liquid state, the LHV analyses In principle the amount of flue gas emitted
in Table 5 is not completely balanced. For a should be related to the extent of fired primary
perfect balance the heat of evaporation of water reforming, but generalizations are questionable,
(as a fictive heating value) would have to be because sometimes the plant layout, as dictated
included. by site requirements, may considerably change
the picture for the specific flue gas value.
1.1.4. Commercial Steam Reforming 1.1.4.1. Advanced Conventional Processes

Ammonia Processes
Kellogg Low-Energy Ammonia Process
Especially with ammonia processes based on [247, 248, 342347, 364]. The Kellogg process is
steam reforming technology it has become a along traditional lines, operating with steam/
habit to differentiate between processes from carbon ratio of about 3.3 and stoichiometric
various licensors and engineering contractors. amount of process air and low methane slip from
This is not so much the case for partial oxidation the secondary reformer. The synthesis pressure
plants (see Section 1.2). Strong competition to- depends on plant size and is between 140 and
gether with increased plant size and the associ- 180 bar. Temperatures of the mixed feed enter-
ated financial commitment has reduced the num- ing the primary reformer and of the process air
ber of licensors and engineering contractors to a entering the secondary reformer are raised to the
few companies capable of offering world-scale maximum extent possible with todays metallur-
plants, often on a lump-sum turnkey basis. In gy. This allows reformer firing to be reduced and,
some cases these companies sub-license their conversely, the reforming pressure to be in-
creased to some extent to save compression costs. Figure 4 shows a simplified flowsheet of the
An important contribution comes from Kelloggs process [347] with Selexol CO2 removal systems
proprietary cross-flow horizontal converter, (other options are, e.g., Benfield or BASF
which operates with catalyst of small particle aMDEA).
size, low inlet ammonia concentration, and high
conversion. Low-energy carbon removal sys- Haldor Topse Process. In addition to tech-
tems (Benfield LoHeat, aMDEA, Selexol) con- nology supply, Haldor Topse also produces the
tribute to the energy optimization. full catalyst range needed in ammonia plants.
When possibilities to export steam or power The energy consumption of a basically classic
are limited, part of the secondary reformer plant configuration has been reduced consider-
waste-heat is used, in addition to steam genera- ably by applying systematic analysis and pro-
tion, for steam superheating, a feature in com- cesses engineering. Descriptions and operational
mon with other modern concepts. Proprietary experience are given in [82, 12, 223, 254265].
items in addition to the horizontal converter are Topse offers two process versions. The first
the traditional Kellogg reformer, transfer line operates at steam/carbon ratio of 3.3 and with
and secondary reformer arrangement, waste- rather high residual methane content from the
heat boiler, and unitized chiller in the refrigera- secondary reformer. Shift conversion is conven-
tion section. tional, the Benfield or Vetrokoke process is used
According to Kellogg 27.9 GJ per tonne NH3 for carbon dioxide removal, and the synthesis
can be achieved in a natural gas based plant with pressure depends on plant size ranging between
minimum energy export, but with export of larger 140 and 220 bar when the proprietary Topse
quantities of steam this value could probably be two-bed radial converter S 200 is used. A sim-
brought down to about 27 GJ per tonne NH3. plified flowsheet is presented in Figure 5.
Figure 4. M.W. Kelloggs low energy process

a) Feed gas compressor; b) Desulfurization; d) Primary reformer; e) Air compressor; f) Secondary reformer; g) Heat recovery;
h) High temperature shift converter; i) Low temperature shift converter; j) Condensate stripper; k) CO2 absorber; l) CO2 flash
drum; m) Recycle compressor; n) Semi-lean Pump; o) Stripper (other options are, e.g., Benfield or BASF aMDEA); p) Stripper
air blower; q) CO2 lean pump; r) Methanator feed preheater; s) Methanator; t) Synthesis gas compressor; u) Dryer; v) Purge gas
H2 recovery; w) Ammonia converter; x) Start-up heater; y) Refrigeration exchanger; z) Refrigeration compressor
Figure 5. Haldor Topses low energy process

a) Desulfurization; b) Primary reformer; c) Secondary reformer; d) Shift conversion; e) CO2 removal; f) Methanation; g) Main
compressor; h) Recycle compressor; i) Heat recovery; j) Converter
An actual plant has reported a consumption of outlet header, also well proven in many installa-
29.2 GJ per tonne NH3 [263]. tions for hydrogen and methanol service. Steam
The second version has a S/C ratio of 2.5 and to carbon ratio is around 3 and methane slip from
shift conversion with medium- and low-temper- the secondary reformer is about 0.6 mol % (dry
ature catalysts, both copper-based. For CO2 basis). The temperature of the mixed feed was
removal Selexol or aMDEA is chosen. The syn- raised to 580 C and that of the process air to
thesis is performed at 140 bar with a Topse 600 C. Shift conversion and methanation have a
two-bed S 200 radial converter, followed by a standard configuration, and for CO2 removal
single-bed radial S 50 converter (S 250 configu- BASFs aMDEA process (1340 kJ/Nm3 CO2) is
ration). After the converters, high-pressure steam preferred. Synthesis is performed at about
is generated. An additional proprietary item is the 180 bar in Uhdes proprietary converter concept
side-fired reformer. with two catalyst beds in the first pressure vessel
For this most energy-efficient concept a figure and the third catalyst bed in the second vessel.
of 27.9 GJ per tonne NH3 is claimed [262]. After each converter vessel high pressure
steam (125 130 bar, up to 1.5 t per tonne NH3)
Uhde Process. Uhde, in the ammonia busi- is generated (Uhde also offers its own boiler
ness since 1928, markets a low-energy ammonia design in cooperation with an experienced boiler
plant with classic process sequence and catalysts maker). Heat exchange between inlet and outlet
[266273, 382]. High plant reliability at compet- of the first bed is performed in the first vessel, and
itive overall costs was a major objective. A gas flow in all beds is radial. When only a
process flow diagram together with the main minimum of energy export (steam or power) is
process stream is presented in Figure 2. possible, the process heat from the secondary
Key features are the high reforming pressure reformer outlet is partly used to raise high-
(up to 43 bar) to save compression energy, use of pressure steam, and partly for superheating
Uhdes proprietary reformer design [267] with high-pressure steam. Refrigeration uses screw
rigid connection of the reformer tubes to the compressors with high operational flexibility and
efficiency. Instead of the standard synloop Uhde quoted. In the synthesis section either an axial
offers the Dual Pressure Process for very large flow quench converter or a radial flow converter
capacities (! Ammonia, 2. Production Pro- with indirect cooling is used. CO2 removal is
cesses, Fig. 51) (see ! Ammonia, 2. Production performed with a physical solvent, and there are
Processes, Section 6.3.2). In this variant a once- no special features compared to other conven-
through converter at lower pressure (100 bar), tional process configurations.
which produces about one third of the capacity, Integrating the ammonia and urea process into
is followed by Uhdes standard loop (! Am- a single train was proposed by Snam Progetti to
monia, 2. Production Processes, Fig. 50) at reduce investment and operating costs [302].
around 200 bar [382, 390394].
Achieved net energy consumption is about 1.1.4.2. Processes with Reduced Primary
28 GJ per tonne NH3 and Uhdes engineers Reformer Firing
expect values of below 27 GJ per tonne NH3
when a gas turbine and large steam export is Braun Purifier Process [18, 9092, 119, 274,
included [271]. 277, 278, 349356]. Characteristic of the low-
energy Braun purifier process (Fig. 6) is the
LEAD Process (Humphreys & Glasgow, reduced primary reformer duty, which is
now Jacobs) [119, 249]. The LEAD process is achieved by shifting a proportion of the reform-
a highly optimized conventional approach with ing reaction to the secondary reformer by using
synthesis at 125 bar and two converter vessels, about 150 % of the stoichiometric air flow. The
the first of which contains two catalyst beds with excess nitrogen introduced in this way is re-
axial-flow quenching, while the second has a moved after the methanation step in a cryogenic
third bed with small particle size catalyst and unit known as a purifier [351], which also re-
radial flow. A consumption of 29.3 GJ per tonne moves the methane and part of the argon. The
NH3 is claimed. result is a purer synthesis gas compared to con-
ventional processes, and only minimal purge
Exxon Chemical Process. The Exxon from the loop is required. A typical flow diagram
Chemical process [275, 276], was specifically of this process is shown in Figure 6.
designed for the companys own site in Canada Synthesis is carried out in the proprietary
and so far not built for third parties. It uses a Braun adiabatic hot-wall converter vessels (!
proprietary bottom-fired primary reformer fur- Ammonia, 2. Production Processes, Fig. 49).
nace and a proprietary hot potash carbon dioxide Each catalyst bed (of which three are now used
removal system with a sterically hindered amine in newer plants [350]) is accommodated in a
activator. Synthesis loop and converter are li- separate vessel with an inlet outlet heat ex-
censed by Haldor Topse A/S. Synthesis is car- changer after the first and high-pressure steam
ried out at 140 bar in a Topse S-200 converter boilers after the following. The smaller furnace
and total energy consumption is reported to be produces less flue gas and consequently less
29 GJ per tonne NH3. waste-heat, which makes it easier to design a
balanced plant with no energy export. The lower
Fluor Process. The Fluor process [2, 117, reforming temperature allows a reduction of the
119, 246] uses the proprietary propylene carbon- steam/carbon ratio to about 2.75 without adverse
ate based CO2 removal system with adsorption effects on the HT shift, because of the less
refrigeration using low level heat downstream of reductive character of the raw gas on account of
the low-temperature shift. Methanation and CO2 its higher CO2 content. In energy balanced plants,
removal are placed between the compression the use of waste-heat in the secondary reformer
stages and thus operate at higher pressure. With effluent is split between steam raising and steam
a value of 32 GJ per tonne NH3 [117] this is not superheating.
really a low-energy concept. The concept shows great flexibility [352] for
design options. It is possible, for example, to aim
Lummus Process. For the Lummus Process for minimal natural gas consumption, even at the
schemes [2, 119, 250, 252, 253] a consumption of cost of importing some electric power. On the
29.6 [119] to 33.5 GJ per tonne NH3 [251] is other hand, it is possible to improve the overall
Figure 6. The Braun purifier ammonia process

a) Sulfur removal; b) Primary reformer; c) Convection section; d) Secondary reformer; e) waste-heat boiler; f) Process air
compressor; g) Gas turbine; h) High- and low-temperature shift converters; i) CO2 removal solvent reboiler; k) CO2 absorber;
l) CO2 desorber; m) CO2 stripper; n) Methanator; o) Driers; p) Purifier heat exchanger; q) Expansion turbine; r) Purifier column;
s) Synthesis gas compressor; t) Synthesis converters; u) waste-heat boiler; v) High-pressure ammonia separator; w) Ammonia
letdown vessel; x) Ammonia recovery from purge gas
efficiency further by exporting a greater amount version of the classical iron catalyst. The proto-
of energy. In this latter case it is advantageous to type was commissioned 1985 at Nitrogen Pro-
incorporate a gas turbine to drive the process air ducts (formerly CIL) in Canada, followed by
compressor. The hot exhaust (about 500 C) of additional plants in China. A flow sheet is shown
the turbine contains 16 17 mol % of oxygen in Figure 7.
and can serve as preheated combustion air of the In the Canadian plant, only the air compressor
primary reformer. In addition it is possible to is driven by a steam turbine, which receives the
include an electric generator to cover the plant total steam generated in the plant and has an
demand and export the surplus. The C. F. Braun electric generator on the same shaft. All other
process can attain 28 GJ per tonne NH3 in a consumers, including synthesis gas compressor,
balanced plant, but with steam export and reali- are driven by electric motors. Separate machines
zation of the available improvement possibilities are used for make-up gas and recycle compres-
a value of 27 GJ per tonne NH3 seems feasible. sion. The make-up gas compressor is located
upstream of the methanator to make use of the
ICI AMV Process. The ICI AMV process compression heat to warm up the cold gas coming
[19, 265, 279291, 415] also operates with re- from the Selexol carbon dioxide scrubber.
duced primary reforming (steam/carbon ratio A further key feature is that about half of the
2.8) and a surplus of process air in the secondary process steam is supplied by feed gas saturation.
reformer, which has a methane leakage of around The synthesis converter is a three-bed design
1 %. The nitrogen surplus is allowed to enter the with quench between the first two beds and an
synthesis loop, which operates at the very low exchanger after the second bed to raise the gas
pressure of 90 bar with an unusually large cata- temperature of the feed to the first bed. Excess
lyst volume, the catalyst being a cobalt-enhanced nitrogen and inerts (methane and argon) are
Figure 7. ICI AMV process

a) Desulfurization; b) Natural gas saturation; c) Process air compression; d1) Primary reformer; d2) Secondary Reformer;
e) Boiler; f) High temperature shift; g) Low temperature shift; h) Selexol CO2 removal; h1) CO2 absorber; h2) Regenerator;
i) Single stage compression; j) Methanation; k) Cooling and drying; l) Circulator; m) Hydrogen recovery; n) Ammonia
converter; o) Refrigeration system
removed by taking a purge gas stream from the feed is sent directly to the secondary reformer,
circulator delivery and treating it in a cryogenic bypassing the fired primary reformer; use of
unit operating at loop pressure. The recovered excess air in the secondary reformer; installation
hydrogen is returned to the circulator suction. of a cryogenic unit as last step of make-up gas
Demonstrated efficiency is 28.5 GJ per tonne production to remove excess nitrogen, residual
NH3. methane, and the majority of the argon. As a
consequence the inert level in the loop can be
Foster Wheeler AM2 Process. The Foster kept rather low, with only a small withdrawal of
Wheeler AM2 process [238, 292], also belongs to purge gas. An energy consumption as low as
the group of processes that shift load from the 28.7 GJ per tonne NH3 is claimed [358]. The
primary to the secondary reformer, but differs process is especially suited for revamps, where it
from the preceding concepts in that only 20 allows plant capacity to be increased.
50 % of the total feedstock is treated in the tubular
primary reformer. The remaining feed is directly Jacobs Plus Ammonia Technology [242]
sent to the secondary (autothermal) reformer is especially tailored for small capacities in the
which operates with a high surplus of process 300 to 450 t/d range, with a load shift from
air (up to 200 %) and a rather high methane slip of primary to secondary reformer and use of excess
2.75 % (dry basis). After conventional shift, fur- process air. To produce a stoichiometric synthe-
ther purification is performed by Selexol CO2 sis gas the surplus nitrogen has to be rejected in
removal, methanation, and molecular sieve dry- the final purification. This is done in a PSA unit,
ing. A cryogenic unit operating at synthesis which receives the purge gas and part of the
pressure rejects the nitrogen surplus from the synthesis gas taken ahead of the methanation
loop. An energy consumption of 29.3 GJ per step. All nitrogen, methane, residual carbon oxi-
tonne NH3 is claimed. des, and argon are adsorbed to give a stream of
pure hydrogen. Hydrogen and the remainder of
Humphreys & Glasgow BYAS Process. the synthesis gas downstream of methanation are
The Humphreys & Glasgow (now Jacobs) mixed to achieve a 3:1 H2:N2 gas composition,
BYAS process [239, 289, 357] resembles the with a lower inerts content than the synthesis gas
above-described processes in its principal pro- after methanation. The consumption figure re-
cess features: a considerable proportion of the ported for a totally energy-balanced plant is
28.8 GJ per tonne NH3, and with substantial a 50 bar pilot plant, an energy consumption of
steam export a value of 26.8 GJ per tonne NH3 28.1 GJ per tonne NH3 is claimed [241].
is claimed.
Kelloggs LEAP Process. In the late 1970s
Montedison Low-Pressure Process. The Kellogg [2, 118, 119, 294] proposed a process
Montedison low-pressure process [119, 241, which extends the basic idea of the concept
295, 301] involves a split flow to two primary described above even further. The flow of the
reformers. About 65 % of the feed steam mix- preheated gas stream mixture is split into three
ture flows conventionally through the radiant streams, with 47 % through catalyst tubes in the
tubes of a fired primary reformer followed by radiant section of the fired primary reformer,
a secondary reformer. The balance of the feed 12 % through catalyst tubes in the convection
steam mixture passes through the tubes of a section, and 41 % through the tubes of an ex-
vertical exchanger reformer. This exchanger re- changer reformer heated by the effluent of a
former has a tubesheet for the catalyst tubes at the secondary reformer. It was intended to operate
mixed feed inlet. There is no tubesheet at the the ammonia synthesis at the pressure of the front
bottom of the tubes, where the reformed gas end by using no synthesis gas compression or
mixes directly with the secondary reformer ef- only a small booster. An enormous quantity of
fluent. The combined streams flow on the shell the classical ammonia synthesis catalyst would
side to heat the reformer tubes in a manner similar have been necessary, and for recovery of the
to that described for the M. W. Kellogg KRES ammonia from the loop a water wash with
reformer, see Section and ! Ammonia, 2. Pro- subsequent distillation was suggested, using
duction Processes, Section 6.1.1). The process air low-level heat in an integrated absorption refrig-
flow is stoichiometric. Synthesis is performed at erator. A consumption below 28 GJ per tonne
60 bar in a proprietary three-bed indirectly NH3 was calculated.
cooled converter with ammonia separation by
water, from which ammonia is then recovered by 1.1.4.3. Processes without a Fired Primary
distillation using low-grade heat. Other process Reformer (Exchanger Reformer)
steps are conventional. As driver of the process
air compressor the installation of a gas turbine is ICI LCA Process. The ICI LCA process
suggested with use of the hot exhaust as pre- [296300] is a radical breakaway from the design
heated combustion air for the fired primary re- philosophy of the highly integrated large plant
former. For this process, which has been tested in used successfully for the last 25 years. Figure 8
Figure 8. ICI LCA process (core unit)

a) Process air compressor; b) Start-up air heater; c) Hydrodesulfurization; d) Saturator; e) GHR; f) Secondary reformer; g) Shift
converter; h) Desaturator; i) PSA system; j) Methanator; k) Gas dryer; l) Ammonia converter; m) Two-stage flash cooling (one
stage shown); n) Chiller; o) Catchpot; p) Flash vessel q) Syngas compressor
Figure 9. Arrangement of core units and utility section
shows a diagram of the so-called core unit which with a special copper zinc alumina-based
includes only the sections essential for ammonia catalyst that operates in quasi-isothermal fash-
production (up to 450 t/d). A separate utility ion and is equipped with cooling tubes in which
section, shown in Figure 9, supplies refrigera- hot water circulates, whereby the absorbed heat
tion, steam, electricity, includes cooling and is used for feed gas saturation, as described
water-demineralization system, and, if needed, above. CO2 removal and further purification is
recovers pure carbon dioxide. Both figures show effected by a PSA system, followed by metha-
the configuration of the first two plants built at nation and drying.
Severnside (UK) with a capacity of 450 t/d each. Synthesis operates at 82 bar [415] in a propri-
Feed gas is purified in a hydrodesulfurization etary tubular converter loaded with a cobalt-
unit operating at lower than usual temperatures enhanced formulation of the classical iron cata-
and passes through a saturator to supply a part of lyst. Purge gas is recycled to the PSA unit, and
the process steam, while the balance is injected pure CO2 is recovered from the PSA waste gas by
as steam. Heated in an inlet outlet exchanger an aMDEA wash. Very little steam is generated
to 425 C the mixed feed enters the ICI gas in the synthesis loop and from waste gases and
heated reformer (GHR) [2022] at 41 bar, pass- some natural gas in the utility boiler in the utility
ing to the secondary reformer at 715 C. The section (60 bar), and all drivers are electric.
shell side entrance temperature of the GHR The original intention was to design an am-
(secondary reformer exit) is 970 C, falling to monia plant which can compete with modern
540 C at the exit of the GHR. Methane levels at large capacity plants in consumption and specific
the GHR exit and the secondary reformer are investment, and, by means of lower energy inte-
25 % and 0.67 % respectively (dry basis). Over- gration, to achieve greater flexibility for start-up
all steam to carbon ratio is 2.5 2.7. The gas, and reduced-load operation, needing minimum
cooled to 265 C in the inlet/outlet exchanger, staffing. The basic plant features (GHR, isother-
enters a single-stage shift conversion reactor mal shift, and synthesis) can in principal be
Figure 10. KBR KAAPplus Process

a) Air compressor; b) Sulfur removal; c) Process heater; d) Automatic reformer (ATR); e) Reforming exchanger (KRES);
f) Condensate stripper; g) CO2 absorber; h) Methanator; i) CO2 stripper; j) Dryer; k) Expander; l) Feed/effluent exchanger;
m) Condenser; n) Rectifier column; o) Synthesis gas compressor; p) KAAP ammonia converter; q) Refrigeration compressor;
r) Refrigeration exchanger
applied to larger capacities. The flow sheet ener- the the gas emerging from the tubes. The shell
gy consumption is 29.3 GJ per tonne NH3. side gas leaves the vessel at 40 bar. The purifier
Kellogg, today Kellogg Brown and Root removes the nitrogen surplus together with re-
(KBR), offers several process schemes with use sidual methane and part of the argon.
of its KRES exchanger reformer and its KAAP Synthesis proceeds at about 90 bar in a four-
ammonia technology [2528]. With including bed radial-flow converter (! Ammonia, 2. Pro-
the Purifier (of C.F. Braun, later Braun and Root) duction Processes, Fig. 53) (hot-wall design)
KBR offers now the KAAPplusProcess [371, with interbed exchangers. The first bed is charged
372, 400402] shown in Figure 10. with conventional iron-based catalyst for bulk
Desulfurized gas is mixed with steam and then conversion and the others with Kelloggs high
split into two streams in approximate ratio 2:1. activity ruthenium-based catalyst, allowing an
These are separately heated in a fired heater. The exit ammonia concentration in excess of 20 % to
smaller of the two enters the exchanger reformer be obtained. The other process steps are more
at 550 550 C, while the remainder is passed along traditional lines. The overall energy con-
directly to the autothermal reformer at 600 sumption claimed for this process can be as low
640 C. The exchanger reformer and the auto- as 27.2 GJ per tonne NH3.
thermal reformer use conventional nickel-based The LCA and KAAPplusProcess are environ-
primary and secondary reforming catalysts, re- mentally favorable because atmospheric emis-
spectively. To satisfy the heat balance, the auto- sions of both nitrogen oxides and carbon dioxide
thermal reformer operates with surplus of air. are dramatically reduced as there is no reforming
The required heat for the endothermic reaction in furnace.
the tubes of the exchanger reformer comes from
the gases on the shell side, comprising a mixture Chiyoda Process [243]. In this process the
of the effluent from the autothermal reformer and traditional fired primary reformer is also replaced
Figure 11. Comparison of Linde LAC process with a conventional process
by an exchanger reformer and the heat balance ammonia synthesis loop. In principle it is similar
requires excess air in the secondary reformer to the PARC process, but designed for world-
with the consequence of a cryogenic unit as final scale capacities. First application was for a
step in the make-up gas preparation to remove the 1350 t/d plant in India. Figure 11 compares the
surplus of nitrogen. Additionally, gas turbines LAC process to a conventional one. If pure CO2
are proposed as drivers for the process air com- is needed, it can be recovered by scrubbing the
pressor and synthesis gas compressor with the hot off-gas from the PSA unit at low pressure or,
exhaust being used for steam generation and feed probably with better energy efficiency, by instal-
gas preheating. ling the CO2 removal unit directly in the synthe-
Topse has described the lay-out for an am- sis gas train ahead of the PSA system. The
monia plant based on fully autothemic reforming synthesis converter and loop are based on ICI
[370]. and Casale know-how. According to Linde the
process should consume about 28.5 GJ per tonne
1.1.4.4. Processes without a Secondary NH3 or, with inclusion of pure CO2 recovery,
Reformer (Nitrogen from Air Separation) 29.3 GJ per tonne NH3.
KTI PARC Process. The KTI PARC am- Humphreys & Glasgow MDF Process
monia process [87, 289, 309, 310, 312315, 348] (now Jacobs) [2, 93, 94, 251, 253, 308, 307,
uses the following process elements: air separa- 323, 324]. This concept has a configuration simi-
tion unit, classical primary reformer at 29 bar, lar to the Linde LAC process. Energy consump-
standard HT shift, power generation in a Rankine tion with inclusion of pure CO2 recovery (which
cycle with CFC to generate electric power (op- is optional) is 32.8 GJ per tonne NH3.
tional), carbon dioxide removal (optional, only
when pure CO2 product is required), PSA, nitro-
gen addition, synthesis loop. In this concept four 1.2. Ammonia Plants based on Partial
sections of the classical process sequence (sec- Oxidation
ondary reforming, LT shift, CO2 removal, metha-
nation) can be replaced by the fully automatic 1.2.1. Ammonia Plants Based on Heavy
high-efficiency PSA system, which has a propri- Hydrocarbons
etary configuration (UOP) in which nitrogen
flushing enhances hydrogen recovery. The over- Although partial oxidation processes can gasify
all efficiency ranges from 29.3 to 31.8 GJ per any hydrocarbon feedstock, on account of its
tonne NH3. higher energy consumption and investment
costs, commercial use of this technology is re-
Linde LAC Process. The Linde LAC pro- stricted to the processing of higher hydrocarbons,
cess [317321] consists essentially of a hydrogen often containing as much as 7 % sulfur. Where
plant with only a PSA unit to purify the synthesis natural gas is unavailable or the heavy feedstock
gas, a standard cryogenic nitrogen unit, and an can be obtained at a competitive price, this
gasification technology can be an economic nace, there is no large amount of flue gas and
choice. consequently less waste-heat is available. There-
There are two commercially proven partial fore, a separate auxiliary boiler is normally nec-
oxidation routes for heavy feedstocks: the Shell essary to provide steam for mechanical energy
process and the Texaco process. In contrast to the and power generation. Nevertheless, some opti-
steam reforming, for which most contractors mization has successfully reduced the overall
have their own proprietary technology for the energy consumption, for which in older installa-
individual process steps, the engineering firms tions values of around 38 GJ per tonne NH3 were
which offer ammonia plants based on heavy reported. More recent commercial bids quote
hydrocarbons have often to rely for the individual values as low as 33.5 GJ per tonne NH3.
process stages on different licensors. Lurgi, for The arguments presented above suggest de-
example, has built very large capacity ammonia scribing the two principal routes, Shell and Tex-
plants that use Shells gasification process, its aco, which differ in the gasification process,
own proprietary version of the Rectisol process rather than listing all individual contractor design
[412], Lindes air separation and liquid nitrogen approaches. Figure 12 shows the classical se-
wash, and Topses technology for synthesis quence of process steps for both cases.
converter and loop.
Independent, experienced engineering com- Processes Using Shell Gasification (e.g.,
panies, not directly active in ammonia plant Lurgi) [29, 3543, 50]. A cryogenic air separa-
design may be used as general contractors to tion plant provides oxygen for the gasification
coordinate a number of subcontractors supplying and the nitrogen for the liquid nitrogen wash and
the different technologies required. This is in line for supplying the stoichiometric amount for the
with the fact that the degree of energy integration synthesis of ammonia. Oil enters the alumina-
is usually lower than in steam reforming tech- lined gasification vessel through a central jet in
nology, because in absence of a large fired fur- the burner nozzle. A substantial pressure drop is
Figure 12. Flow diagrams of ammonia production from fuel oil or heavy residues by the Shell (A) and the Texaco (B) process
(standard configuration)
needed to ensure atomization of the oil and installations (e.g., Linde) use pumps for liquid
proper mixing with oxygen, fed through the oxygen instead of oxygen compressors. In con-
annulus between the jet and the outer case of the trast to the Shell arrangement, oxygen enters the
burner nozzle. The temperature in the gasifica- gasifier through the central nozzle of the burner,
tion vessel (generator) is between 1200 and and oil is fed through the annular space between
1400 C, and the pressure between 35 and central nozzle and outer burner tube. Instead of a
65 bar. waste-heat boiler a direct water quench is applied
The hot gas contains soot, formed because of for cooling the raw synthesis gas, which is sub-
insufficient mixing of the reactants, and fly ash. A sequently scrubbed first in a Venturi scrubber and
waste-heat boiler, a proprietary item of the Shell then in a packed tower to remove the soot.
process, raises 100 bar steam and cools the gas to Texaco also offers a version operating with a
340 C. Soot is removed from the raw gas in a waste-heat boiler instead of a water quench.
two-stage water wash. Older installations used an Although this is preferable when producing
elaborate technique to remove the soot from the CO-rich synthesis gases (e.g., methanol or ox-
water by extraction with naphtha and light oil to ogas), quench is thought to be more economical
form soot pellets which could be burnt or re- when hydrogen-rich gases are manufactured.
cycled to the feed oil. In newer installations the Soot recovery from the water is performed by
carbon water slurry is filtered off in automatic extraction with naphtha. The soot naphtha sus-
filters, and the moist filter cake is subjected to a pension is mixed with feed oil, and the naphtha is
controlled oxidation in a multiple-hearth furnace. distilled off and recycled to the extraction stage.
A selective Rectisol unit with methanol of The shift reaction uses a cobalt molybdenum
about 30 C as solvent is used to remove H2S alumina catalyst [6, 7, 8486, 89] which is not
and COS (together with some CO2) to less than only sulfur-tolerant but also requires a minimum
0.1 %. (see also ! Gas Production, 2. Process- sulfur content in the gas for proper performance.
es). The removed sulfur-rich fraction is sent to a The conversion is subdivided into stages with
Claus plant for recovery of elemental sulfur or intermediate cooling by raising steam. The fol-
converted to sulfuric acid. The gas is heated lowing Rectisol process has a somewhat more
subsequently by heat exchange, supplied with elaborate configuration than the version used in
steam in a saturator, and then fed to shift conver- the Shell route. The large amount of carbon
sion, which proceeds stepwise with intermediate dioxide formed in shift conversion lowers the
heat removal. The gas is cooled by a direct water H2S concentration in the sour gas, and for this
cooler, and the hot water is recycled to the reason a special concentration step is required for
saturator. methanol regeneration to obtain pure CO2 and a
A second Rectisol wash stage follows to fraction sufficiently rich in H2S for a Claus plant
remove CO2 by absorption at 65 C in metha- or a sulfuric acid plant. The remaining process
nol, which is regenerated by flashing and strip- steps are identical with the Shell route. Figure 13
ping. Molecular sieve adsorption then removes gives an example of a Linde flow diagram.
residual traces of methanol and CO2. To remove Descriptions of plants using the Texaco process
residual CO a liquid nitrogen wash is applied for can be found in [5, 7].
final purification with the advantage of also
lowering the argon content in the make-up gas, Topse Process. A concept using enriched
which is adjusted by nitrogen addition to the air instead of pure oxygen and methanation
stoichiometric ratio N2 :H2 1 : 3. Converter instead of a liquid nitrogen wash was proposed
and synthesis loop configuration depend on the by Topse [326, 327]. A Shell gasifier with a
licensor chosen. Plant descriptions are given in waste-heat boiler or a Texaco generator with a
[311, 316, 322, 325]. quench are equally well suited to this process.
After soot removal, shift conversion is performed
Processes Using Texaco Gasification (e.g., on a sulfur-tolerant catalyst in several beds
Foster Wheeler, Linde, Uhde). Temperatures in with intermediate cooling, leaving a residual CO
the generator are similar to those in the Shell content of 0.6 mol %. An appropriate process
process; units with operating pressures up to (Rectisol or amine based) removes the sour gases
90 bar are in operation [9, 4449]. Some modern H2S, COS, and CO2, and this is followed by
Figure 13. Ammonia production based on heavy fuel oil (Linde flow scheme with Texaco gasification)
a) Air separation unit; b) Soot extraction; c) CO2 absorption; d) Methanol/H2O distillation; e) Stripper; f) Hot regenerator;
g) Refrigerant; h) Dryer; i) Liquid N2 scrubber; j) Syngas compressor; k) NH3 reactor
Material Balance
methanation. Make-up gas drying, compression, Foster Wheeler Air Partial Oxidation
and synthesis loop have no special features. The Process [238, 328] is a proposed modification
anticipated energy consumption is 34.8 GJ per of the Texaco gasification process. It is intended
tonne NH3. A basically similar synthesis gas to operate at 70 bar with highly preheated air
preparation, but based on gasification with pure (815 C) instead of pure oxygen. The synthesis
oxygen, is already used in large commercial plant gas purification train comprises soot scrubbing
in Japan [361]. followed by shift conversion, acid gas removal
(for example Selexol), and methanation. The gas [51, 5457, 59, 341, 373375, 408]. The Shell
is dried and finally fed to a cryogenic unit, which process, demonstrated commercially in another
removes the surplus nitrogen by condensation application with a capacity equivalent to a world-
together with methane, argon, and residual car- scale ammonia plant, is also a potential candidate
bon monoxide. The rejected nitrogen is heated for ammonia production processes.
and expanded in a turbine, which helps to drive In recent years little development work has
the air compressor. been done on complete ammonia plant concepts
A major aspect in the design concept is the based on coal. The traditional leading ammonia
separation of nitrogen and oxygen. A conven- contractors have to rely on proprietary processes
tional air separation plant is based on the frac- licensed from different companies, which simi-
tional distillation of oxygen and nitrogen, which larly tend not to have specific ammonia technol-
differ in boiling point by only 13 C. In the ogy of their own. Again, compared to a steam
cryogenic unit for the Foster Wheeler process reforming plant, the degree of integration is
a lesser quantity of nitrogen is separated from considerably lower; power generation facilities
hydrogen with a much higher boiling point dif- are usually separate. Thus it is difficult to identify
ference (57 C). According to Foster Wheeler specific ammonia processes for the individual
this leads to considerable saving in capital in- contractors and the following descriptions serve
vestment and energy consumption compared to as examples, without striving for completeness.
the traditional approach using pure oxygen from
an air separation plant and a liquid nitrogen wash The Koppers Totzek Process gasifies
for gas purification. A figure of 35.6 37.6 GJ coal dust with oxygen in the temperature range
per tonne NH3 is claimed for heavy oil feedstock 1500 1600 C at about atmospheric pressure.
and 31.4 32.7 for natural gas as feedstock. A For a more detailed description of the gasification,
similar variant also using air instead of pure refer to ! Ammonia, 2. Production Processes,
oxygen is offered by Humphreys & Glasgow Section 6.1.1 and [6066]. The cooled gas, free of
(now Jacobs) [365]. coal dust and fly ash, contains about 60 % of CO.
The next step is compression to about 30 bar,
followed by sulfur removal at 38 C with chilled
1.2.2. Ammonia Plants Using Coal as methanol (Rectisol process). Steam is added for
Feedstock the shift conversion, carried out stepwise with
intermediate heat removal and with a standard
In the early days the entire ammonia industry was HTS catalyst. A second Rectisol stage, operating
based on coal feedstock. Today coal or coke at 58 C and 50 bar, removes the CO2, and the
(including coke oven gas) are used as feed for final purification step is a liquid nitrogen wash.
only a smaller part of world-wide ammonia Any of the well known converter and synthesis
production. In 1990, for example, only 13.5 % loop concepts may be used, with no purge or
of the world ammonia capacity used this raw minimal purge, due to the practically inert-free
material [58]. A newer statistic estimates a figure make-up gas. Several plants are operating in
of 19 % for 2001 [408]. But with the enormous South Africa [329, 330] and India [331].
increase of the natural gas prices in the USA the The atmospheric-pressure gasification is a
share of coal in the feedstock pattern of ammonia considerable disadvantage of this process route,
might become larger in the future (see ! Am- which substantially increases equipment dimen-
monia, 1. Introduction, Chapter 8). sions and costs, as well as the power required for
Apart from a few plants operating in India and synthesis gas compression. An energy input of
South Africa, the majority of coal-based ammo- 51.5 GJ per tonne NH3 (LHV) has been reported.
nia plants are found in China. Commercially According to [80], the atmospheric ACGP gas-
proven coal gasification processes are Lurgi (dry ifier could lower the consumption to 44 GJ per
gasifier), British Gas/Lurgi (slagging gasifier), tonne NH3 (HHV).
Winkler/HTW, Koppers Totzek, Shell, Texa-
co, and Dow, [5153, 61]. So far only the Kop- Lurgi Process. Lurgi [52, 53, 75, 76, 78,
pers Totzek, Texaco, and Lurgi processes have 79, 77, 332] offers a concept using its proprie-
been used commercially for ammonia production tary Lurgi dry bottom gasifier, described in
! Ammonia, 2. Production Processes, Section to be appropriate. The operating conditions for

6.1.1. The moving-bed generator, which can the boilers are more severe than those normally
handle any sort of coal (ash content may exceed encountered in power plants; on account of the
30 %), operates at 30 bar, and the product gas high pressure on both sides the heat transfer rates
contains up to 15 % CH4, higher hydrocarbons, and thus the thermal stresses induced are much
troublesome phenolic material, and tars. After higher.
washing with process condensates to remove In steam reforming plants, for example, the
ash and dust, the gas is cooled further with temperature of the gas from the secondary re-
recovery of waste-heat. Several process steps former has to be reduced from 1000 C to 350 C
treat the separated gas liquor to recover tar, before entering the HT shift vessel. In earlier
phenols, and some ammonia. Shift conversion, plant generations two boilers were usually in-
Rectisol process, and liquid nitrogen wash are stalled in series, with a bypass around the second
the further operations in the production of make- to control the inlet temperature for the HT shift.
up gas. The liquid nitrogen wash produces a Common practice for a long time was to use a
methane-rich fraction, which is separately pro- boiler with water tube design. A famous example
cessed in a steam reformer, and the reformed gas is the Kellogg bayonet-tube boiler, applied in
rejoins the main stream at the Rectisol unit for more than 100 plants. Besause of size limitations
purification. The gasification has a power con- two parallel units were installed. For sufficient
sumption of 32 34 GJ per tonne NH3, and natural water circulation these boilers needed a
steam generation consumes 18 22 GJ per steam drum at a rather high elevation and a
tonne NH3, resulting in a total energy consump- considerable number of downcomers (feed wa-
tion of 50 56 GJ per tonne NH3. ter) and risers (steam/water mixture). An alter-
native tube-bundle design which can directly
The Texaco Coal Gasification Process [53, substitute the bayonet-tube internals was recent-
6774, 333336, 359, 360] (see ! Ammonia, 2. ly developed. This concept uses twisted tubes
Production Processes, Section 6.1.1) originates [399].
from Texacos partial oxidation process for In contrast fire-tube boilers are much better
heavy oil fractions and processes a coal water suited for natural circulation and the steam drum
slurry containing 60 70 % coal. A lock hopper can sit in a piggyback fashion right on top of the
system removes ash and glassy slag as a suspen- boiler. This makes it possible to provide each
sion from the quench compartment of the gener- boiler with its own separate steam drum, which
ator. The process can handle bituminous and sub- allows a greater flexibility in the plot plan. In a
bituminous coal but not lignite. The further gas fire-tube boiler, the inlet tubesheet and the tube-
purification steps used to arrive at pure make-up sheet welds are exposed to the extreme tempera-
gas correspond to those described for an ammo- ture of the reformed gas, which creates rather
nia plant using the Texaco partial oxidation of large temperature gradients and therefore high
heavy oil fractions. expansive stress. A positive feature of the design,
Ube Industries commissioned a 1000 t/d am- however, is that debris in feed water (mainly
monia plant in 1984 using Texacos coal gasifi- magnetite particles spalling from the water side
cation process [361, 362]. An energy consump- of the tubes) can collect at the bottom of the
tion of 44.3 GJ per tonne NH3 is stated, which is horizontally mounted vessel without creating
lower than the 48.5 GJ per tonne NH3 quoted for diffficulties and are removed easily by blow-
another Texaco coal gasification-based ammonia down. Water-tube boilers, especially bayonet-
plant [52]. types, are very sensitive in this respect, because
the deposits may collect in the lowest and most
intensively heated part of the tube. In an extreme
1.3. Waste-Heat Boilers for case of scaling, this may restrict the water flow to
High-Pressure Steam Generation the point where boiling occurs irregularly (film
boiling). The risk is overheating and tube failure.
Because of its great influence on reliability and The key factor which allowed the use of fire-
efficiency of all ammonia plants a special section tube boilers after the secondary reformer was the
for the generation of high-pressure steam seems development of thin-tubesheet designs. Thick
tubesheets in this kind of service are too rigid and

have too high a temperature gradient, and the
resultant stress on the tube-to-tubesheet welds
can lead to cracks. The inherent flexibility of thin
tubesheets assists in dispersing stresses and re-
duces the risk of fatigue failure of the tube-to-
tubesheet welds and tubesheet-to-shell welds. In
all the various designs of this concept, the tube-
sheet is only 20 30 mm thick. The hot inlet
channel and the tubesheet are shielded by a
refractory layer, and the tube inlets are protected
by ferrules. In one concept (Uhde [114, 115],
Steinm uller [376]) the flexible tubesheet is an-
chored to and supported by the tubes to withstand
the differential pressure, which poses some re-
striction on the tube length. The tubesheet of
Babcock-Borsig (today Borsig) [112, 377, 378]
is reinforced by stiffening plates on the back side
(Fig. 14). Both solutions have full penetration
tube-to-tubesheet welds. Steinm ullers waste-
heat boiler product line is now owned by Borsig.
A critical analysis of the two concepts is given in
[379]. Figure 15. Uhde U-tube synthesis loop boiler
In the synthesis loop boilers at the exit of the
converter up to 50 % of the total steam is gener-
ated. As much as 1.5 t of steam per tonne 383], KBR [113], and Borsig [386, 384]. A
ammonia, equivalent to 90 % of the reaction heat horizontal synthesis waste-heat boiler was devel-
can be generated. For this service also fire-tube oped by Balcke Durr with straight tubes and
versions have been used, including Borsigss thick tubesheets on both ends [110, 385].
thin-tubesheet design. But compared to the sec- A special design is Borsigs hot/cold tubesheet.
ondary reformer service, where the gas pressure The hot and cold end of the tube are arranged
is lower than the steam pressure, the conditions alternately, so that a hot shank is always to a cold
and stress pattern are different. In the synthesis shank and vice versa. The advantage is that the
loop boiler the opposite is the case with the result tubesheet can kept below 380 C [111, 369].
that the tubes are subjected to longitudinal com- Waste-heat boilers in partial oxidation plants,
pression instead of beeing under tension. Several which cool the exit gas of the generator from
failures in this application have been been re- 1400 C to around 350 C, face additional diffi-
ported [116, 380]. culties. The gas contains soot and probably some
The thick-tubesheet concepts in various con- fly ash particles. Very high gas velocities and
figurations are more generally accepted now. appropriate design are necessary to prevent any
Proven U-type designs (Fig. 15) are available deposition on the heat-exchange surfaces and to
from Uhde [381, 392], Balcke D urr [108, 109, reduce the danger of attrition as well. A special
design for Texaco gasifications (orginally by
Schmidtsche Heidampf GmbH and Steinmul-
ler GmbH) is offered now in an improved version
(Fig. 16) by Borsig [387]. Forced water circula-
tion around the entrance nozzles helps to stand
the high heat flux (700 kJ m2s1) at this loca-
tion. The Shell process uses propretary designs
Figure 14. Reinforced tubesheet of the Borsig boiler
(Fasel Lentjes) [388].
a) Tubesheeet; b) Tube; c) TIG welded root pass; d) Shell; Additional information on waste-heat boilers
e) Supporting ring; f) Stiffener plate; g) Anchor is found in [100, 101, 3, 4, 372]. Many papers on
this subject were presented at the AIChE An-

nual Symposia for Safety In Ammonia Plants and
Related Facilities [389].
1.4. Single-Train Capacity

Limitations Mega-Ammonia Plants
The principle of the economy of scale is well

known in production processes. For ammonia
plants a scale exponent 0.7 is widely used as a
rule of thumb:
cost2 cost1 capacity2 /capacity1 0:7
The advantage of larger plants is not only the

investment but also the reduction of fixed costs,
such as labor, maintenance, and overhead ex-
penses. But the simple formula should be han-
dled with care because it is only valid as long as a
given process configuration is scaled up and the
dimensions of the equipment for very large
capacities do not lead to disproportionate price
increases. For example there may be fewer ven-
dors or special fabrication procedures might
become necessary. So the scale factor could
increase for very large single-train capacities.
Nevertheless the specific investment will de-
crease with the increase of capacity. On the other
hand certain process developments like autother-
mal reforming and exchanger reforming could
reduce the investment for the higher capacities.
For export-orientated plants at locations with
cheap natural gas there is growing interest in very
large capacities. Several studies [368, 394,
402407] have been made by various contractors
to investigate the feasibility and the size limita-
tions for steam reforming plants. According to
most of these studies a capacity of 5000 t/d seems
to be possible. With a conventional process
concept for the front end there is no restriction
for producing syngas for 5000 t/d of ammonia.
Steam reforming furnaces of the required size
have already been built for other applications
(methanol) and neccessary vessel diameters
seem also to be fabricable. A limitation could
be the synthesis compressor which can probably
Figure 16. Borsig syngas waste-heat boiler for Texaco be designed for 4500 t/d only. The KBR KAAP
gasification process has there an advantage because of its low
synthesis pressure. This also holds true for the
Dual Pressure Process of Uhde, where just
the loop which produces only two thirds of the
ammonia is at high pressure whereas the once- lysts. More active LT shift catalysts lower the
through converter is at lower pressure. Another residual CO content, which will reduce H2 loss
capacity limiting factor is pipe diameter in the (methanation) and inert content in the make-up
synthesis section. The largest plant so far was gas. Drying of the make-up gas, addition of
built by Uhde in Saudi-Arabia. It has a capacity hydrogen recovery from purge gas, and installing
of 3300 t/d and came on-stream in 2006. a more effective CO2 removal are other options.
With the aMDEA system, which can be flexibly
tailored to fit into existing process configurations,
2. Modernization of Older Plants it is, for example, possible to simply replace the
(Revamping) MEA solvent with the aMDEA solution, adjust-
ing the activator concentration accordingly to
With rising feedstock prices and hard competi- achieve zero or only minor equipment modifica-
tion in the market, many producers have looked tion. Also hot potash processes have been con-
for possibilities to revamp or modernize their verted in this way to aMDEA.
older, less efficient plants so that they can stay Other measures, involving more additional
competitive. Most revamp projects have been hardware and engineering work, are introduction
combined with a moderate capacity increase of combustion air preheating and reducing the
because some of the original equipment was primary reformer load. This latter option is used
oversized and only specific bottlenecks had to when the revamp objective is capacity increase
be eliminated, not entailing excessive cost. As and the primary reformer is identified as a bot-
the market possibilities for a company do not tleneck. One possibility is to increase the duty of
increase in steps of 1000 or 1500 t/d but slowly the secondary reformer and use air in excess
and continuously, such a moderate capacity ad- of the stoichiometric demand. Elegant variants
dition will involve less risk and will be more of this principle are the Jacobs BYAS process
economical than building a new plant. [239, 289, 357] and the Foster Wheeler AM2
For a revamp project first an updated base-line process [238, 292, 293]. Another method is to
flow sheet of the existing plant should be pre- perform a part of the primary reforming in a pre-
pared from which the proposed improvement can reformer [1017] that uses low-level heat. Alter-
be measured [207209]. Depending on the ob- native methods to enlarge the reforming capacity
jective (energy saving and/or capacity increase) make use of the process heat of the secondary
the following guidelines should be kept in mind: reformer in an exchanger reformer such as ICIs
maximum use of capacity reserves in existing GHR [236] or Kelloggs KRES [27, 413]. If
equipment; shifting duties from overtaxed units oxygen is available, installation of a parallel
to oversized ones; if possible, simple modifica- autothermal reformer or a parallel Uhde CAR
tions of existing equipment are preferable to unit [3034], (see also ! Ammonia, 2. Produc-
replacement; the amount of additional equipment tion Processes, Section 6.1.1) could be consid-
should be kept to a minimum [208]. ered. Description of executed revamp projects
To give an exhaustive list or description of the are given in [358, 224229].
individual modification options is beyond the Similarly, numerous modernization possibili-
scope of this article, but reviews on this subject ties exist for partial oxidation plants, and they
and useful information are given in [210222, may even outnumber those for steam reforming
303306, 342, 410, 414]. Section 1.1.2 describes plants. Common to both plant types is the poten-
modifications that lower the energy consumption tial for improvement of the synthesis loop and
in newer plant generations compared to the first converter. Application of indirect cooling and
generation of single-train ammonia plants, and smaller catalyst particles are frequently chosen to
this also represents an overview of the revamp reduce energy consumption through lower pres-
options for existing steam reforming plants. sure drop, reduced synthesis pressure, higher
Just a few of the frequently used revamp conversion, or a combination thereof. Apart from
possibilities should be mentioned here. In steam replacing existing ammonia converters, in situ
reforming plants it is often possible to lower the modification of the internals of installed conver-
steam/carbon ratio by using improved reforming ters is a very economic approach. Topse [216,
catalysts and copper-promoted HT shift cata- 231] mostly uses its Series 200 configuration; and
Ammonia Casale [101103, 232, 233, 104107] 3. Material Considerations for

its proprietary ACAR technology, with which Equipment Fabrication
more than 90 plants have been revamped so far.
With a split-flow configuration Kellogg pro- Hydrogen Attack. In several steps of the
posed an in situ revamp option to change its four- ammonia production process, especially in the
bed quench converter into a two-stage inter- synthesis section, the pressure shells of reaction
cooled converter (with two parallel beds for the vessels as well as the connecting pipes are in
second stage) using smaller catalyst particles of contact with hydrogen at elevated pressure and
1.5 3.5 mm and 3 6 mm [366, 367]. A prom- temperature with a potential risk of material
ising loop modernization option for the future deterioration [121123].
will be the Kellogg KAAP process [28, 234, 413].
The fact that more than 45 % of world ammo- Chemical Hydrogen Attack. Under certain
nia plants are older than 30 35 years suggests conditions chemical hydrogen attack [124,
that there is a major potential for revamp projects, 125, 127, 418] can occur. Hydrogen diffuses into
even in plants which have already made mod- the steel and reacts with the carbon that is re-
ifications. Revamp histories are a constant topic sponsible for the strength of the material to form
at the AIChE Annual Symposium Ammonia methane, which on account of its higher molec-
Plant and Related Facilities [389] and a wealth ular volume cannot escape. The resulting pres-
of information and practical experience can be sure causes cavity growth along the grain bound-
found there. aries, transforming the steel from a ductile to a
A special revamping option is the integration brittle state. This may finally reach a point where
of other processes into an ammonia plant [369]. the affected vessel or pipe ruptures, in most cases
For example a CO production from a side stream without any significant prior deformation. This
upstream of the HT shift is possible [395]. Hy- phenomenon was already recognized and princi-
drogen can also be produced from a side stream pally understood by BOSCH et al. [1] when they
by using PSA. An example of coproduction of developed the first ammonia process. The resis-
methanol is shown in Figure 17. tance of steel against this sort of attack can be
In the less integrated partial oxidation plants enhanced by alloy components which react with
coproduction schemes are easier to be incorpo- the carbon to form stable carbides (e.g., molyb-
rated and there are several large installations denum, chromium, tungsten, and others). The
which were directly designed to produce ammo- rate of deterioration of the material depends on
nia, methanol and hydrogen [396, 397]. the pressure of the trapped methane, the creep
rate of the material, and its grain structure. Areas
highly susceptible to attack are those which have
the greatest probability of containing unstable
carbides, such as welding seams [126]. The type
of carbides and their activity are strongly influ-
enced by the quality of post-weld heat treatment
(PWHT). The risk of attack may exist at quite
moderate temperatures (ca. 200 C) and a hy-
drogen partial pressure as low as 7 bar.
Numerous studies, experiments and careful
investigations of failures have made it possible to
largely prevent hydrogen attack in modern am-
monia plants by proper selection of hydrogen-
tolerant alloys with the appropriate content of
metals that form stable alloys. Of great impor-
tance in this field was the work of NELSON [120,
Figure 17. Methanol coproduction (side-stream loop)
a) Secondary reformer; b) Waste-heat boiler; c) HT shift;
127, 128], who summarized available experi-
d) LT shift; e) Purification; f) Steam drum; g) Methanol con- mental and operational experience in graphical
verter; h) Catchpot; I) Syngas compressor; j) Let-down vessel form. These Nelson diagrams give the stability
limits for various steels as a function of temper- It has been reported [131, 132] that hot-wall
ature and hydrogen partial pressure. In [129, converters in which the pressure shell is in con-
130], CLASS gives an extensive survey, still valid tact with ammonia-containing synthesis gas at
today, on this subject. Newer experience gained 400 C have developed cracks in circumferential
in industrial applications required several revi- welding seams to a depth nearly approaching the
sions of the original Nelson diagram. For exam- wall thickness in places. This was surprising
ple, 0.25 and 0.5 Mo steels are now regarded as because the operating conditions for the material
ordinary nonalloyed steels with respect to their (2.25 Cr/1 Mo) were well below the Nelson
hydrogen resistance [124]. curve. One investigation [133] concluded that
hydrogen attack had occurred by a special
Physical Hydrogen Attack. A related phe- mechanism at temperatures lower than predicted
nomenon is physical hydrogen attack, which may by the Nelson diagram. Nitriding proceeding
happen simultaneously with chemical attack. It along microcracks could transform carbides nor-
occurs when adsorbed molecular hydrogen dis- mally stable against hydrogen into nitrides and
sociates at higher temperatures into atomic hy- carbonitrides to give free active carbon, which is
drogen, which can diffuse through the material hydrogenated to methane. High residual welding
structure. Wherever hydrogen atoms recombine stress and internal pressure are considered to be
to molecules in the material structure (at second- essential for the propagation of the cracks. A rival
phase particles or material defects such as dis- theory [132, 134] attributes the damage to physi-
locations) internal stress becomes established cal hydrogen attack resulting from the use of
within the material. The result is a progressive agglomerated hygroscopic flux in combination
deterioration of the material that lowers its tough- with insufficient soaking. However, for a longer
ness until the affected piece of equipment cracks time no problems were experienced for the same
and ultimately ruptures. converter design in other cases where non-
The phenomenon is also referred to as hy- hygroscopic flux was used for welding and a
drogen embrittlement. It is most likely to occur more conservative vessel code was adopted,
in welds that not received proper PWHT. Hold- leading to less stress on account of thicker walls.
ing a weld and the heat-affected zone for a But in the meantime also these converters devel-
prolonged period at elevated temperature (an oped cracks. So there are still questions left
operation known as soaking) allows the majo- regarding the two theories.
rity of included hydrogen to diffuse out of the
material. But this may not be sufficient if mois- Nitriding is a problem specific to the am-
ture was present during the original welding monia converter. It occurs in the presence of
operation (for example if wet electrodes or ammonia on the surface of steel at temperatures
hygroscopic fluxes were used), because traces above 300 C [137140]. With unalloyed and
of atomic hydrogen are formed by thermal low-alloy steels, the nitride layer grows with time
decomposition of water under the intense heat to a thickness of several millimeters. Austenitic
of the welding procedure. Highly critical in this steel, used for the converter basket, develops
respect are dissimilar welds [417], such as those very thin but hard and brittle nitride layers, which
between ferritic and austenitic steels [135], tend to flake off. In the nitrided areas, the risk of
where the formation of martensite, which is formation of brittle surface cracks exists.
sensitive to hydrogen attack, may increase the
risk of brittle fracture. Temper Embrittlement. For heat-resistant
At higher temperature and partial pressure, steels long-term service at temperatures above
hydrogen is always soluble to a minor extent in 400 C (e.g., high-pressure steam pipes) can lead
construction steels. For this reason it is advisable to a decline in impact strength [416]. Normally,
not to cool vessels too rapidly when taking them transition temperatures (precipitous decline of
out of service, and to hold them at atmospheric notched bar impact values) of below 0 C are
pressure for some hours at 300 C so that the encountered, but this can increase to 60 C and
hydrogen can largely diffuse out (soaking). In more (temper embrittlement).
contrast to the hydrogen attack described above The susceptibility to temper embrittlement
this phenomenon is reversible. can be reduced by controlling the level of trace
elements (Si, Mn, P, Sn) in steels [141, 142]. at the metal surface which catalyze the Boudourd
Vessels for which temper embrittlement is antic- reaction can be poisoned by H2S, thus inhibiting
ipated should not be pressurized below a certain the initiation of metal dusting [148].
temperature.
Hydrogen Sulfide Corrosion. Corrosion by
Metal Dusting. Metal dusting [3, 143149, hydrogen sulfide in partial oxidation plants can
369, 409] is a corrosion phenomenon which has be controlled by the use of austenitic steels, but
come into focus again in the last few years with special care to ensure proper stress relief of welds
the introduction of exchanger reformer technol- is advisable to avoid stress corrosion cracking in
ogy and the operation of steam superheaters in these plants caused by traces of chlorine some-
the hot process gas downstream of the secondary times present in the feed oil.
reformer waste-heat boiler. Conventional carbu-
rization is a familiar problem with high-temper- Stress Corrosion Cracking. Stress corro-
ature alloys in steam reforming furnaces caused sion cracking (SCC) of many steels in liquid
by inward migration of carbon leading to forma- ammonia is a peculiar phenomenon. It occurs at
tion of carbides in the metal matrix. It happens at ambient temperature under pressure as well as
high temperatures, typically above 800 C, and in atmospheric storage tanks at 33 C. Exten-
the carbon originates from cracking of hydro- sive studies [136, 150, 153163] have defined
carbons. In contrast, metal dusting occurs at the conditions under which SSC in liquid am-
500 800 C on iron nickel and iron cobalt monia is likely to occur and how it may largely
based alloys with gases containing carbon mon- be prevented, but the mechanism is so far not
oxide. The Boudouard reaction, strongly cata- fully understood. Preventive measures include
lyzed by iron, nickel, and cobalt, is generally maintaining a certain water content in the
regarded as the source of the carbon in this case. It ammonia and excluding even traces of oxygen
is assumed that thermodynamically favored sites and carbon dioxide. Welds in pressurized ves-
exist for these elements at the surface and en- sels must be properly stress-relieved, and in
hance the carbon deposition if the gas composi- atmospheric tanks it is important to select the
tion corresponds to a carbon activity >1 [147, appropriate welding electrodes, avoid exces-
148]. sive differences of the thickness of plates
As the name implies, the affected material welded together and choose the correct geom-
disintegrates into fine metal and metal oxide etry of welding seams.
particles mixed with carbon. Depending on the
defects in a protective oxide film on the metal
surface and the ability of the material to sustain References
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26 Ammonia, Kellogg brochure, HG 1/96. 62 Hydrocarbon Process. 63 (1984) no. 4, 94.
27 J. R. LeBlanc, R. Schneider, K. W. Wright, 40th AIChE 63 H. J. Michaels, H. F. Leonard, Chem. Eng. Prog. 74
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28 T. A. Czuppon, S. A. Knez, 41th AIChE Ammonia 64 H. Staege, Hydrocarbon Process. 61 (1982) no. 3, 92.
Safety Symp., Boston 1996. 65 J. E. Franzen, E. K. Goeke, Hydrocarbon Process. 55
29 G. J. van den Berg et al., Hydrocarbon Process. 45 (1976) no. 11, 134.
(1966) no. 5, 193. 66 A. D. Engelbrecht, Tennessee Valley Authority Sympo-
30 H. D. Marsch, N. Thiagarajan, 33rd AIChE Ammonia sium in Muscle Shoals, Alabama 1979.
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31 H. J. Herbort, Uhde Ammonia Symp., Dortmund 1992. ical Plants, Antwerpen 1982.
32 N. Thiagarajan, Uhde Ammonia Symp., Dortmund 68 E. T. Child, Tennessee Valley Authority Symposium in
1992. Muscle Shoals, Alabama 1979.
33 H. D. Marsch, N. Thiagarajan, 37th AIChE Ammonia 69 B. Cornils et al., Hydrocarbon Process. 60 (1981) no. 1,
Safety Symp., San Antonio 1992. 149.
34 Nitrogen 214 (1996) 46. 70 B. Cornils et al., Chem. Ing. Tech. 52 (1980) no. 1, 12.
35 L. W. ter Haar, Ind. Chim. Belge 33 (1968) 655. 71 Hydrocarbon Process. 63 (1984) no. 4, 97.
36 P. D. Becker et al., Chem. Process Eng. (London) 52 72 W. Konkol et al., Hydrocarbon Process. 61 (1982) no. 3,
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37 C. L. Reed, C. J. Kuhre, Hydrocarbon Process. 58 (1979) 73 D. E. Nichols, P. C.Williamson in A. I. More (ed.), Proc.
no. 9, 191. Br. Sulphur Corp. Int. Conf. Fert. Technol. 4th 1981
38 Lurgi Gas Production Technology: The Shell Process 1982, 53.
Lurgi comp. brochure 189e/6.92/2.20. 74 B. Cornils et al., CEER Chem. Econ. Eng. Rev. 12 (1980)
39 C. Higmann, Perspectives and Experience with Partial no. 6 7, 7.
Oxidation of Heavy Residues, Lurgi company brochure. 75 T. J. Pollaert, Chem. Eng. Prog. 74 (1978) no. 8, 95.
40 Integrated Gasification Combined Cycle Process, Lurgi 76 Hydrocarbon Process. 60 (1980) no. 11, 130.
information paper, 1995. 77 M. K. Schad, C. F. Hafke, Chem. Eng. Prog. 79 (1983)
41 W. Liebner, N. Hauser, ERPI Conference on Power no. 5, 45.
Generation and the Environment, London 1990. 78 H. Hiller, Erd ol Kohle Erdgas Petrochem. 28 (1975)
42 C. Higmann, G. Grunfelder, Conference on Gasification no. 2, 74.
Power Plants, San Francisco 1984. 79 P. D. Becker, Tennessee Valley Authority Symposium in
43 W. Soyez, 33rd AIChE Ammonia Safety Symp., Denver Muscle Shoals, Alabama 1979.
1988. 80 W. L. E. Davey, E. L. Taylor, M. D. Newton, P. S.
44 Nitrogen 83 (1973) 40. Larsen, P. S. Weitzel, Asia Nitrogen, Br. Sulphur
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81 A. P. Ting, Shen-Wu-Wan, Chem. Eng. (N.Y.) 76 (1969) brochure.
no. 11, 185. 112 K. Nassauer, M. Fix, AFA/Abu Qir Ammonia/Urea
82 I. Dybkjaer in A. I. More (ed.), Proc. Br. Sulphur Corp. Technol. Symp., 1996.
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83 J. D. Rankin, J. G. Livingstone, Ammonia Plant Saf. 23 San Francisco 1989.
(1981) 203. 114 H. W. Graewe, 25th AIChE Ammonia Safety Symp.,
84 Hydrocarbon Process. 61 (1982) no. 4, 154. Portland 1980.
85 I. Dybkjaer, H. Bohlbro, Ammonia Plant Saf. 21 (1979) 115 H. W. Graewe, Chem. Eng. Progr. 77 (1981) no. 10, 54.
145. 116 H. Lachmann, D. Fromm, 32nd AIChE Ammonia Safety
86 I. Dybkjaer, in: Ammonia from Coal Symposium, TVA Symp., Minneapolis 1987.
Muscle Schoals Alabama, USA p. 133. 117 M. J. P. Bogart, Hydrocarbon Process. 57 (1978) no. 4,
87 K. J. Stokes, Nitrogen 131 (1981) 35. K. J. Stokes in A. I. 145.
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88 K. F. Butwell, D. J. Kubek, P. W. Sigmund, Ammonia (1981) no. 7, 99.
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no. 2, 75. K. F. Butwell, D. J. Kubek, Hydrocarbon Institute, Washington, D.C., June 1977.
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89 BASF, DE-AS 1250792, 1959. Industry, Akademiai Kiado, Budapest 1976, p. 701
90 Nitrogen 144 (1983) 30. 706.
91 B. J. Grotz, G. Good, (1980) Chem. Age (London) 122 C. A. Vancini: La Sintesi dell Amoniaca, Hoepli, Milano
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92 C. K. Wilson et al., Nitrogen 151 (1984) 31. 123 Nitrogen 16 (1962) 48.
93 P. Taffe, J. Joseph, Chem. Age 1978 (October) 14. 124 Steel for Hydrogen Service at Elevated Temperatures
94 P. R. Savage, Chem. Eng. (N.Y.) 82 (1978) no. 25, 68D. and Pressures in Petrochemical Refineries and Petro-
95 S. D. Caplow, S. A. Bresler, Chem. Eng. (New York) 74 chemical Plants, API Publ. 941, Am. Petrol. Inst. 1990.
(1967) no. 7, 103. 125 W. Hausmann et al., Stahl Eisen 107 (1987) no. 12,
96 K. J. Stokes, Chem. Eng. Prog. 75 (1979) no. 7, 88. 45 53.
97 GB 1134 621, 1968 (D. R. Twist, D. W. Stanbridge). 126 B. Granville, Welding in the World 31 (1993) no. 5, 308.
98 S. Ujii, M. Ikeda, Hydrocarbon Process. 60 (1981) no. 7, 127 W. A. Bonner, Hydrocarbon Process. (1951) no. 5, 165.
94. 128 G. A. Nelson, Transactions of ASME 56 (1977) 205
99 W. Rall, 35th AIChE Ammonia Safety Symp., San 213.
Diego 1990. 129 I. Class, Stahl Eisen 80 (1960) 11, 17.
100 Nitrogen 81 (1973) 29, 37. 130 I. Class, Stahl Eisen 85 (1965) 149.
101 U. Zardi, E. Commandini, C. Gallazzi in A. I. More (ed.), 131 A. Heuser, 37th AIChE Ammonia Safety Symp., Los
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1981 1982, 173. 132 G. R. Prescott, 37th AIChE Ammonia Safety Symp., Los
102 Ammonia Casale, DE-OS 3146778, 1981 (U. Zardi, E. Angeles 1991.
Commandini). 133 G. H. Wagner, A. Heuser, G. Heinke, 37th AIChE
103 E. Commandini, U. Zardi: Fertilizer 83, Br. Sulphur Ammonia Safety Symp., Los Angeles 1991.
Corp. 7th Int. Conf., London 1983, Proceedings of the 134 G. R. Prescott, B. J. Grotz, 39th AIChE Ammonia Safety
Conf., p. 179. Symp., Vancouver 1994.
104 Nitrogen 169 (1987) 33. 135 G. R. Prescott, Plant Oper. Prog. 1 (1982) no. 2, 94.
105 E. Commandini, U. Zardi, Fertilizer Latin America, Int. 136 A. W. Loginow, E. H. Phelps, Corrosion-NACE 31
Conf. British Sulphur, Caracas 1989. (1975) no. 11, 404.
106 L. Sutherland, B. Wallace, 33rd AIChE Ammonia Safety 137 H. D. Marsch, Plant Oper. Prog. 1 (1982) no. 3, 152.
Symp., Denver 1988. 138 U. Jakel, W. Schwenk, Werkst. Korros. 22 (1971) no. 1,
107 G. Pagani, U. Zardi, FAI Seminar 1988, The Fertilizer 1.
Society of India, New Dehli, S II/119. 139 S. Y. Sathe, T. M. OConnor 32nd AIChE Ammonia
108 G. R. Prescott et al., 33rd AIChE Ammonia Safety Safety Symp., Denver, 1988.
Symp., Denver 1988. 140 C. A. van Grieken, 33rd AIChE Ammonia Safety Symp.,
109 NH3GasSynthesis, Balke-Durr comp. brochure, Minneapolis, 1987.
CBA 100o-7.91, 1991. 141 Y. Murakami, T. Nomura, J. Watanabe, MPC/ASTM
110 M. Podhorsky et al., 40th AIChE Ammonia Safety Symposium on the Application of 2 1/4 Cr-1 Mo Steel
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Ammonia Safety Symp, San Francisco 1989. Watanabe et al., 29th Petroleum Mechanical Engineer-
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55 (1983) no. 2, 93. 81.
142 R. Bruscato, Weld. J. (Miami) 49 (1970) no. 4, 148. 180 J. M. Blanken, 33rd AIChE Ammonia Safety Symp.,
143 J. A. Richardson, Nitrogen 205 (1993) 49 52. Denver 1988.
144 H. Stahl, S. G. Thomson, 40th AIChE Ammonia Safety 181 F. C. Brown, Nitrogen 100 (1976) 65.
Symp., Tucson 1995. 182 K. J. Mundo, Erd ol, Kohle, Erdgas Petrochemie 31
145 T. Shibasaki et al., 40th AIChE Ammonia Safety Symp., (1978) 74.
Tucson 1995. 183 Nitrogen 182 (1989) 25.
146 R. J. Gommans, T. L. Huurdeman, 39th AIChE Ammo- 184 J. B. LeBlanc, M. N. Shah, L. J. Buividas, Hydrocarbon
nia Safety Symp., Vancouver 1994. Process. 59 (1980) no. 4, 68-G.
147 J. DeJaeger, L. Guns, J. Korkhaus, 39th AIChE Ammo- 185 Hydrocarbon Process. 62 (1983) no. 11, 81.
nia Safety Symp., Vancouver 1994. 186 P. Tjissen, 21nd AIChE Ammonia Safety Symp., Atlan-
148 J. A. Richardson, Boudouard Carbon and Metal Dusting, tic City 1976.
ICI Catalco Tech. paper. 187 G. R. Nieman, L. C. Daigre, III, 18th AIChE Ammonia
149 O. J. Dunmore, Proc. of UK Corrosion Conf., 1982. Safety Symp., Vancouver 1973.
150 A. W. Loginow, E. H. Phelps, Corrosion (Houston) 18 188 C. C. Yost, C. R. Curtis, C. J. Ryskamp, 24th AIChE
(1962) 299. Ammonia Safety Symp., San Francisco 1979.
151 H. Grabke, R. Krajak, J. C. Nava Paz, Corrosion Science 189 Nitrogen 65 (1970) 32.
35 (1993) 1141. 190 T. L. Huurdeman, 33rd AIChE Ammonia Safety Symp.,
152 R. F. Hochmann, 4th Int. Congr. on Metal Corrosion, Denver 1988.
Nat. Corr. Engineers, 1972. 191 R. L. Allen, Jr., G. A. Moser, 36th AIChE Ammonia
153 L. Lunde, Ammonia Plant Saf. 24 (1984) 154. J. M. Safety Symp., Los Angeles 1991.
Blanken, Ammonia Plant Saf. 24 (1984) 140. 192 D. Dekmush et al., 37th AIChE Ammonia Safety Symp.,
154 Plant Oper. Prog. 2 (1983) no. 3, 247. San Antonio 1992.
155 Dechema-Werkstoff-Tabelle/Chem. Bestandigkeit, key- 193 E. Futterer, E. Pattas, Chem. Ztg. 98 (1974) no. 9, 438.
word Ammoniak, sheet 4, Nov. 1978. 194 S. Madhaven, Plant /Oper. Progr. 3 (1984) no. 1, 14.
156 I. Class, K. Gering, Werkst. Korros. 25 (1974) no. 5, 314. 195 S. M. Solomon, 29th AIChE Ammonia Safety Symp.,
157 A. W. Loginow, Mater. Perform. 15 (1976) no. 6, 33. San Francisco 1984.
158 B. E. Wilde, Corrosion-NACE 37 (1981) no. 3, 131. 196 S C. Moore, T. M. Piper, C. C. Chen, 30th AIChE
159 R. S. Brown, Plant Oper. Prog. 1 (1982) no. 2, 97. Ammonia Safety Symp., Seattle 1985.
160 T. Kawamoto et al., IHI Eng. Rev. 10 (1977) no. 4, 17. 197 Nitrogen 169 (1987) 35.
161 N. K. Roy, Fert. Technol. 18 (1981) no. 12, 1. 198 S. Mani, S. K. Shoor, H. S. Pedersen, 33rd AIChE
162 P. B. Ludwigsen, H. Arup, Corrosion (Houston) 32 Ammonia Safety Symp., Denver 1988;Plant /Oper.
(1976) no. 11, 430. Progr. 8 (1989) 33.
163 E. H. Phelps, Ammonia Plant Saf. 16 (1974) 32. 199 G. Grossman, J. Dejaeger, 37th AIChE Ammonia Safety
164 O. J. Quartulli, W. Turner, Nitrogen 80 (1972) 28. Symp., Los Angeles 1991.
165 O. J. Quartulli, W. Turner, Nitrogen 81 (1973) 32. 200 K.-J. Mundo, Chem. Anlagen Verfahren 1972, no. 6, 49.
166 L. Silberring, Nitrogen 120 (1979) 35. 201 I. Dybkjaer in A. Nielsen (ed.): Ammonia Catalysis and
167 P. Hinchley, Chem. Eng. (N.Y.) 86 (1979) no. 17, 120. P. Manufacture, Springer, New York 1995 p. 262, 263.
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168 H. Lachmann, Ammonia Plant Saf. 23 (1981) 51. Manufacture, Springer, New York 1995 p. 258
169 H. Weber et al., Chem. Ing. Tech. 56 (1984) no. 5, 356. 261; 269 271 .
170 Nitrogen 162 (1986). 203 P. Radke, Nitrogen 225 (1997) 27.
171 J. G. Livingstone, A. Pinto, 27th AIChE Ammonia 204 J. S. Campbell, J. W. Marshall, Nitrogen 1976, no. 103,
Safety Symposium, Los Angeles 1982. 33.
172 W. K. Taylor, A. Pinto, 31st AIChE Ammonia Safety 205 L. J. Buividas, Hydrocarbon Process. 58 (1979) no. 5,
Symposium, Boston 1986. 257.
173 Ammonia Uhdes low energy technology, Uhde 206 G. D. Honti in A. I. More (ed.), Proc. Br. Sulphur Corp.
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174 O. J. Quartulli, D. Wagener, Erd ol Kohle Erdgas Pet- 207 D. C. Thomson, 4th Int. Conf. on Fertilizer Technol.,
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175 U. Zardi, A. Antonini, Nitrogen 122 (1979) 33. 208 J. A. Tonna, F. C. Brown, T. W. Nurse, Nitrogen 91: Brit.
176 G. D. Honti, 4th Int. Conf on Fertilizer Technol., London Sulphur Conf., Copenhagen 1991, p. 127 139.
1991, Conf. Proc., p. 1. 209 S. Madhavan, B. Landry, Nitrogen 91: Brit. Sulphur
177 F. Saviano, W. Lagana, P. Bisi, Hydrocarbon Process. Conf., Copenhagen 1991, p. 127 139.
60 (1981) 99. 210 G. R. James, 32nd AIChE Ammonia Safety Symp.,
178 I. Dybkjaer, ECN Europ. Chemical News: Fertilizers 83 Minneapolis 1987. USA 1981. G. R. James, K. J. Stokes,
(suppl.), 1983, p.15. Chem. Eng. Prog. 80 (1984) no. 6, 33.
211 R. W. Parrish, Process Improvements, Gulf Coast Am- 242 Jacobs Ammonia Technology, Jacobs company bro-
monia Producers Meeting, Baton Rouge 1991. chure, 1996.
212 J. R. LeBlanc, Hydrocarbon Process. 65 (1986) no. 8, 243 T. Miyasugi et al., Chem. Eng. Prog. 80 (1984) no. 7, 41.
39 44. T. Miyasugi et al., Ammonia Plant Saf. 24 (1984) 64.
213 M. Jung, Nitrogen 191 (1991) 42 52. 244 S. Uji, M. Ikeda, Hydrocarbon Process. 60 (1981) no. 7,
214 Nitrogen 141 (1983) 38. 94.
215 F. C. Brown, ECN Europ. Chem. News, Proc. Rev. 8 245 E. Nobles, J. C. Stover, Chem. Eng. Prog. 80 (1984)
(1982). no. 1, 81. E. Nobles, J. C. Stover, Ammonia Plant Saf. 24
216 I. Dybkjaer, Fertilizer Latin America, Int. Conf. Brit (1984) 41.
Sulphur, Caracas 1989. 246 Chem. Eng. (N.Y.) 86 (1979) no. 26, 88.
217 A. Nielsen et al., Plant/Oper. Progr. 1 (1982) no. 3, 186. 247 Oilweek (Calgary, Alberta) (May 23, 1983) 12.
218 H. Graewe, Nitrogen 88: 12th Int. Conf. Brit. Sulphur, 248 Chem. Week 134 (March 21, 1984) 15.
Geneva 1988, p. 77. 249 F. C. Brown in A. I. More (ed.), Proc. Br. Sulphur Corp.
219 A. M. Dark, E. A. Stallworthy, Nitrogen 153 (1985) 25 Int. Conf. Fert. Technol. 4th 1981 1982, 39.
220 D. Singh, Process Plant Eng. 73 (1986) Jan March. 250 L. J. Ricci, Chem. Eng. (N.Y.) 86 (1979) no. 3, 50, 54.
221 J. R. LeBlanc, D. O. Moore, R. V. Schneider, III, Oil Gas 251 V. Pachaiyappan, Fertilizer News 1979, 41.
J. 80 (1982) 115. 252 Oil Gas J. 76 (1978) no. 49, 34.
222 R. Darjat, J. R. LeBlanc, Nitrogen 88: 12th Int. Conf. 253 P. Taffe, Chem. Age (London) 117 (Dec. 15, 1978) 8.
Brit. Sulphur, Geneva 1988, p. 77. 254 CEER Chem. Econ. Eng. Rev. 11 (1979) no. 5, 24.
223 I. Dybkjaer, Eur. Chem. News 1983, Feb. 21, 15 (Fer- 255 I. Dybkjaer in A. Nielsen (ed.): Ammonia Catalysis
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224 H. Bendix, L. Lenz, 33rd AIChE Ammonia Safety 263.
Symp., Denver 1988. 256 I. Dybkjaer, Fertilizer Latin America Int. Conf., Caracas
225 D. L. MacLean, C. E. Prince, Y. C. Chae, 24th AIChE 1989; Brit. Sulphur Corp. Proc., vol. 1, p. 77.
Ammonia Safety Symp., San Francisco 1979; Chem. 257 I. Dybkjaer, FAI Seminar 1990, The Fertilizer Assoc. of
Eng. Progr. 1980, 98 104. India, New Delhi, p. SIII1.
226 R. G. Howerton, 24th AIChE Ammonia Safety Symp., 258 T. Bajpai, Nitrogen 88, Brit. Sulphur 12th Int. Conf.,
San Francisco 1979. Geneva 1988.
227 N. W. Patel, S. I. Wang, K. J. Kittelstad, 33rd AIChE 259 T. S. Hariharan, J. Tech. Dev. 7 (1987) no. 4, 42.
Ammonia Safety Symp., Denver 1988. 260 S. R. Sahore, T. S. Krishnan, Fertilizer News 15 (1989).
228 M. Tsujimoto et al., 34th AIChE Ammonia Safety 261 I. Dybkjaer, Fertilizer Industry Ann. Rev. XIII (1990)
Symp., San Francisco 1989. 42a.
229 M. Tsujimoto et al., Nitrogen 91: Brit. Sulphur Conf., 262 I. Dybkjaer, IFA Technical Conf., The Hague 1992.
Copenhagen 1991, p. 127 139. 263 I. Dybkjaer, IFA FADINAP Regional Conf. for Asia
230 A. Pinto, P. L. Rogerson, Chem. Eng. Prog. 73 (1977) and Pacific, Bali 1992
no. 7, 95. 264 Hydrocarbon Process. 62 (1983) no. 11, 79.
231 R. L. Newland, J. D. Pierce, D. M. Borzik, 32nd AIChE 265 F. Brown, Proceedings no. 218, The Fertilizer Society,
Ammonia Safety Symp., Minneapolis 1987. London 1983.
232 Fertilizer News (1987) (December) 19. 266 Hydrocarbon Process. 60 (1981) no. 11, 132.
233 F. C. Brown, U. Zardi, G. Pangani, Nitrogen 88: 12th 267 The Uhde Reformer: High Pressure, High Temperature
Brit. Sulphur Int. Conf., Geneva 1988, p. 1159 139. ServiceUhde Brochure Hi 18 1500 11/1991.
234 T. Czuppon et al., 38th AIChE Ammonia Safety Symp., 268 Energy Efficient Ammonia Production Uhde Eng. News.
Orlando 1993. 3 (1991)
235 K. J. Mundo, Erd ol Kohle Erdgas Petrochem. 31 (1978) 269 Ammonia Plant Energy Integration Uhde Eng. News.
no. 2, 74. 2 (1991).
236 D. Kitchen, A. Pinto, 35th AIChE Ammonia Safety 270 Uhdes Ammonia Technology Uhde Brochure Hi 18
Symp., San Diego 1990. 1500 11/1991; RRD, 1992.
237 A. Nielsen et al., Plant Oper. Prog. 1 (1982) no. 3, 186. 271 Ammonia, Uhdes Low Energy Technology Uhde Eng.
238 P. H. Brook: Fertilizer 83, Br. Sulphur Corp. 7th Int. News. 1 (1991).
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239 F. C. Brown, Eur. Chem. News 1982, no. 15, 10 (Process India, New Delhi, p. SIII3.
Review Suppl.). 273 J. Dejaeger, E. Das, 38th AIChE Ammonia Safety
240 Pullman Inc., US 4079017 (D. B. Crawford, C. L. Symp., Orlando 1993.
Becker, J. R. LeBlanc); US 4162290, 1979 (D. B. 274 B. J. Grotz, Nitrogen 100 (1976) 71.
Crawford, C. L. Becker, J. R. LeBlanc). 275 P. A. Ruziska, C. C. Song, 29th AIChE Ammonia Safety
241 G. Pagani, G. Brusasco, G. Gramatica in A. I. More (ed.), Symp., San Francisco 1984.
Proc. Br. Sulphur Corp. Int. Conf. Fert. Technol. 4th 276 P. A. Ruziska, P. Dranze, C. C. Song, Nitrogen 86, Brit.
1981 1982, 195. Sulphur conf., Amsterdam 1986.
277 B. Grotz, G. Good, Chem. Age (London) 121 (Nov. 14, 313 J. J. Westenbrink, J. Voogd, Nitrogen 86, Brit. Sulphur
1980) S 18. Int. Conf., Amsterdam 1986.
278 Nitrogen 144 (1983) 30. 314 J. J. Westenbrink, J. Voogd, FAI Seminar, New Delhi
279 ICI, EP-A 49967, 1982 (A. Pinto). 1995.
280 J. G. Livingstone, A. Pinto, 27th AIChE Ammonia 315 W. F. van Weenen, J. Tielroy, Proc. Fertilizer Soc.
Safety Symp., Los Angeles 1982. (London) (1980) no. 191, 1.
281 Fertilizer Industry Annual Review, vol. XI, 1988 316 G. Kammholz, G.-A. Muller, Erd ol Kohle Erdgas Pet-
282 S. A. Topham, S. A. Hall, D. G. Heath, ICI/CFDC Tech. rochem. 26 (1973) no. 12, 695.
Symp., Shanghai 1989. 317 Nitrogen 208 (1994) 44 49.
283 W. K. Taylor, A. Pinto, Commisioning CILs Am- 318 M. Lembeck, Asia Nitrogen 96: Brit. Sulphur Int. Conf.,
monia Plant, 31st AIChE Ammonia Safety Symp., Singapore 1996.
Boston 1986; Plant/Operations Prog. 6 (1987) 106 319 M. Lembeck, Fertilizer News (1993) 15.
111. 320 The Linde Ammonia Concept, Linde Comp. publ. 1995.
284 M. P. Robert, C. W. Hooper, ICI/CFDC Tech. Symp., 321 J. Ilg, B. Kandziora, 41st AIChE Ammonia Safety
Shanghai 1989. Symp., Boston 1996.
285 K. J. Elkins et al., Asia Nitrogen, Int. Conf., (Brit. 322 H. E. Butzert, Chem. Eng. Prog. 72 (1976) no. 1, 56;
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286 K. J. Elkins et al., ICIs AMV Ammonia Technology ICI 323 ECN Euro Chem News 20 (1978) 39.
Catalco tech. paper 246W/126/3/AMM. 324 F. C. Brown, Proc. Dev. Symp. 1978, The Inst. of
287 Nitrogen 162 (1989) 32 37. Engineers, p. 1.
288 J. G. Livingstone, A. Pinto, Fertilizer 83, Int. Conf. (Brit. 325 E. Supp, Nitrogen 109 (1977) 36.
Sulphur), London 1988. 326 CEER Chem. Econ. Eng. Rev. 12 (1980) no. 6 7, 33.
289 Nitrogen 141 (1983) 37. 327 J. Dybkjaer, J. Hansen Chem. Age India 31 (1980) (12):
290 Chem. Week 132 (Jan. 5, 1983) 23. DEV. 3/1
291 Hydrocarbon Process. 62 (1983) no. 11, 80. 328 G. F. Skinner in A. I. More (ed.), Proc. Br. Sulphur Corp.
292 D. L. Banquy, Ammonia Plant Saf. 24 (1984) 8. Int. Conf. Fert. Technol. 4th 1981 1982, 491.
293 Foster Wheeler, US 4296 085, 1981 (D. L. Banquy). 329 R. A. Sharpe, Hydrocarbon Process. 55 (1976) no. 11,
294 Pullman Inc., US 4148866, 1979 (C. L. Becker); US 171.
4153673, 1979 (C. L. Becker). 330 L. J. Partridge, Chem. Eng. Prog. 72 (1976) no. 8, 57;
295 Chem. Eng. (N.Y.) 88 (1981) no. 10, 33. Ammonia Plant Saf. 18 (1976) 73.
296 Nitrogen 178 (1989) 30 39. 331 S. McQueen, Chem. Eng. (N.Y.) 85 (1978) no. 25,
297 J. M. Halstead, A. Pinto, FAI Seminar, Delhi 1988. 68 H.
298 A. Pinto, J. M. S. Moss, T. C. Hicks, 34th AIChE 332 Lurgi Express Information O 1323/5.79, Ammonia
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299 K. Elkins, I. R. Barton, 39th AIChE Ammonia Safety 333 Chem. Eng. News 57 (1977) no. 23, 27.
Symp., Vancouver 1994; Operational Performance of 334 G. W. Alves, D. A. Waitzmann, Erd ol Kohle Erdgas
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403 J. Abughazaleh, J. Gosnell, R. Strait, paper presented at sium on Safety in Ammonia Plants and Related Facili-
47th AIChE Symposium on Safety in Ammonia Plants ties, San Diego 2002.
and Related Facilities, San Diego 2002. 417 J. B. Sievert, paper presented at 46th AIChE Symposium
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Conference & Exhibition, British Sulphur Publishing.
408 Coal as feedstock Nitrogen 2003, Warsaw (February T. Eggeman: Ammonia, Kirk Othmer Encyclopedia of Chem-
2003), International Conference & Exhibition, British ical Technology, 5th edition, vol. 2, p. 678710, John
Sulphur Publishing. Wiley & Sons, Hoboken, NJ, 2004, online: DOI: 10.1002/
409 GHR out of the wood yet Nitrogen & Methanol 266 0471238961.0113131503262116.a01.pub3 (April 2010).
(2003) 3340. G. Kreysa, M. Schutze (eds.): Corrosion handbook, 2. ed.,
410 T. Evans, Nitrogen & Methanol 232 (1998) 4152. Dechema; Wiley-VCH, Weinheim 2007.
411 The chemical bearings of the ammonia process Ni- G.-J. Monteny, E. Hartung: Ammonia emissions in agricul-
trogen & Methanol 244 (2000) 3139. ture, Wageningen Academic Publ., Wageningen 2007.
412 By no means a foregone conclusion, Nitrogen &
Methanol 252 (2001) 3351.

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Article No : o02_o12

Ammonia, 3. Production Plants

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

Year 1966 1973 1977 1980 1991

Feed 23.90 23.32 23.48 23.36 22.65

Figure 3. Steam system of a modern steam reforming

Table 4. Specific energy requirement for ammonia production com-

Classical Haber Bosch (coke) 80 90 (338 431)

1.1.4. Commercial Steam Reforming 1.1.4.1. Advanced Conventional Processes

Figure 4. M.W. Kelloggs low energy process

Figure 5. Haldor Topses low energy process

Figure 6. The Braun purifier ammonia process

Figure 7. ICI AMV process

Figure 8. ICI LCA process (core unit)

Figure 9. Arrangement of core units and utility section

Figure 10. KBR KAAPplus Process

Figure 11. Comparison of Linde LAC process with a conventional process

! Ammonia, 2. Production Processes, Section to be appropriate. The operating conditions for

tubesheets in this kind of service are too rigid and

this subject were presented at the AIChE An-

1.4. Single-Train Capacity

The principle of the economy of scale is well

The advantage of larger plants is not only the

Ammonia Casale [101103, 232, 233, 104107] 3. Material Considerations for

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