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Article No : o02_o11
Ammonia, 2. Production Processes

MAX APPL, Dannstadt-Schauernheim, Germany
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . 139 6.1. Synthesis Gas Production . . . . . . . . . . . . . 173

2. Historical Development . . . . . . . . . . . . . . . 140 6.1.1. Feedstock Pretreatment and Raw Gas
3. Thermodynamic Data . . . . . . . . . . . . . . . . 142 Production. . . . . . . . . . . . . . . . . . . . . . . . . . 174
4. Ammonia Synthesis Reaction. . . . . . . . . . . 143 6.1.2. Carbon Monoxide Shift Conversion . . . . . . . 179
4.1. General Aspects . . . . . . . . . . . . . . . . . . . . . 143 6.1.3. Gas Purification. . . . . . . . . . . . . . . . . . . . . . 182
4.2. Catalyst Surface and Reaction Mechanism 145 6.2. Compression . . . . . . . . . . . . . . . . . . . . . . . 186
4.3. Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . 149 6.3. Ammonia Synthesis . . . . . . . . . . . . . . . . . . 190
5. Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . 153 6.3.1. Synthesis Loop Configurations . . . . . . . . . . . 190
5.1. Classical Iron Catalysts . . . . . . . . . . . . . . . 155 6.3.2. Formation of Ammonia in the Converter . . . 191
5.1.1. Composition . . . . . . . . . . . . . . . . . . . . . . . . 155 6.3.3. Waste-Heat Utilization and Cooling . . . . . . . 204
5.1.2. Particle Size and Shape . . . . . . . . . . . . . . . . 161 6.3.4. Ammonia Recovery from the
5.1.3. Catalyst-Precursor Manufacture . . . . . . . . . . 163 Ammonia Synthesis Loop . . . . . . . . . . . . . . 206
5.1.4. Catalyst Reduction . . . . . . . . . . . . . . . . . . . 164 6.3.5. Inert-Gas and Purge-Gas Management . . . . . 207
5.1.5. Catalyst Poisons . . . . . . . . . . . . . . . . . . . . . 167 6.3.6. Influence of Pressure and other Variables of the
5.2. Other Catalysts . . . . . . . . . . . . . . . . . . . . . 169 Synthesis Loop . . . . . . . . . . . . . . . . . . . . . . 209
5.2.1. General Aspects . . . . . . . . . . . . . . . . . . . . . 169 6.3.7. Example of an Industrial Synthesis Loop . . . 211
5.2.2. Metals with Catalytic Potential. . . . . . . . . . . 170 References . . . . . . . . . . . . . . . . . . . . . . . . . 210
5.2.3. Commercial Ruthenium Catalysts. . . . . . . . . 171
6. Process Steps of Ammonia Production . . . 172
1. Introduction slightly lower synthesis pressure and is used in

a few world-size plants (KAAP process of Kel-
Ammonia is the second largest synthetic chemi- logg Braun Root [868870].
cal product; more than 90 % of world consump- BOSCH was already well aware that the pro-
tion is manufactured from the elements nitrogen duction of a pure hydrogen nitrogen mixture
and hydrogen in a catalytic process originally is the largest single contributor to the total
developed by FRITZ HABER and CARL BOSCH using production cost of ammonia [18]. So, in contrast
a promoted iron catalyst discovered by ALWIN to the synthesis reaction, dramatic changes
MITTASCH. Since the early days there has been no happened over the years in the technology of
fundamental change in this process. Even today synthesis-gas generation, and technical ammo-
the synthesis section of practically every ammonia processes differ today mainly with respect to
nia plant has the same basic configuration as the synthesis-gas preparation and purification. The
first plants. A hydrogen nitrogen mixture re- elements nitrogen and hydrogen are abundantly
acts over the iron catalyst (todays formulation available in the form of air and water, from
differs little from the original) at elevated tem- which they can be separated by physical meth-
perature in the range of 400 500 C (originally ods and/or chemical reactions using almost
up to 600 C ) and pressures above 100 bar with exclusively fossil energy. The predominant
recycle of the unconverted part of the synthesis fossil fuels are natural gas, liquefied petroleum
gas and separation of the ammonia product under gas (LPG), naphtha, and higher petroleum
high pressure. End of the 1990s a ruthenium- fractions; coal or coke is used only under special
based catalyst was introduced which allows economic and geographical conditions (China,
2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.o02_o11
140 Ammonia, 2. Production Processes Vol. 3
India, South Africa). Recovery of ammonia The availability of cheap hydrolelectric power
as byproduct of other production processes, in Norway and the United States stimulated the
e.g., coke ovens, is no longer of great development of the electric arc process. Air was
importance. passed through an electric arc which raised its
Of course, some of the hydrogen comes also temperature to 3000 C, where nitrogen and
from the hydrocarbons themselves (methane has oxygen combine to give nitric oxide. In 1904
the highest content), and the carbon acts as a CHRISTIAN BIRKELAND performed successful
reducing agent for water and in some processes experiments and, together with SAM EYDE, an
may also facilitate the separation of oxygen from industrial process was developed and a commer-
nitrogen by formation of carbon dioxide which cial plant was built, which by 1908 was already
can be removed by various operations. producing 7000 t of fixed nitrogen. Working
in parallel, SCHOENHERR at BASF developed a
different electric arc furnace in 1905. The Nor-
2. Historical Development wegians and BASF combined forces in 1912 to
build a new commercial plant in Norway. How-
The catalytic synthesis of ammonia from its ever, since at this time pilot-plant operation of
elements is one of the greatest achievements of ammonia synthesis was already successful,
industrial chemistry. This process not only BASF withdrew from this joint venture soon
solved a fundamental problem in securing our after. Nevertheless, the Norwegian plants oper-
food supply by production of fertilizers but also ated throughout World War I and had total
opened a new phase of industrial chemistry by production of 28 000 t/a of fixed nitrogen with
laying the foundations for subsequent high- a power consumption of 210 000 kW [2]. The
pressure processes like methanol synthesis, specific energy consumption was tremendous:
oxo synthesis, Fischer Tropsch Process, coal 60 000 kW per tonne of fixed nitrogen. Had this
liquefaction, and Reppe reactions. Continuous electricity been generated from fossil fuels this
ammonia production with high space yields on figure would correspond to about 600 GJ per
large scale combined with the ammonia oxida- tonne nitrogen, which is about 17 times the
tion process for nitric acid, which was devel- consumption of an advanced steam-reforming
oped immediately after ammonia synthesis, ammonia plant in 1996.
enabled the chemical industry for the first time The cyanamide process, [25], developed by
to compete successfully against a cheap natural FRANK and CARO in 1898, was commercially
bulk product, namely, sodium nitrate imported established by 1910. Calcium carbide, formed
from Chile. from coke and lime in a carbide furnace (!
The driving force in the search for methods of Calcium Carbide), reacts with nitrogen to give
nitrogen fixation, of course, was to produce calcium cyanamide, which can be decomposed
fertilizers. In principle there are three ways of with water to yield ammonia. The process was
breaking the bond of the nitrogen molecule and energetically very inefficient, consuming
fixing the element in a compound: 190 GJ per tonne of ammonia. Some other
routes via barium cyanide produced from bary-
1. To combine the atmospheric elements nitro- tes, coke and nitrogen, or using the formation of
gen and oxygen directly to form nitric oxides titanium nitride were investigated in Ludwig-
2. To combine nitrogen and hydrogen to give shafen by BOSCH and MITTASCH but did not
ammonia appear promising. In 1934, 11 % of world nitro-
3. To use compounds capable of fixing nitrogen gen production (about 2 106 t/a) [6] was still
in their structure under certain reaction based on the cyanamide process, and some
conditions. plants even continued to operate after World
War II.
A vast amount of research in all three directions After BERTHOLLET proved in 1784 that am-
led to commercial processes for each of them: the monia consists of nitrogen and hydrogen and
electric arc process, the cyanamid process, and was also able to establish the approximate ratio
ammonia synthesis, which finally displaced the between these elements, many experiments in
other two and rendered them obsolete. the 1800s were aimed at its direct synthesis, but
Vol. 3 Ammonia, 2. Production Processes 141
remained unsuccessful [79]. One of the rea- ammonia formation reaction sufficiently (about
sons for the lack of success was the limited 18 C temperature rise for a 1 % increase of
knowledge of thermodynamics and the incom- the ammonia concentration in converted syn-
plete understanding of the law of mass action thesis gas).
and chemical equilibrium. It was the new In 1908 HABER approached BASF (Badische
science of physical chemistry, which developed Anilin & Soda Fabrik at that time) to seek
rapidly in the late 1800s, that enabled chemists support for his work and to discuss the possibil-
to investigate ammonia formation more ities for the realization of an industrial process.
systematically. His successful demonstration in April 1909 of a
Around 1900 FRITZ HABER began to investi- small laboratory scale ammonia plant having all
gate the ammonia equilibrium [10] at atmospher- the features described above finally convinced
ic pressure and found minimal ammonia concen- the BASF representatives, and the companys
trations at around 1000 C (0.012 %). Apart from board decided to pursue the technical develop-
HABER, OSTWALD and NERNST were also closely ment of the process with all available resources.
involved in the ammonia synthesis problem, but In an unprecedented effort, CARL BOSCH, togeth-
a series of mistakes and misunderstandings er with a team of dedicated and highly skilled
occurred during the research. For example, OST- co-workers, succeeded in developing a com-
WALD withdrew a patent application for an iron mercial process in less than five years
ammonia synthesis catalyst because of an erro- [1623]. The first plant started production at
neous experiment, while NERNST concluded that Oppau in September 1913 and had a daily
commercial ammonia synthesis was not feasible capacity of 30 t of ammonia. Expansions in-
in view of the low conversion he found when he creased the capacity to about 250 t/d in 1916/17
first measured the equilibrium at 50 70 bar and a second plant with a capacity of 36 000 t/a
[182, 11]. went on stream in 1917 in Leuna. Further step-
After a controversy with NERNST, HABER re- wise expansions, finally reaching 240 000 t/a,
peated his measurements at atmospheric pressure already decided in 1916, came in full production
and subsequently at higher pressures [1215], only after World War I [3]. After World War I
overcoming his colleagues preoccupation with ammonia plants were built in England, France,
the unfavorable equilibrium concentrations. Italy, and many other countries based on a BASF
HABER concluded that much higher pressures had license or own process developments, with
to be employed and that, perhaps more impor- modified process parameters, but using the same
tantly, a recycle process was necessary. catalyst.
The amount of ammonia formed in a single Up to the end of World War II, plant capacities
pass of the synthesis gas over the catalyst is were expanded by installing parallel lines of
much too small to be of interest for an economic 70 120-t/d units, and synthesis-gas generation
production. HABER therefore recycled the continued to be based on coal until the 1950s.
unconverted synthesis gas. After separating the With growing availability of cheap petrochemi-
ammonia by condensation under synthesis pres- cal feedstocks and novel cost-saving gasification
sure and supplementing with fresh synthesis gas processes (steam reforming and partial oxida-
to make-up for the portion converted to ammo- tion) a new age dawned in the ammonia industry.
nia, the gas was recirculated by means of a The development started in the USA, where
circulation compressor to the catalyst-contain- steam reforming of natural gas was used for
ing reactor. This process, described in the patent synthesis gas production. This process was orig-
DRP 235 421 (1908), became the basis for the inally developed by BASF and greatly improved
industrial manufacture of ammonia and since by ICI, who extended it to naphtha feedstocks.
then the same principle has found widespread Before natural gas became available in large
application in numerous high-pressure proces- quantities in Europe, partial oxidation of heavy
ses. HABER also anticipated the preheating of the oil fractions was used in several plants. The next
synthesis gas to reaction temperature (at that revolution in the ammonia industry was the
time 600 C ) by heat exchange with the hot advent of the single-train steam reforming
exhaust gas from the reactor, the temperature ammonia plants, pioneered by M. W. KELLOGG
of which would be raised by the exothermic and others. The design philosophy was to use a
single-train for large capacities (no parallel lines) theoretically many times. Values for the equilib-
and to be as far as possible energetically self- rium constant are available for pressures up to
sufficient (no energy import) by having a high 350 MPa (3500 bar).
degree of energy integration (process steps in GILLESPIE and BEATTIE [26] (see also [1]) were
surplus supplying those in deficit). Only through by far the most successful experimentally in
this innovative plant concept with its drastic establishing a firm basis for an analytical expres-
reduction in feedstock consumption and invest- sion of the equilibrium constant in the range of
ment costs, could the enormous increase in world industrial interest. The values in Tables 2 and 3
capacity in the following years became possible. were calculated using their equation. A detailed
Increasing competition and rising feedstock description, with literature data and many tables,
prices in the 1970s and 1980s forced industry appears in [1]. A description of the equilibrium
and engineering companies to improve the pro- using the REDLICH KWONG equation of state is
cesses further. given in [325].
The LCA process of ICI (page 97) and the
KRES/KAAP process, which is the first process Heat of Reaction. HABER investigated the
since 1913 to use a non-iron synthesis catalyst, heat of reaction at atmospheric pressure [27].
are recent advances that make a radical break- Numerous authors have estimated the pressure
away from established technology. dependence under various assumptions. Today,
A short survey of the history of ammonia most people use the Gillespie Beattie equation
process technology can be found in [20, 21, [28]. This equation was used in calculating the
24, 25, 331, 834, 841, 874]. values in Table 4. For further data see, for exam-
ple, [1]. Reference [29] contains test results for
the range 120 200 MPa (1200 2000 bar)
3. Thermodynamic Data and 450 525 C. Additional literature can be
found in [30]
Ammonia synthesis proceeds according to the
following reaction: Physical Properties of the Reactants. Var-
ious authors have measured the p V T be-
0:5 N2 1:5 H2
NH3 DH 298 46:22 kJ=mol
havior of nitrogen, hydrogen, and 3 : 1
To fix a kilogram of nitrogen in ammonia hydrogen nitrogen mixtures. Reference [1]
requires reacting 2.4 m3 (STP) of hydrogen and contains a survey. For the specific heat, thermal
0.8 m3 (STP) of nitrogen. About 3.27 MJ of heat conductivity, and viscosity of the reactants,
is evolved. Table 1 is a compilation of the most see [31, 32]. It is to be noted that heats of
important thermodynamic data for the reaction at mixing must be considered for synthesis gas.
atmospheric pressure. This applies especially for high pressures and
low temperatures. Reference [33] gives viscosi-
Chemical Equilibrium. The reaction equi- ties of hydrogen nitrogen and hydrogen
librium has been investigated experimentally and ammonia mixtures.
Table 1. Thermodynamic data for the reaction 0.5 N21.5 H2

NH3 at atmospheric pressure
t, K
300 400 500 600 700 800 900 1000
DH, kJ 46.35 48.48 50.58 52.04 53.26 54.28 55.06 55.68

DS, J K1 99.35 105.63 110.03 112.71 114.55 115.89 116.77 117.48
DG/T, J K1 55.22 15.66 8.88 26.25 38.48 48.02 55.56 61.81
cp, NH3, J mol1 K1 35.52 38.80 41.97 45.04 47.98 50.80 53.49 56.03
cp, H2, J mol1 K1 28.868 29.199 29.278 29.341 29.454 29.634 29.89 30.216
cp, N2, J mol1 K1 29.144 29.270 29.601 30.132 30.777 31.451 32.117 32.724
Table 2. Ammonia content (in mol %) in equilibrium synthesis gas; N2 :H21 : 3
t, C pabs, MPa
5 10 20 30 40 50 60 70 80 90 100
300 39.38 52.79 66.43 74.20 79.49 83.38 86.37 88.72 90.61 92.14 93.39
310 36.21 49.63 63.63 71.75 77.35 81.51 84.73 87.29 89.35 91.03 92.42
320 33.19 46.51 60.79 69.23 75.12 79.53 82.98 85.74 87.98 89.83 91.35
330 30.33 43.45 57.92 66.64 72.79 77.46 81.13 84.09 86.52 88.52 90.20
340 27.64 40.48 55.04 63.99 70.39 75.29 79.18 82.34 84.95 87.12 88.94
350 25.12 37.60 52.17 61.31 67.93 73.04 77.14 80.49 83.28 85.62 87.59
360 22.79 34.84 49.33 58.61 65.41 70.72 75.01 78.55 81.52 84.02 86.15
370 20.64 32.21 46.53 55.89 62.85 68.33 72.80 76.52 79.66 82.33 84.61
380 18.67 29.71 43.79 53.19 60.26 65.89 70.53 74.42 77.72 80.54 82.97
390 16.87 27.36 41.12 50.50 57.66 63.41 68.19 72.23 75.69 78.67 81.25
400 15.23 25.15 38.53 47.86 55.06 60.91 65.81 69.99 73.59 76.71 79.43
410 13.74 23.08 36.04 45.26 52.47 58.39 63.40 67.69 71.42 74.68 77.54
420 12.40 21.16 33.65 42.72 49.91 55.87 60.96 65.36 69.20 72.58 75.57
430 11.19 19.38 31.37 40.26 47.39 53.37 58.50 62.99 66.93 70.43 73.53
440 10.10 17.74 29.20 37.87 44.92 50.88 56.05 60.60 64.63 68.22 71.43
450 9.12 16.23 27.15 35.57 42.50 48.43 53.61 58.20 62.29 65.97 69.28
460 8.24 14.84 25.21 33.36 40.16 46.03 51.19 55.80 59.95 63.69 67.08
470 7.46 13.57 23.39 31.26 37.89 43.67 48.81 53.42 57.60 61.39 64.85
480 6.75 12.41 21.69 29.55 35.71 41.38 46.46 51.06 55.25 59.09 62.60
490 6.12 11.36 20.10 27.34 33.61 39.16 44.17 48.74 52.92 56.78 60.33
500 5.56 10.39 18.61 25.54 31.60 37.02 41.94 46.46 50.62 54.48 58.06
510 5.05 9.52 17.24 23.84 29.68 34.95 39.77 44.22 48.36 52.20 55.80
520 4.59 8.72 15.96 22.24 27.86 32.97 37.68 42.05 46.13 49.96 53.55
530 4.19 8.00 14.77 20.74 26.13 31.07 35.65 39.94 43.96 47.75 51.32
540 3.82 7.34 13.68 19.34 24.49 29.26 33.71 37.89 41.84 45.58 49.13
550 3.49 6.74 12.67 18.02 22.95 27.54 31.85 35.92 39.79 43.47 46.97
560 3.20 6.20 11.74 16.80 21.49 25.90 30.06 34.02 37.80 41.41 44.86
570 2.93 5.70 10.88 15.65 20.13 24.35 28.37 32.20 35.88 39.41 42.81
580 2.69 5.26 10.09 14.59 18.84 22.88 26.75 30.46 34.04 37.48 40.81
590 2.47 4.85 9.36 13.60 17.64 21.50 25.22 28.80 32.26 35.62 38.87
600 2.28 4.48 8.69 12.69 16.52 20.20 23.76 27.22 30.57 33.83 37.00
4. Ammonia Synthesis Reaction reasonable pressures, the theoretically achiev-

able ammonia yield is extremely small because
4.1. General Aspects of the unfavorable position of the thermodynam-
ic equilibrium. In fact, all older attempts to
Usually, a system having an exothermic heat of combine molecular nitrogen purely thermally
reaction under operating conditions should react with atomic or molecular hydrogen failed. On
spontaneously. However, to form ammonia from the other hand, both ammonia and hydrazine
hydrogen and nitrogen molecules, significant result from reacting atomic nitrogen with atomic
energy input is required for the nitrogen molecule hydrogen (see for example [34, p. 186]).
to achieve the activated state. This is because of At pressures above 200 MPa (2000 bar),
its high dissociation energy of 941 kJ/mol, which the synthesis of ammonia proceeds even in the
is considerably higher than that of hydrogen. absence of specific catalysts. At such extreme
According to estimates [34], initiation of ammo- pressures the vessel walls appear to catalyze the
nia synthesis homogeneously in the gas phase formation of ammonia.
requires an activation energy of 230 420 kJ/ In the homogeneous phase under thermody-
mol. For purely thermal energy supply with a namically favorable temperature conditions, the
favorable collision yield, this activation barrier formation of ammonia may be forced by employ-
requires temperatures well above 800 1200 K ing other forms of energy, such as electrical
to achieve measurable reaction rates. However, energy or ionizing radiation. The principal diffi-
at such high temperatures and industrially culty with these so-called plasma processes,
Table 3. Equilibrium ammonia content (in mol %) in the presence of inert gases (2.5 mol % Ar; 7.5 mol % CH4); N2 :H21 : 3
t, C pabs, MPa
5 10 20 30 40 50 60 70 80 90 100
300 32.11 43.10 54.27 60.62 64.95 68.12 70.56 72.49 74.03 75.28 76.31
310 29.52 40.51 51.98 58.63 63.20 66.59 69.22 71.31 72.99 74.37 75.51
320 27.05 37.96 49.66 56.57 61.38 64.98 67.79 70.04 71.87 73.38 74.63
330 24.71 35.46 47.32 54.45 59.48 63.29 66.28 68.70 70.67 72.31 73.68
340 22.51 33.03 44.96 52.30 57.52 61.52 64.69 67.27 69.39 71.16 72.65
350 20.46 30.68 42.62 50.11 55.51 59.68 63.02 65.76 68.03 69.93 71.54
360 18.56 28.42 40.30 47.90 53.46 57.79 61.29 64.18 66.59 68.63 70.36
370 16.80 26.27 38.01 45.69 51.37 55.85 59.49 62.52 65.08 67.24 69.10
380 15.19 24.33 35.77 43.48 49.26 53.86 57.64 60.81 63.49 65.79 67.77
390 13.72 22.31 33.59 41.29 47.14 51.85 55.74 59.03 61.84 64.27 66.36
400 12.39 20.50 31.48 39.13 45.02 49.81 53.81 57.21 60.14 62.68 64.89
410 11.18 18.81 29.44 37.01 42.91 47.76 51.84 55.34 58.38 61.03 63.35
420 10.08 17.24 27.49 34.93 40.83 45.71 49.86 53.44 56.57 59.32 61.75
430 9.10 15.79 25.62 32.92 38.77 43.67 47.86 51.52 54.73 57.57 60.09
440 8.21 14.45 23.85 30.97 36.75 41.64 45.87 49.58 52.86 55.78 58.39
450 7.41 13.22 22.17 29.09 34.78 39.65 43.88 47.63 50.97 53.96 56.65
460 6.70 12.09 20.59 27.29 32.87 37.68 41.92 45.68 49.06 52.11 54.87
470 6.06 11.05 19.10 25.56 31.02 35.77 39.97 43.75 47.16 50.25 53.06
480 5.49 10.11 17.71 23.92 29.23 33.90 38.06 41.83 45.25 48.38 51.24
490 4.97 9.24 16.41 22.36 27.51 32.08 36.20 39.94 43.36 46.51 49.40
500 4.51 8.46 15.19 20.89 25.87 30.33 34.37 38.08 41.49 44.64 47.56
510 4.10 7.74 14.07 19.50 24.30 28.64 32.61 36.26 39.65 42.79 45.72
520 3.73 7.09 13.02 18.19 22.81 27.02 30.89 34.49 37.84 40.97 43.90
530 3.40 6.50 12.05 16.96 21.39 25.46 29.24 32.76 36.07 39.17 42.09
540 3.10 5.97 11.16 15.81 20.05 23.98 27.65 31.09 34.34 37.41 40.31
550 2.83 5.48 10.33 14.73 18.79 22.57 26.12 29.48 32.66 35.68 38.56
560 2.59 5.04 9.57 13.73 17.60 21.23 24.67 27.93 31.04 34.01 36.84
570 2.38 4.64 8.87 12.79 16.48 19.96 23.28 26.44 29.47 32.38 35.17
580 2.18 4.27 8.22 11.92 15.43 18.76 21.95 25.01 27.96 30.80 33.54
590 2.01 3.94 7.63 11.12 14.44 17.63 20.69 23.65 26.51 29.28 31.96
600 1.85 3.64 7.08 10.37 13.52 16.56 19.50 22.35 25.12 27.81 30.43
which also impedes their economic use, is that until today in commercial production units are
the energy supplied is useful only in part for composed in unreduced form of iron oxides
ammonia formation. A greater part is trans- (mainly magnetite) and a few percent of Al, Ca,
formed in primary collision and exothermic sec- and K; other elements such as Mg and Si may also
ondary processes into undesirable heat or unus- be present in small amounts. Activation is usually
able incidental radiation. accomplished in situ by reduction with synthesis
In the catalytic combination of nitrogen and gas. Prereduced catalysts are also commercially
hydrogen, the molecules lose their translational available.
degrees of freedom by fixation on the catalyst Numerous investigations have been per-
surface. This drastically reduces the required formed to elucidate the mechanism of catalytic
energy of activation, for example, to 103 kJ/mol reaction of nitrogen and hydrogen to form am-
on iron [35]. The reaction may then proceed in monia. References [3639] give reviews of the
the temperature range 250 400 C. In 1972, it older and some of the newer literature. Since the
was discovered that electron donor acceptor 1980s a large variety of surface science techni-
(EDA) complexes permit making ammonia with ques involving Auger electron spectroscopy, X-
measurable reaction rate at room temperature. ray photoelectron spectroscopy, work-function
This section concentrates mainly on the am- measurements, temperature-programmed ad-
monia synthesis reaction over iron catalysts and sorption and desorption, scanning tunnelling
refers only briefly to reactions with non-iron microscopy, and others have been developed
catalysts. Iron catalysts which are generally used [42, 43]. Many of these methods are based on
Table 4. Heat of reaction DH (in kJ) for the reaction 0.5 N21.5 H2
NH3, from [26]
t, C pabs, MPa
0 (ideal) 10 20 30 40 50 60 70 80 90 100
0 44.39 55.20 66.02 76.84 87.66 98.47 109.29 120.11 130.92 141.74 152.56
25 44.92 53.48 62.03 70.59 79.15 87.70 96.26 104.82 113.38 121.93 130.49
50 45.44 52.37 59.30 66.23 73.16 80.09 87.02 93.95 100.88 107.80 114.73
75 45.96 51.69 57.41 63.14 68.86 74.58 80.31 86.03 91.76 97.48 103.20
100 46.47 51.28 56.10 60.91 65.72 70.53 75.34 80.16 84.97 89.78 94.59
125 46.97 51.08 55.19 59.29 63.40 67.51 71.62 75.72 79.83 83.94 88.04
150 47.46 51.02 54.57 58.12 61.68 65.23 68.78 72.34 75.89 79.44 83.00
175 47.95 51.06 54.17 57.28 60.39 63.50 66.61 69.72 72.83 75.94 79.05
200 48.42 51.17 53.92 56.68 59.43 62.18 64.93 67.69 70.44 73.19 75.94
225 48.88 51.34 53.80 56.26 58.71 61.17 63.63 66.09 68.55 71.01 73.47
250 49.33 51.54 53.76 55.97 58.19 60.40 62.62 64.84 67.05 69.27 71.48
275 49.76 51.77 53.79 55.80 57.81 59.82 61.84 63.85 65.86 67.87 69.88
300 50.18 52.02 53.86 55.70 57.54 59.38 61.22 63.06 64.90 66.74 68.59
325 50.59 52.28 53.98 55.67 57.37 59.06 60.75 62.45 64.14 65.83 67.53
350 50.99 52.55 54.12 55.69 57.26 58.82 60.39 61.96 63.53 65.10 66.66
375 51.36 52.82 54.28 55.74 57.20 58.66 60.12 61.58 63.04 64.49 65.95
400 51.73 53.09 54.46 55.82 57.18 58.55 59.91 61.28 62.64 64.00 65.37
425 52.07 53.35 54.64 55.92 57.20 58.48 59.76 61.04 62.32 63.60 64.88
450 52.40 53.61 54.82 56.03 57.23 58.44 59.65 60.86 62.06 63.27 64.48
475 52.71 53.86 55.00 56.14 57.29 58.43 59.57 60.72 61.86 63.00 64.14
500 53.01 54.09 55.18 56.26 57.35 58.43 59.52 60.60 61.69 62.78 63.86
525 53.28 54.31 55.35 56.38 57.42 58.45 59.48 60.52 61.55 62.58 63.62
550 53.53 54.52 55.51 56.50 57.48 58.47 59.46 60.45 61.44 62.42 63.41
575 53.76 54.71 55.66 56.60 57.55 58.50 59.44 60.39 61.33 62.28 63.23
600 53.98 54.88 55.79 56.70 57.61 58.52 59.43 60.34 61.24 62.15 63.06
interaction of slow electrons, ions, or neutral 4. Desorption of the ammonia formed into the
particles and exhibit high sensitivity to surface gas phase
structures. With these powerful tools the kinetics 5. Transport of the ammonia through the pore
of nitrogen and hydrogen adsorption and desorp- system and the laminar boundary layer into
tion could be investigated, and it was also possi- the bulk gas stream
ble to identify adsorbed intermediates. The re-
sults of these experiments allow the mechanism Only the portion of the sequence that occurs
of ammonia synthesis in the pressure range of on the catalyst surface is significant for the
industrial interest to be elucidated [40, 41, 44]. intrinsic catalytic reaction. Of special impor-
As with every catalytic gas-phase reaction, the tance is the adsorption of nitrogen. This assump-
course of ammonia synthesis by the Haber tion is decisive in representing the synthesis
Bosch process can be divided into the following reaction kinetics. The transport processes occur-
steps: ring in the pores of the catalyst in accordance
with the classical laws of diffusion are of impor-
1. Transport of the reactants by diffusion and tance in industrial synthesis (see also Sections
convection out of the bulk gas stream, through 5.1.2 and 4.3).
a laminar boundary layer, to the outer surface
of the catalyst particles, and further through
the pore system to the inner surface (pore 4.2. Catalyst Surface and Reaction
walls) Mechanism
2. Adsorption of the reactants (and catalyst poi-
sons) on the inner surface Earlier studies [67, 6975, 82, 197] had already
3. Reaction of the adsorbed species, if need be suggested that on iron catalysts nitrogen adsorp-
with participation by hydrogen from the gas tion and dissociation can be regarded as the rate-
phase, to form activated intermediate determining step for the intrinsic reaction. This
compounds has now been fully confirmed by microkinetic
simulations based on the results of surface sci-

ence studies [40, 54, 76]. In single-crystal
experiments it was found that the activation
energy for dissociative nitrogen adsorption is
not constant; it increases as the surface becomes
increasingly covered with adsorbed nitrogen
species. Under reaction conditions it can attain
values of 63 84 kJ/mol [44, 66, 69, 70] which
are typical for ammonia synthesis. In the case of
nitrogen the first step seems to be an adsorption in
molecular state followed by chemisorption in the
atomic state. From experimental results it was
concluded that for hydrogen a direct transition
from the gaseous H2 molecule into the chemi-
sorbed Had is most likely, and evidence for the
stepwise hydrogenation of surface nitrogen
atomic species was found. In IR spectroscopic
investigations, NH and NH2 species were identi-
fied [77], and secondary ion emissions detecting
NH also confirmed the presence of NH species
on the surface [105]. It was further shown that at
lower temperatures nitrogen becomes adsorbed
only in the molecular state, but subsequently
dissociates when the temperature is raised. Iso-
topic experiments with 30N2 and 29N2 showed
that the surface species resulting from low-
temperature adsorption was molecular, whereas
that from high-temperature adsorption was atom-
ic [107]. Ammonia synthesis is highly sensitive
to the orientation of the different crystal planes
of iron in the catalyst [99103]. Measurements
on defined single crystal surfaces of pure iron
performed under ultrahigh vacuum [7880]
clearly showed that Fe(111) is the most active
surface. This was also demonstrated by the rate
of ammonia formation on five different crystal-
lographic planes for unpromoted iron at 20 bar,
as shown in Figure 1.
Activation energy, reactivity, adhesion coef-
ficient (the probability that a nitrogen molecule
striking the surface will be adsorbed dissocia-
tively) and work function show a clear depen-
dence on surface orientation [48, 98]:
Ammonia synthesis activity:

(111) > (211) > (100) > (210) > (110)
Activation energy of nitrogen adsorption:
(111) > (100) > (110) Figure 1. Ammonia formation rate on different iron surfaces
Work function: [48, 76]
(210) > (111) > (211) > (100) > (110)
Surface roughness:
(210) > (111) > (211) > (100) > (110)
Ultrahigh vacuum (UHV) experiments with Based on these experimental results a reaction
single crystals show that the activation energy scheme for the ammonia synthesis may be
of the nitrogen adsorption at zero coverage in- formulated comprising the following sequence
creases from about zero for Fe(111) to 21 kJ/mol of individual steps [40]:
for Fe(110) [40, 69, 9597]. These values in-
H2
2 Had 1
crease significantly for higher coverage [96, 97].
Adsorption and desorption under higher pressure
N2
N2;ad 2
on finely dispersed catalyst indicate that the
reaction is highly activated under these condi-
tions with high coverage, about 100 kJ/mol [67, N2;ad
2 Nad 3
68].
According to [95, 96] adsorption on the planes Nad Had
NHad 4
Fe(111) and Fe(110) is associated with a regroup-
ing of the surface atoms. NHad Had
NH2;ad 5
A possible explanation for the high activity of
faces (111) and (211) is that these are the only NH2;ad Had
NH3;ad 6
surfaces which expose C7 sites (iron with seven
nearest neighbors) to the reactant gases. There NH3;ad
NH3 7
are theoretical arguments [85] that highly coor-
dinated surface atoms should show increased The progress of the reaction may be described
catalytic activity due to low-energy charge fluc- in the form of an energy profile, as shown in
tuations in the d-bands of these highly coordinat- Figure 2. Industrial ammonia synthesis in the
ed atoms. This argument might probably be the homogeneous gas phase is not feasible because
key for the special role of C7 sites. Other reasons of the high dissociation energies for the initial
discussed are based on charge transfer and inter- steps. The reaction over a catalyst avoids this
action of iron d-bands with antibonding 2 p* problem since the energy gain associated with
orbitals of nitrogen [81]. the surface atom bonds overcompensates these
Promotion with potassium of single iron dissociation energies and the first steps have
crystals enhances the sticking probability for actually become exothermic.
nitrogen dissociation much more on the Fe(100) Dissociative nitrogen adsorption remains
and (110) than on the Fe(111) (factors 280, ca. nevertheless the rate-determinating step, not so
1000 and 8, respectively) to the effect that the much on account of its activation barrier but
differences in surface orientation disappear rather because of the very unfavorable pre-
[839]. A similar effect was not found for the exponential factor in its rate constant. The
ammonia synthesis at 20 bar and catalyst tem- subsequent hydrogenation steps are energetically
perature of 400 C: only a two-fold increase of uphill, but the energy differences involved can
the ammonia formation rate was measured for easily be overcome at the temperatures (ca.
Fe(111) and Fe(100), and the face (110) was 700 K) used in industrial ammonia synthesis. It
found to be inactive with and without potassium is, however, quite apparent that the rate-control-
[48]. Other experiments [83] show that even the ling step would switch from dissociative nitrogen
least active face Fe(110) becomes as active for adsorption to hydrogenation of adsorbed atomic
the synthesis as Fe(111) after addition of alumi- nitrogen species if the temperature were lowered
na with subsequent annealing with oxygen and sufficiently because of these differences in
water vapor. A proposed mechanism for these activation energy.
findings backed by X-ray photoelectron spec- Some critics [86] of the above energy diagram
troscopy, temperature programmed desorption question the low net activation barrier from the
and electron microscopy assumes that first gas phase. The arguments are based on an analy-
alumina forms an iron aluminate FeAl2O4 sis of activation energies from early measure-
on the surface. This new surface then may serve ments of the nitrogen adsorption kinetics on
as a template on which iron grows with (111) singly (Al2O3) promoted catalysts and on the
and (211) orientation upon exposure to the results of experiments with supersonic molecular
synthesis-gas mixture in the reaction [84]. beams [87, 88].
Figure 2. Schematic energy profile of the progress of ammonia synthesis on Fe (energies in kJ/mol) [40]
An attempt to explain these differences is has a significantly better activity at lower tem-
given in [89]. In more recent investigations of perature than magnetite. Wustite is a nonstoi-
the adsorbed nitrogen species [9194] a second chiometric iron oxide(Fe1xO) with a cubic crys-
molecularly adsorbed species was detected. This tal structure, x ranging from 0.03 to 0.15. With
so-called a state was interpreted as a bridge- still (111) faces present in the reduced state the
bonded species with electron donation from the catalyst has a higher specific surface area and an
surface to the antibonding p levels of N2, whereas improved pore structure.
the g state is regarded as a terminally bound A critical evaluation of the present knowledge
species. Thus the following picture for the nitro- of the mechanism of the synthesis reaction was
gen adsorption emerges: made by SCHLOGL [97].
Other reaction mechanisms have been de-
N2 !S N2 g state!S N2 S a state bated for reaction temperatures below 330 C
!2 S Nb state [51, 102, 104115]. These propose participa-
tion of diatomic nitrogen, or of adsorption
where S* denotes a surface atom. complexes containing diatomic nitrogen, in the
For industrial catalysts made by careful re- rate-determining step (see [36, 37] for further
duction of magnetite fused with nonreducible literature).
oxide promoters the important role of the NIELSEN et al. investigated ammonia synthesis
(111) face seems to be confirmed [47]. However, on a commercial Topse catalyst, KM IR, over a
the question whether the active industrial catalyst wide temperature range. They found evidence
exposes mostly (111) faces remains unresolved. that a different reaction mechanism predomi-
If not, further improvements of the catalyst are at nates below and above 330 C [116]. Also, at
least theoretically possible [90]. This was indeed low temperatures, chemisorbed hydrogen blocks
the case with the new AmoMax-10 catalyst [844, the catalyst surface [117]. The latter finding is in
845] of S udchemie. This catalyst in its oxidic agreement with the observations of ERTLs group
form is based on wustite instead of magnetite and [66].
Reaction Mechanism on Non-Iron Cata-

lysts. Non-iron systems which exhibit some
potential to catalyze ammonia synthesis can be
divided into the following groups [120]:
. Platinum group metals such as Ru, Os Ir, Pt (no

nitrides)
. Mn, Co, Ni, Tc, Rh and their alloys (no nitride
formation under synthesis conditions)
. Mn, Mo, V (present as nitrides under the
reaction conditions)
In the non-iron systems the rate-determining

step is also dissociative adsorption of nitrogen
and the catalyst effectivity seems to be primarily
dictated by the activation energy of the dissocia-
tion reaction [120]. This is somewhat surprising
in view of the marked differences in the heats of
adsorption of nitrogen and the adsorption activa-
tion energy. This even holds for tungsten, which
has no significant activation energy and a high Figure 3. Reaction rate for NH3 synthesis. Dependence on
adsorption enthalpy for nitrogen, so that hydro- the ammonia concentration at various pressures
genation of adsorbed atomic nitrogen could be
expected to be the rate-determining step. The driving force. Therefore, the rate of formation
factor common with the iron catalyst is the at first increases with rising temperature but
structure sensitivity. then goes through a maximum as the system
The only system which seems to be promising approaches thermodynamic equilibrium (Fig. 4).
for industrial application is ruthenium promoted
with rubidium on graphite as carrier (see Sec-
tion 5.2.3). Further information on structure,
activity and reaction mechanism of non-iron
catalysts is given in [37, 120122, 127]. Specific
references: vanadium [118], uranium [119], mo-
lybdenum [123125], tungsten [126].
4.3. Kinetics
Knowledge of the reaction kinetics is important

for designing industrial ammonia synthesis re-
actors, for determining the optimal operating
conditions, and for computer control of ammonia
plants. This means predicting the technical de-
pendence on operating variables of the rate of
formation of ammonia in an integral catalyst
volume element of a converter.
High pressure promotes a high rate of ammo-
nia formation; high ammonia concentration in
the synthesis gas (recycle gas) restricts it
(Fig. 3). High temperatures accelerate ammonia
formation but imply a lower value of the equi- Figure 4. Reaction rate for NH3 synthesis. Dependence on
librium ammonia concentration and so a lower the temperature at various pressures
or from empirical evaluations. A critical review

of the data and equations published up to 1959
appears in [128]. A discussion of kinetics
proposed up to 1970, insofar as they have been
based on measurements in the operating range
of commercial interest, can be found in [51].
An evaluation of present knowledge is given in
[40, 5254].
Contradictory data on the kinetics of ammo-
nia synthesis, especially in the earlier literature,
in some circumstances may reflect a lack of
attention to the influence of impurities in the
gas. If oxygen compounds are present in the
synthesis gas, reversible poisoning of the adsorb-
ing areas, in accordance with an equilibrium
depending on the temperature and the water
vapor hydrogen partial pressure ratio, must be
taken into account when developing rate equa-
tions (see also Section 5.1.4).
Experimental Measurements of Reaction

Kinetics. The reaction expressions discussed in
the following model the intrinsic reaction on the
catalyst surface, free of mass-transfer restric-
Figure 5. Ammonia synthesis rate constant dependence on
hydrogen nitrogen ratio
tions. Experimental measurements, usually
made with very fine particles, are described by
theoretically deduced formulas, the validity of
A similar situation exists for the dependence of which is tested experimentally by their possibil-
the reaction rate on the ratio of the hydrogen and ity for extrapolation to other reaction conditions.
nitrogen partial pressures; with lower tempera- Commonly the isothermal integral reactor is used
ture, the maximum rate shifts to a lower hydro- with catalyst crushed to a size of 0.5 1.5 mm to
gen nitrogen ratio (Fig. 5). Figure 5 presents avoid pore diffusion restriction and heat-transfer
data obtained using a commercial iron catalyst, resistance in the catalyst particles. To exclude
Topse KMIR. The data show a sharp drop in maldistribution effects and back mixing, a high
reaction rate with declining temperature at H2 / ratio of bed length to bed diameter is chosen.
N2 3 : 1 ratio in contrast to a H2 /N2 1 : 1 Sometimes the catalyst is also diluted with inert
ratio. This may be attributed to a hindering effect material. In some investigations, differential
of adsorbed hydrogen at low temperature [117]. reactors were used. To exclude any poisoning
Equations for describing ammonia synthesis by the synthesis gas, very pure reactants were
under industrial operating conditions must rep- prepared by decomposition of anhydrous ammo-
resent the influence of the temperature, the pres- nia [52].
sure, the gas composition, and the equilibrium
composition. Moreover, they must also take into Classical Expressions for Ammonia Syn-
consideration the dependence of the ammonia thesis Kinetics. The first expression useful for
formation rate on the concentration of catalyst engineering purposes was the Temkin Pyzhev
poisons and the influence of mass-transfer resis- Equation (1) proposed in 1940 [129, 130]. It is
tances, which are significant in industrial ammo- based on the assumption that dissociative adsorp-
nia synthesis. tion is the rate-determining step, that hydrogen
Since the beginning of commercial ammonia and ammonia have no significant influence on
synthesis, a large number of different kinetic nitrogen adsorption, and that the kinetics of
equations have been suggested, emanating in nitrogen adsorption and desorption can be
each case from a proposed reaction mechanism described adequately by Elovich-type adsorption
on an energetically inhomogeneous surface. For thermodynamical equilibrium, Equation (3)

many years this kinetic expression was the basic transforms into Equation (1) [116, 51].
design equation for ammonia converters. Values
for the factors a between 0.5 [132134] and 0.75 Surface Science Based Ammonia Kinetics
[1, 135, 136] were used. A problem with this [40, 41, 52, 53] are presently still viewed as an
equation was that the a values (reaction order) academic exercise rather than as a practical
were dependent on temperature, and the rate tool for engineering. The large amount of
constants on pressure [116, 135139]. More available data on nitrogen and hydrogen ad-
serious (not so much for industrial purposes, sorption from ultrahigh-vacuum studies on
where the converter feed has always a certain clean iron surfaces, acquired with all the mod-
ammonia content) was the fact that for zero ern spectroscopic techniques, has prompted
ammonia content, as in some laboratory mea- some research groups, such as BOWKER et al.
surements, the equation gives an infinitely high [151, 152] and STOLTZE and NRSKOW [153,
reaction rate. To avoid this, a simpler expression 154], to attempt the generation of a kinetic
(Eq. 2) was often used [137, 138]. expression for ammonia synthesis from a
An important modification was made by detailed microscopic model of the reaction

TEMKIN [131] who incorporated hydrogen ad- mechanism consisting of a number of discrete
dition to the adsorbed nitrogen as a second rate- steps at molecular and atomic level. Potential
determining step (Eq. 4). ICI demonstrated that energy diagrams for the various intermediate
this equation gives a better fit with experimental steps and species, were set up and Arrhenius
data [143]. It was also shown later that the expressions for each single step with known or
original Equation (1) is a simplified form of a estimated values for all pre-factors and activa-
more general model which can be derived from tion energies were formulated. The best results
the concept of energetically homogeneous have been achieved so far by calculating the
(Langmuir Hinshelwood adsorption iso- overall rate from the rate of dissociation of the
therm) as well as for heterogeneous surfaces adsorbed nitrogen and equilibrium constants
(Elovich-type isotherm). The applicability of a for all other reaction steps. The adsorption
particular equation resulting from this concept desorption equilibria were treated with approx-
also depends on the state of reduction of the imation of competitive Langmuir-type adsorp-
catalyst [139, 140] and the type of promoter tion and by evaluation of the partition func-
[141]. Equation (3), used by NIELSEN et al. tions for the gaseous and adsorbed species.
[144], is a combination of these model equa- The data from single-crystal experiments for
tions, developed by OZAKI et al. [145], that uses potassium-promoted Fe(111) surface were
fugacities instead of partial pressures. A similar used for the rate of the dissociative nitrogen
equation is found in [142]. Additionally, a num- adsorption. Comparison of the calculated am-
ber of modified equations were proposed monia yields with those determined experi-
and tested with existing experimental data mentally on a commercial Topse KM1 cata-
and industrial plant results [146149]. Near the lyst showed an agreement within a factor
passing through the converter creates sufficient

turbulence to keep the film thickness rather small
in relation to the catalyst grain size. For this
reason the largest concentration gradient (with
respect to the concentration in the bulk gas
stream) is within the catalyst particles. Since the
thermal conductivity of the iron catalysts is much
higher than that of the synthesis gas, the major
temperature difference is in the external gas film,
while the catalyst particles themselves operate
under approximately isothermal conditions. As
can be seen from Table 5 the differences in
temperature and ammonia concentration be-
tween the bulk gas stream and the external cata-
lyst surface are small. It also appears that the
effects are oppositely directed and will partly
Figure 6. Comparison of ammonia concentrations calculated compensate each other. So it can be concluded
from surface science kinetics with experimentally measured that their combined influence on the reaction rate
values [154, 155]
is negligible compared to inaccuracies of the
experimental data for the intrinsic catalyst
better than 2. Figure 6 demonstrates these activity [52].
encouraging results. These conclusions have For the particle sizes used in industrial reac-
been confirmed by calculations results of an- tors (1.5 mm), intra particle transport of the
other independent group [54, 156]. reactants and ammonia to and from the active
To compete with the empirical models (Tem- inner catalyst surface may be slower than
kin and improved expressions) for the best fit to the intrinsic reaction rate and therefore cannot
experimental data cannot be the prime objective be neglected. The overall reaction can in this way
of the microkinetic approaches. Rather, they are be considerably limited by ammonia diffusion
means of checking whether our knowledge and through the pores within the catalysts [150]. The
understanding of the elementary steps corre- ratio of the actual reaction rate to the intrinsic
spond to the reality of catalysts under industrial reaction rate (absence of mass transport restric-
synthesis conditions. tion) has been termed as pore effectiveness factor
E. This is often used as a correction factor for the
Transport Phenomena. For practical ap- rate equation constants in the engineering design
plication, the above kinetic equations have to be of ammonia converters.
modified to make allowance for mass and energy For pore diffusion resistances in reactions
transfer since the reaction rates actually observed having moderate heat evolution, the following
in a commercial converter are lower. One aspect phenomena characteristically hold true in indus-
is interparticle mass transfer and heat transfer trial ammonia synthesis [157]: in the temperature
through the stagnant film which surrounds the range in which transport limitation is operative,
catalyst particles. The high velocity of the gas the apparent energy of activation falls to about
Table 5. Mass and heat transfer effects at the external surface of catalyst particle
Position in catalyst bed, NH3 concentration NH3 concentration at Temperature in Temperature at

vol% from inlet in bulk gas, mol% catalyst surface, mol% bulk gas, C catalyst surface, C
0 2.500 2.592 400.0 401.4

20 4.500 4.288 428.1 429.5
40 5.960 6.045 455.1 456.5
60 7.000 7.778 481.9 483.2
80 9.300 9.361 505.5 506.6
100 10.500 10.536 522.7 523.3
where
deff effective particle diameter
Deff effective diffusion coefficient of ammonia
in the catalyst particle
kv reaction rate constant referred to a unit of
particle volume
tnh hyperbolic tangent
The practical application of kinetic equations
to the mathematical calculation of ammonia
synthesis converters is described in [143, 163,
Figure 7. Ammonia content in the bulk stream (1) and in the
167173].
catalyst pores (at r 0.5 R) (2) and pore effectiveness factor,
E (3)
21.4 MPa; 12 % inerts; SV 15000 h1; particle diameter, 5. Catalysts
2 R 5.7 mm
The ammonia synthesis catalyst may be viewed
as the heart of an ammonia plant. For a given
half its value at low temperatures; the apparent operating pressure and desired production, it
activation energy and reaction order, as well as determines the operating temperature range, re-
the ammonia production per unit volume of cycle gas flow, and refrigeration requirement. As
catalyst, decrease with increasing catalyst parti- a result, it directly fixes vessel and exchanger
cle size [150][158160]. For example at the gas design in the synthesis loop. It also indirectly
inlet to a TVA converter, the effective rate of influences the make-up gas purity requirement,
formation of ammonia on 5.7-mm particles is and so the operating pressure, and capital cost,
only about a quarter of the rate measured on very and energy consumption for synthesis gas pro-
much smaller grains (Fig. 7) [51]. duction and purification. Although the propor-
Mathematical models for calculating these tionate cost of catalysts compared to the total cost
effectiveness factors involve simultaneous dif- of a modern ammonia synthesis plant is negligi-
ferential equations, which on account of the ble, the economics of the total process are deter-
complex kinetics of ammonia synthesis cannot mined considerably by the performance of the
be solved analytically. Exact numerical inte- ammonia catalyst [174].
gration procedures, as adopted by various re- Industrial catalysts for ammonia synthesis
search groups [51, 163165], are rather trou- must satisfy the following requirements:
blesome and time consuming even for a fast
computer. A simplification [166] can be used 1. High catalyst activity at the lowest possible
which can be integrated analytically when the reaction temperatures in order to take advan-
ammonia kinetics are approximated by a pseu- tage of the favorable thermodynamic equilib-
do-first-order reaction [159161], according to rium situation at low temperatures. Average
the equation: commercial catalysts yield about 25 vol %
r kv cNH3;equilibrium cNH3 8
ammonia when operating at 40 MPa
(400 bar) and 480 C catalyst end tempera-
ture, which corresponds to a 535 C equilib-
For this case, the pore effectiveness factor E is a rium temperature. With catalysts that would
function of the so-called Thiele modulus m function at a reaction temperature about
[162]: 100 K lower, a yield of 45 vol % ammonia
can be expected with the same approach to
3 1 1
E 9 equilibrium, or the pressure may be reduced to
m tnhm m
15 MPa (compare Tables 1 and 2).
The Thiele modulus m is defined by 2. The highest possible insensitivity to oxygen-
r and chlorine-containing catalyst poisons,
deff kv which may be present in even the very effec-
m 10
2 Deff tively purified synthesis gas of a modern
process (see Sections 5.1.5, and 6.1.3). In Table 6. Effectiveness of various elements as catalysts, promoters, or
catalyst poisons
assessing the newly developed catalyst
systems recommended for operation at very Catalysts Promoters Poisons
low temperatures (see Section 5.2), it must be
I Li, Na, K, Rb, Cs
kept in mind that the effect of poisons, for II Be, Mg, Ca, Ba, Sr Cd, Zn
example, oxygen compounds, may become III Ce and rare earths Al, Y, La, Ce and B, Tl
more severe as temperature declines (see rare earths
Fig. 19). IV (Ti), (Zr) Si, Ti, Zr, Th Sn, Pb, C
V (V) Nb, Ta P, As, Bi
3. Long life, which is determined essentially by VI (Cr), Mo, W, U Cr, Mo, W, U O, S, Se, Te
resistance to thermal degradation and to irre- VII (Mn), Re F, Cl, Br, I
versible poisoning (see Section 5.1.4). In VIII Fe, Ni, Co, Ru,
older high-pressure plants (60 100 MPa), (Rh), Os, (Ir)
catalyst life was a big issue; because the

catalysts in these plants showed a markedly
reduced life owing to the severe operating activation or inactivation in doubly promoted
conditions, the necessary downtime for re- systems.
moving, replacing, and reducing the catalyst In principle, metals or metal alloys are
had a considerable effect on the ammonia suitable as ammonia catalysts, above all those
manufacturing cost. In modern single-train from the transition-metal group [177] (Table 6).
ammonia plants, conventional iron catalysts Metals or metal compounds for which the chem-
achieve service lifetimes up to 14 years. isorption energy of nitrogen is neither too high
4. Mechanical Strength. Insufficient pressure nor too low show the greatest effectiveness
and abrasion resistance may lead to an exces- (Figs. 89), [178, 179], so the magnetite-based
sive increase in converter pressure drop, and catalyst proved suitable for industrial use.
so to a premature plant shutdown. For exam-
ple, mechanical disintegration during opera-
tion along with oxygen sensitivity thwarted
the industrial application of uranium carbide
catalysts [175].
5. Because of the high and increasing world
demand for ammonia, a reliable primary raw
material source. For example, osmium,
which was planned as the first industrial
catalyst, is so scarce that, in 1910, as a pre-
cautionary measure for this option, BASF had
secured almost the total world supply [175].
The ammonia synthesis catalyst problem has

been more intensively studied than the catalysis
of any other industrial reaction. At BASF A.
MITTASCH et al. started a tremendous program, in
which up to 1911 more than 2500 different
formulations were testet in more than 6500 runs.
The experiments were finally brought to an end
in 1922 after a total of 22 000 tests. They tested
almost all elements of the periodic table for their
suitability as ammonia catalysts [7, 176]. From
these experiments came a series of technical
findings, for example, concerning the relation-
Figure 8. The rate constants of ammonia decomposition
ships between catalytic effectiveness and the (A) on and the ammonia synthesis capacities (B) of metals
strength of the nitrogen bond and reducibility, as a function of DH00 . (Mol. denotes molecule, mol denotes
or relating to the mechanism of opposing mole)
Table 7. Effect of various elements or their oxides on the activity of

iron catalysts in ammonia synthesis
a) positive:
Al, Ba, Be, Ca, Ce, Cr, Er, K, La, Li, Mg, Mn, Mo, Na,
Nb, Nd, Rb, Sm, Sr, Ta, Th, Ti, U, V, W, Y, Zr
b) negative:
As, B, Bi, Br, C, Cd, Cl, F, J, P, Pb, S, Sb, Sn, Te, Tl, Zn
c) doubtful:
Au, Co, Cu, Hg, Ir, Ni, Os, Pd, Pt, Si
oxides [176] (Table 7). The iron catalysts pro-

moted with aluminum and potassium oxides
proved to be most serviceable [183]. Later,
calcium was added as the third activator. Devel-
opment work in the United States from 1922 can
be found in [184].
Modern catalysts additionally contain other
promoters that were present in the older cata-
lysts only as natural impurities from the raw
Figure 9. Catalytic activity of carbon-supported metals pro- materials. Onstream life and performance were
moted by metallic potassium as a function of DH00 . enhanced considerably by optimizing the com-
A) The rate of isotopic equilibration of N2 at 623 K, 20 kPa of
pN2 (Mol. denotes molecule, mol denotes mole); ponent ratios (Section 5.1.1), conditions of
B) The rate of ammonia synthesis at 523 K, 80 kPa of total preparation (Section 5.1.3), and catalyst parti-
pressure cle size and form (Section 5.1.2). The high-
purity gas of modern processes and the trend
to lower synthesis pressures especially favor the
5.1. Classical Iron Catalysts development of more active and easily reduc-
ible types of catalysts, at some sacrifice in
From the early days of ammonia production to temperature stability and resistance to poisons.
the present, the only catalysts that have been used To some extent even today, ammonia plant
have been iron catalysts promoted with nonre- operating conditions and types of converters
ducible oxides. Recently, a ruthenium-based (Section 6.3.2) can differ greatly one from
catalyst promoted with rubidium has found in- another. Thus, individual catalyst manufac-
dustrial application. The basic composition of turers now offer several catalyst types in various
iron catalysts is still very similar to that of the first particle size distributions, in oxidic and prere-
catalyst developed by BASF. duced states.
The catalytic activity of iron was already
known well before the advent of industrial
ammonia synthesis. RAMSAY and YOUNG used 5.1.1. Composition
metallic iron for decomposing ammonia. PERMAN
[180], as well as HABER and ORDT [181], con- Table 8 gives a composition survey of commer-
ducted the first catalytic synthesis experiments cial ammonia catalysts in the years 1964 1966.
with iron at atmospheric pressure. NERNST [182] The principal component of oxidic catalysts is
used elevated pressures of 5 7 MPa. Pure iron more or less stoichiometric magnetite, Fe3O4 ,
showed noticeable initial activity which, how- which transforms after reduction into the cata-
ever, could be maintained for longer operating lytically active form of a-iron.
periods only with extremely pure synthesis gas. The degree of oxidation of industrial catalysts
The ammonia synthesis catalyst problem has a considerable influence on their catalytic
could be considered solved when the catalytic properties. MITTASCH in 1909 established that
effectiveness of iron in conversion and its catalysts manufactured by reducing a magnetite
onstream life were successfully and substantially phase were superior to those prepared from other
improved by adding reduction-resistant metal oxides. For industrial catalysts, the highest
Table 8. Examples of commercial ammonia catalysts from the years 1964 1966. Values for the composition in weight %. The numbers at the
beginning of the lines are keyed to the catalyst origin
Origin, type Fe total FeO Fe2O3 Al2O3 MgO SiO2 CaO K2O Other Particle size, Bulk density,
mm kg/L
1 68.6 36.07 57.85 3.30 0.09 0.75 2.13 1.13 2 4 2.37

2 normal 60.0 32.91 60.18 2.90 0.37 0.35 2.80 0.54 4 10 2.94
2 68.2 31.30 62.53 2.90 0.30 0.35 1.65 0.97 6 10 2.80
2 HT 66.9 32.47 59.18 2.95 1.55 0.40 2.95 0.50 6 10 2.80
2 prereduced 88.1 3.70 0.43 0.45 3.60 0.70 6 10 2.30
3 71.3 39.22 58.2 1.80 0.18 0.27 1.43 0.89 2 4 2.86
4 66.3 22.27 49.0 0.59 4.47 0.77 0.65 0.50 0.7 Cr2O3
4 prereduced 90.6 0.10 6.08 1.23 0.10 0.86 1.05 Cr2O3
5 71.5 33.0 65.5 2.96 1.55 0.20 0.01
6 (1964) 69.5 23.85 3.15 0.26 0.40 1.85 1.10 3 9 2.71
6 (1966) 66.9 2.73 0.29 0.43 1.84 1.15 5 10 2.73
7 prereduced 90.4 3.12 1.00 0.46 0.25 0.58 0.4 MnO 5/5 2.55
8 68.4 35.35 3.16 0.56 0.50 3.54 0.58 2 4 2.61
9 70.0 32.14 3.17 0.28 0.10 2.40 0.32 2 4 2.81
10 70.8 33.62 1.58 0.28 1.14 0.67 1.57 2 4 2.66
11 normal (1964) 66.7 35.95 56.97 3.27 0.67 0.55 3.00 0.65
11 (1966) 68.2 38.70 54.60 2.42 0.35 0.64 2.85 0.58
11 normal (1964) 3.0 0.3 0.5 2.0 1.0
11 (1966) 69.5 38.20 56.70 2.34 0.35 0.57 1.85 0.57
11 HT 66.3 38.22 52.38 2.94 3.56 0.30 2.66 0.63
11 prereduced 84.9 3.62 0.43 0.94 4.70 0.68 5 11 2.11
12 3.9 4.0 0.8 2.3 1.8
13 23.15 2.9 0.1 0.42 3.12 0.52
14 4 0.7 3 1
ammonia yields are observed with an Fe(II) Fe platinum [191]. Reference [192] describes cesi-
(III) ratio of 0.5 0.6, about the degree of um-containing catalysts. Catalysts patented by
oxidation of stoichiometrically composed mag- Lummus [193] and Ammonia Casale [194] con-
netite [185187] (Fig. 10). To obtain optimal tain cerium as additional promoter. ICI [195] has
catalyst composition, careful control of the developed a cobalt-containing catalyst, as has
manufacturing process, especially the melting Grande Paroisse [196].
conditions, which determine the oxygen content,
is necessary. Nature of the Surface of Commercial Iron
In general, the catalysts contain varying quan- Catalysts. Freshly reduced commercial iron
tities of the oxides of aluminum, potassium, catalysts that contain aluminum, potassium, and
calcium, magnesium, and silicon as promoters. calcium oxides as basic promoters consist of
Patents recommend adding sodium [188], ber- approximately 30-nm primary crystallites; the
yllium [189], vanadium [190], uranium [232], or spaces between them form an interconnecting
system of pores. Besides a maximum at a pore
radius of about 10 nm that originates on reduc-
tion of the Fe3O4 (magnetite) phase of the
nonporous oxidic catalyst, the pore distribution
curve (Fig. 11) generally shows a peak at 25
50 nm that is formed on reduction of the wustite
phase [51, 55]. The pore volume measures
0.09 0.1 cm3/g; with an apparent density of
4.8 4.9 g/cm3, accordingly, the pores repre-
sent 44 46 % of the volume of a catalyst
granule [1]. The surface of the walls of the
Figure 10. Dependence of the ammonia yield on the degree
pores, the so-called inner surface, amounts to
of oxidation of the iron in the unreduced catalyst about 15 m2/g.
The free iron surface of the reduced BASF cata-

lyst [44] and Topse catalyst KM-I [56] com-
prises only a fraction of the total surface, as could
be deduced from the results of prior investiga-
tions [51, 5763].
The aluminum oxide promoter exists partly
in the form of larger crystallites and, moreover,
is relatively homogeneously distributed over
the iron area of the surface, although with low
concentration [44, 56]. After reduction, about
1 wt % of the alumina also remains statistically
distributed in the form of FeAl2O4 molecular
groups built into the a-iron lattice of the
reduced catalyst [64, 65]. According to [44] the
potassium, in the form of a K O adsorbed
layer, covers about 20 50 % of the iron
surface. According to [55, 56], a correlation
exists between the distribution of the potassium
and that of aluminum and/or silicon. Calcium
oxide segregates, essentially at the grain bound-
aries, into separate regions, probably as a mix-
ture of the silicate and ferrite [46]. Auger spec-
troscopic investigations on reduced BASF and
Figure 11. Pore size distribution of a commercial catalyst
Topse catalysts reveal large local differences
after reduction at various temperatures [55] in composition [44, 55]. Large, apparently
homogeneous regions that have originated from
reduction of Fe3O4 crystallites alternate with
The novel AmoMax catalyst [844, 845] of
nonhomogeneous regions that are formed by the
Sudchemie is iron-based but uses wustite instead
reduction of FeO crystals or consist of amor-
of magnetite which previously was considered
phous phases [55].
undispensible for the production of industrial
Extensive studies in the last decade have
ammonia catalysts has an improved pore struc-
provided a more refined picture of the mor-
ture and higher specific surface area.
phology of the active catalyst (reduced state)
The composition of the outermost atomic
and its precursor (oxidic state). A review is
layers of the pore walls deviates considerably
given in [49]. With methods such as scanning
from the overall average concentrations. Auger
transmission electron microscopy (TEM) and
electron spectroscopic (AES) measurements on
electron microdiffraction a textural hierarchy
an industrial catalyst (BASF S 6-10) have shown
has been modeled. Macroscopic particles in the
that a significant enrichment of the promoters
reduced catalyst are confined by fracture lines
into the surface results using the unreduced as
running through a system of blocks consisting
well as the reduced catalyst [44] (see Table 9).
of stacks of slabs in parallel orientation. This
structure is already preformed in the prepara-
Table 9. Composition by volume of an industrial ammonia catalyst in tion of the catalyst precursor, and in the reduc-
comparison to the surface composition before and after reduction (an tion process a further subdivision of the slabs
approximately 104 cm2 size typical surface). Numerical values in
into even smaller platelets might occur. This
atomic % [44]
texture is stabilized by structural promoters,
Fe K Al Ca O which act as spacers and glue, separating
Volume composition 40.5 0.35 2.0 1.7 53.2
neighboring platelets and thus providing voids
Surface composition for the interconnection of the pore system.
before reduction 8.6 36.1 10.7 4.7 40.0 There is also evidence that the basal plane
Surface composition of many platelets has the Fe(111) orientation
after reduction 11.0 27.0 17.0 4.0 41.0
[47, 49].
Influence of the Promoters. Promoters can concentrations have an especially strong influ-
be arranged in different groups according to the ence. Adding magnesium oxide decreases the
specific action of the metal oxides: catalyst performance. If before the test the cata-
Structural stabilizers, such as Al2O3, pro- lyst is overheated at 700 C for 72 h (Fig. 12 C)
duce a high inner surface during reduction or poisoned with 2000 cm3 water vapor per cubic
and stabilize it under thermal stress by restrain- meter of gas at 550 C (Fig. 12 D), the optimum
ing iron crystallite growth [83, 187, 198]. The composition shifts to higher Al2O3 and SiO2 and
ability of the various metal oxides to create a lower K2O and CaO concentrations. Magnesium
high specific surface decreases in the following oxide addition now shows a favorable effect.
order [199]: For ammonia plants operating at pressures up
to 35 MPa (350 bar), catalyst end temperatures
Al2 O3 > TiO2 > Cr2 O3 > MgO > MnO > BeO
of 520 530 C maximum, and with highly
CaO > SiO2 purified synthesis gas, the preferred catalysts
contain 2.5 4.0 % Al2O3 , 0.5 1.2 % K2O,
So-called electronic promoters, such as the 2.0 3.5 % CaO, 0 1.0 % MgO, and a natural
alkali oxides, enhance the specific activity (based content of about 0.2 0.5 % SiO2 [187]. Less
on a unit surface) of iron alumina catalysts. active but more poison- and temperature-resis-
However, they reduce the inner surface or lower tant catalysts containing up to 3.6 % magnesium
the temperature stability and the resistance to oxide were recommended for older plants, for
oxygen-containing catalyst poisons [200, 201]. example, classical Casale plants, which operated
In the alkali-metal series, the promoter effect at up to 80 MPa (800 bar) pressure and in which
increases with increasing atomic radius, and the catalyst end temperature reached 650 C (see for
destructive effect with decreasing atomic radius example [1]). An industrial catalyst for operating
[202]. In striving to improve the activity or temperatures up to 550 C is stabilized against
stability of iron catalysts, a multitude of struc- deterioration by 2 5 % V2O5 besides 3.5
tural and electronic promoters has been investi- 4.0 % Al2O3, 2.0 2.5 % CaO, and 0.7 % K2O
gated, among them rare-earth oxides [203, 204], [190]. For higher operating temperatures, still
such as Sm2O3 [205], Ho2O3, Dy2O3, and Er2O3 higher V2O5 contents are recommended. Silicon
[206]. dioxide additions shift the optimum potassium
Promoter oxides that are reduced to the metal oxide concentration to higher values [200]. For
during the activation process and form an alloy example, the Bulgarian catalyst K-31 contains
with the iron (see also Section 5.1.3) are a special 3.9 % Al2O3, 2.3 % CaO, 0.4 % MgO, 0.8 %
group. Among those in use industrially, cobalt is SiO2, and 1.8 % K2O. An older Norsk Hydro
of special interest [207, 208]. catalyst, besides the usual additives, contained
The effect of a given promoter depends on 1.14 % SiO2 and 1.57 % K2O. The ICI catalyst
concentration and on the type of promoter com- with composition 5.2 % CoO, 1.9 % CaO, 0.8 %
bination and the operating conditions, especially K2O, 2.5 % Al2O3, 0.2 % MgO, 0.5 % SiO2,
the reaction temperature and the synthesis gas remainder Fe3O4, is substantially more active
purity [190, 200, 202, 209212]. than the conventional cobalt-free catalysts
A graphic picture is conveyed in [202] of how [195, 213]. Reducing the synthesis pressure
the activity of a quadruply promoted (4 % Al2O3 , and/or the synthesis temperature should enable
1 % K2O, 1 % CaO, 1 % SiO2 ) catalyst changes application of the Lummus [193, 214] and Am-
with varying promoter concentration and operat- monia Casale [194] cerium-containing catalysts.
ing conditions (Fig. 12). Under normal operating The effect of the promoters on the rate of
conditions [14 45 MPa, 380 550 C, reduction and the temperature required for
3 3 1
10 000 20 000 m m h (STP)], the opti- reducing the iron oxide phase is also significant
mal activity corresponds to a composition of in industrial practice. The structural promoters,
2.5 3.5 % CaO, 2.3 5.0 % Al2O3, 0.8 such as Al2O3, lower the rate of reduction [49,
1.2 % K2O, and 0 1.2 % SiO2 (Fig. 12 B). 215, 216]. Magnesium oxide-activated iron, said
Raising or lowering the concentration of a par- to be thermally stable up to 650 C, needs a
ticular oxide causes a reduction in activity. higher reduction temperature than aluminum
Changes in the potassium and aluminum oxide oxide-promoted iron catalyst [217]. Greater
Figure 12. Dependence of the catalyst activity on various factors

A) Concentration of impurities; B) Concentration of promoters; C) Overheating to 700 C with increasing promoter
concentrations; D) Poisoning with water at increasing promoter concentrations
differences in reducibility have also been (stabilizers), such as Al2O3, is closely associated
observed in commercial catalysts with similar with their solubilities in the iron oxide matrix
chemical composition [218] and in connection of the unreduced catalyst or with the capability
with particular oxide phases, such as CaFe3O5 and of the regular crystallizing magnetite to form
FeO [218220]. Early work [221] referred to the solid solutions with iron aluminum spinels
rough parallels between the reducibility and the [1, 222224]. The solid solutions of Fe3O4 and
thermal stability of catalysts. All published expe- the spinel FeAl2O4 have a miscibility gap below
rience appears to demonstrate that it is not possi- 850 C [225]; at 500 C, the solubility limit in
ble to combine in a catalyst high thermal stability the magnetite mixed crystal is a maximum of
with easy reducibility and high activity at low 7.5 % FeAl2O4 , i.e., 3 % Al2O3, referred to iron.
temperatures. Hence it may be advantageous to Higher alumina contents lead to separation into
use a combination of active and thermally- two phases, whereby only the portion dissolved
resistant catalysts in the same converter. in the magnetite phase appears to be responsible
for the specific promoter action of alumina [57,
Mechanism of the Promoter Effect. The 58, 226]. According to [227], there exists a close
action of the so-called structural promoters connection with the mechanism of the reduction
which consists schematically of the following level on each basic structural unit is not true. The
partial steps [228]: unique texture and anisotropy of the ammonia
catalyst is a thermodynamically metastable state.
1. Phase-boundary reaction of hydrogen with Impurity stabilization (structural promotion)
oxygen ions of the magnetite lattice, with kinetically prevents the transformation of plate-
formation of water vapor and release of let iron into isotropic crystals by Ostwald ripen-
electrons ing [47]. Thus the primary function of alumina is
2. Formation of metallic iron nuclei by combi- to prevent sintering by acting as a spacer, and in
nation the electrons with Fe2 ions part it may also contribute to stabilizing the Fe
3. Diffusion of Fe2 ions and electrons to the (111) faces [50, 90].
nuclei and growth of the nuclei to iron crystals Calcium oxide, which also acts as a structural
of various size promoter [55] has a limited solubility in magne-
tite. It tends to stretch the magnetite lattice [37].
A more detailed discussion of the reduction In the main, on cooling the magnetite melt, it
mechanism is given in Section 5.1.4. separates at the grain boundaries as CaFe3O5
In the presence of dissolved aluminum ions, at (at very rapid cooling rates) [218] and, in the
not too high a temperature, the diffusion rate of presence of SiO2, forms poorly reducible inter-
the iron ions in the magnetite lattice is low. mediate layers of calcium ferrite and silicates
Hence, nucleus formation proceeds rapidly rela- [55, 219]. In the reduced catalysts, it segregates
tive to crystal growth. Therefore, small iron between the iron crystallites [45, 62] and so
crystallites, about 30 nm, form with correspond- possibly prevents sintering together at high
ingly large specific surfaces. The aluminum operating temperatures. One may also presume
probably remains partly in the iron crystallite in that by partial neutralization of the acid com-
the form of very small FeAl2O4 areas statistically ponents by calcium, more potassium is made
distributed over the lattice [64, 65, 227, 230], available for activating the iron [143].
where an FeAl2O4 molecule occupies seven a Fe Potassium is likewise scarcely soluble in
lattice positions [37]. magnetite because of its ionic size [37]. In the
unreduced catalysts, separate potassium- and
iron-rich regions were found [44]. The appear-
ance of a K2Fe22O34 phase besides an unidenti-
fied phase, however, has been proved [233].
According to [234], during reduction, the
emerging K2O migrates to the iron crystallite
According to this concept, the stabilizer func- surface. While doing this it reacts with the more
tion of alumina reduces to paracrystalline lattice or less homogeneously distributed aluminum
defects; an analogous effect is to be expected (silicon) compounds. In this way, it is distribut-
with Cr2O3, Sc2O3 , etc. [64, 230]. Another theory ed over the iron phase. In the reduced catalysts,
is based on the observation that during reduction the potassium exists as a K O adsorption
part of the alumina precipitates with other pro- layer that covers about 20 50 % of the iron
moters into the surface of the iron crystallite in a surface [44]. According to [61, 235], potassium
molecularly dispersed distribution [60, 231] or in associates partly with the alumina in the surface,
small islands [56]. This patchy monolayer of partly as KOH with iron [838]. It was found
alumina acts like a spacer between iron atoms that the enhancement of the catalysts specific
of neighboring crystallites and prevents sintering activity by potassium oxide is accompanied
by means of a skin effect [65]. (See also [37, by a decrease in the electron work function
46, 55].) [235237]. The promoting effect of potassium
Insofar as small crystals of nonreducible oxi- seems to be based on two factors which probably
des dispersed on the internal interfaces of the act simultaneously. One mechanism is the
basic structural units (platelets) will stabilize the lowering of the activation energy for the disso-
active catalyst surface Fe(111), the paracrystal- ciative adsorption of nitrogen [36, 44]. The
linity hypothesis will probably hold true. But the explanation is based on an electrostatic model
assumption that this will happen on a molecular [40, 81, 238]. As indicated by the strong
decrease in the work function upon potassium

adsorption, there is a considerable electronic
charge transfer to the substrate, which creates
a Md Kd dipole. A nitrogen molecule
adsorbed near such a site will experience a more
pronounced back-bonding effect from the metal
to its antibonding p orbitals. This will increase
the bond strength to the metal and further weak-
en the N N bond, as can be seen from a further
reduction of the N N stretching frequency
[239]. The other effect consists of lowering the
adsorption energy of ammonia, which avoids
hindering of nitrogen adsorption by blocking Figure 13. Influence of the particle size on the ammonia
(poisoning) of the catalyst surface by adsorbed production (BASF catalyst).
25 MPa; SV 12 000 m3 m3 h1 (STP); gas composition
ammonia molecules [34, p. 234], [44]; hence, (vol %): N2 20.59, H2 60.06, NH3 2.55, Ar 5, CH4 10
potassium oxide ought to improve the catalyst
performance less at low than at higher operating
From the standpoint of space time yield, it
pressures [135 p. 316], [240].
is desirable to use the finest possible particle,
The negative effect of K2O concentrations
which, practically speaking, is about 1 2 mm
higher than about 0.58 % has not been ex-
(Fig. 13); however, with decreasing particle size,
plained unequivocally [83]. With increasing
the pressure drop and the risk of destructive
potassium concentration, this manifests itself
fluidization of the catalyst increase (Fig. 14).
by the increasing size of the average iron crys-
For processes operating at pressures of 25
tallite or the decreasing specific surface in the
45 MPa (250 450 bar) and at space velocities
reduced catalyst [200, 233]. Since potassium
of 8000 20 000 m3 m3 h1 (STP) a grain size
oxide prevents the formation of solid solutions
of 6 10 mm is preferred. Larger granulations,
between alumina and magnetite to a certain
for example, 8 15 mm or 14 20 mm, are
extent [241], the recrystallization-promoting
used only in plants where the lowest possible
effect of higher K2O concentrations may be
attributed to a lowering of the portion of alu-
mina dissolved in the magnetite phase [233].
Remarks in [234] and [242] reveal another
possible interpretation: the K2O located at the
phase boundary surface and not bound to acid
or amphoteric oxides may be converted by
water vapor concentrations over 102 ppm in
the synthesis gas into potassium hydroxide or
by hydrogen into potassium and potassium
hydroxide, which would exist in molten form
at operating conditions [234, 838].
An extensive review on promoters can be
found in [41].
5.1.2. Particle Size and Shape
The choice of particle size and shape of com-

mercial ammonia catalysts is determined mainly
by two factors:
Figure 14. Pressure drop in the catalyst bed for various
catalyst particle size ranges, from [1].
1. Catalyst performance Depth of the catalyst bed, 7 m; reaction pressure 27.1 MPa;
2. Pressure drop reaction temperature 450 C
pressure drop is essential because of very high Table 10. Effect of catalyst size on catalyst volume
gas velocities. In catalyst zones in which the Catalyst size Approximate Relative
ammonia formation rate is so high that the al- classification, equivalent particle catalyst volume,
lowable temperature limits are exceeded, it may mm diameter, mm %
be advantageous to use coarse particles for sup- 6 10 7.5 100
pressing the reaction. Radial-flow converters 4.5 8 5.5 6.5 92 95
and the horizontal crossflow Kellog converter 36 4.5 4.7 88 90
(Fig. 48), which operate at comparatively low 1.5 3 2.0 2.2 80 82
1 1.5 1.2 1.3 77 79
gas velocities [243], allow the use of small
granulations (1.5 3 or 2 4 mm) with optimal
use of the converter volume. Fluidized-bed pro-
cesses, which were explored especially in the An irregular grain shape, for example with a
Soviet Union, have so far been unsuccessful shape factor of 1.5, has a more favorable effec-
[244, 245]. tive activity for the individual particle and for
Two effects cause the low production capacity radial intermixing of mass and heat in an indus-
of coarse-grained catalyst: first, large grain size trial converter [252] than a more cubic or spher-
retards transport of the ammonia from the parti- ical shape, with a shape factor close to one.
cle interior into the bulk gas stream, because this According to a patent by Chemie Linz AG [253],
proceeds only by slow diffusion through the pore the catalyst particle ought to be 2 20 times as
system. Slow ammonia diffusion inhibits the rate long as it is broad, preferably 5 10 mm long
of reaction. At the high reaction rate typical for and 1 2 mm thick (broad). On the other hand,
the converter inlet layer, only a surface layer of regular shapes have the advantages of greater
the catalyst grains, about 1 2 mm thick, parti- abrasion resistance and lower pressure drop (see
cipates in the reaction. Fig. 15) [326].
The second effect is a consequence of the fact
that a single catalyst grain in the oxidic state is
reduced from the outside to the interior of the
particle [246]: the water vapor produced in the
grain interior by reduction comes into contact
with already reduced catalyst on its way to the
particle outer surface; this induces a severe
recrystallization [1]. The effect is very signifi-
cant. As an example, if the particle size in-
creases from about 1 to 8 mm, the inner surface
decreases from 11 16 m2/g to 3 8 m2/g
[251].
To allow for the influence of various particle
shapes and size distributions within a defined
sieve fraction, in lay-out calculations it is cus-
tomary to employ an effective particle diameter,
deff, as nominal size. The diameter deff is defined
as the ratio of equivalent diameter L and a form
factor y. L is equal to the diameter of a sphere
with a volume equal to the (average) volume of
the particles, and y is the average ratio of the
particle surface to the surface of a sphere of equal
volume.
Table 10 shows the relation between the cat-
alyst size classification, the equivalent particle
diameter, and the percentage saving in catalyst or
converter volume relative to the 6 10 mm Figure 15. Comparison of the Ammonia Casale spherical
standard size [213]. catalyst and irregularly shaped catalyst [213]
The advantages of regular catalyst shapes posed thermally in the presence of hydrogen.
and the need to compensate for the above- The hydrodecomposition proceeds via the car-
described negative effects of larger grain size bide and nitride, finally to a iron. This is acti-
by a system of macropores in the oxidic and vated in the well-known manner by reduction-
reduced catalyst stimulated various attempts to resistant metal oxides. The so-called Mont
manufacture shaped, macroporous catalysts. Cenis process employed such catalysts [266].
Various manufacturing techniques have been Repeatedly described as a means of manufac-
proposed [254263]. As an example, magnetite ture, although only in the scientific literature, is
is melted with the additives at high temperature coprecipitation of the catalyst components, for
(> 1600 C) and the melt is cooled, broken, example, from aqueous solutions of the metal
and ground to powder. After water is added and, salts, with subsequent calcining and reduction
if required, a binding agent, such as bentonite [267270]. With magnesium oxide as support,
[262], or a promoter salt, such as cerium nitrate very small (under 10 nm) iron particles are
[194], the powder is pelletized. The pellets obtained with high specific iron surfaces
subsequently are dried and sintered in an inert [270], similar to those obtained by exchange of
atmosphere at higher temperatures (about magnesium ions by iron ions in the surfaces of
1350 C). magnesium hydroxy carbonate crystals [270,
The application of macroporous catalysts 271]. Granulation and sintering techniques have
ought to be especially useful for very low syn- been used for the preparation of shaped macro-
thesis pressures and in plants in which large porous iron catalysts, which, however, have not
catalyst particles must be used for reasons of gained industrial importance.
low pressure drop. For example, the performance Impregnating the pore surface of prereduced
of the macroporous Topse catalyst KMG 6 mm passivated catalysts is a possibility for incorpo-
at 5 MPa synthesis pressure is said to be at least rating promoters into iron ammonia catalysts.
equivalent to KM I 1.5 3 mm and distinctly A United Kingdom patent [272], by way of
superior to KM I 6 10 mm [264]. example, claims catalysts manufactured by
impregnating the reduced catalysts with cerium
salts. Improving the performance and life of
5.1.3. Catalyst-Precursor Manufacture industrial catalysts by radioactivity and X-rays
[273], treatment with ultrasound [274, 275],
The term ammonia catalyst commonly refers mechanical treatment [276], or high-frequency,
to the oxidic form consisting of magnetite and alternating-field heating [277] has been
oxidic promoters. In fact this is only the catalyst attempted also.
precursor which is transformed into the active The superiority of the catalyst manufacturing
catalyst composed of a-iron and promoters by processes that use a molten iron oxide stage is
reduction with synthesis gas, usually in situ. The mainly due to the fact that above 1000 C in air,
reduction step is very important for catalyst magnetite, Fe3O4 , is the thermodynamically
performance. stable oxide phase of iron [7, 278]. Magnetite
The first effective catalysts were made by the leads to especially efficient catalysts, and its
oxygen-melt process. The purest possible iron electrical conductivity allows the use of econo-
(e.g., Swedish charcoal iron), together with the mical electrical melting processes.
additives, was burned to Fe3O4 in a stream of In 1996 the prices of commercial ammonia
oxygen. This process was largely replaced by catalysts were about 2 $/lb (3.58 e/kg) for
melt processes in which natural or, less frequent- oxidic and about 5.5 $/lb (10.23 e/kg) for pre-
ly, synthetic magnetite, together with the activa- reduced. Therefore, they are among the least
tors, was melted electrically or in electric arc expensive catalysts.
furnaces [186, 265]. The cooled melt is ground to Operating conditions in the individual
the proper granulation and reduced with hydro- manufacturing steps proportioning and mix-
gen nitrogen mixtures. ing the raw materials, melting, cooling, crushing
A process developed by Farbenfabriken or if necessary grinding and preforming, and
(formerly Friedrich Bayer) had only local signif- reduction influence the quality of the finished
icance. Complex iron cyanides were decom- catalyst (Fig. 16) [174].
Figure 16. Ammonia catalyst manufacture

Figure 17. Effect of the melting temperature and rate of
cooling of the melt on the activity of ammonia catalysts
a) Melt overheated to 3500 C (rapid cooling); b) Melt
The raw materials usually, natural magne- temperature 1800 2000 C (rapid cooling); c) Melt tem-
tite, lime, potash, and alumina must, as far perature 1800 2000 C (slow cooling)
as possible, be free of catalyst poisons (see
Section 5.1.5). Many ores have too high a con- Another important factor in catalyst manufac-
tent of free or bound silica, which can be lowered ture is the melt cooling rate, which is affected by
with magnetic separators [279]. Melting is ac- the design and dimensions of the ingot molds.
complished in electrical resistance or induction Quenching or fast cooling in thin sheets leads to a
furnaces (arc furnaces in the past) operating at less abrasion-resistant, sharp-edged chip after
1600 2000 C. The walls of these furnaces crushing. Very slow cooling results in a more
should consist of a weakly basic tamping mate- cubic chip, but with inferior catalyst quality
rial indifferent to the melt, such as magnesium (Fig. 17). In practice, slow cooling is avoided.
oxide, which is also an activating component of With falling temperature, both the solubility
the catalyst [280]. A homogeneous distribution of the activator oxides (see page 31) in magnetite
of the promoters in the magnetite melt and a and the rate of adjustment to the new phase
degree of oxidation at or under that of stoichio- equilibrium decline. Therefore, by rapid cooling
metric magnetite should be obtained. This is said of the melt the activator oxide distribution can be
to be promoted by initially overheating to tem- frozen in a condition corresponding to that of a
peratures up to 3500 C [281] (Fig. 17). It is higher temperature [283]. According to [218],
claimed to be advantageous to bring the promo- there may exist relationships between the melt
ters into the melt as common chemical com- cooling rate, the appearance of certain phases,
pounds that are isomorphous with magnetite and the reducibility of the catalysts.
[282].
Induction furnaces are optimal for the melting
operation. Their good temperature control per- 5.1.4. Catalyst Reduction
mits accurate adjustment of the degree of oxida-
tion. Since the melt is held in constant turbulent The reduction of oxidic catalyst is generally
motion by the magnetic field produced in the effected with synthesis gas. The magnetite is
primary coil, it is well mixed, even for short melt converted into a highly porous, high surface area,
times. In comparison to the most frequently used highly catalytically active form of a-iron. The
resistance furnaces, plant cost and power con- promoters, with the exception of cobalt, are not
sumption are higher. reduced [1].
To ensure maximum effectiveness of the ly, the manufacturers hold these in strict
catalyst, a defined reduction procedure must be secrecy.
followed. Above all, it is important to hold the Some older publications deal with the influ-
partial pressure of the resulting water vapor as ence of catalyst granulation on the optimum
low as possible and to insure that the water reducing conditions [285]. Directions for reduc-
vapor does not come into contact with regions tion in multibed converters that combine fine-
that have already been reduced. High tempera- and coarse-grained catalyst appear in [286]. The
ture and high water vapor partial pressure influence of the hydrogen/nitrogen ratio during
markedly accelerate premature catalyst aging reduction on the catalyst performance after re-
by recrystallization. Therefore, the reduction duction is discussed in [287].
should be carried out at high gas velocities The influence of the reduction conditions
[about 5000 15 000 m3 m3 h1 (STP)], at (gas flow rate, temperature in the range
the lowest temperatures sufficient for complete 300 600 C, nitrogen content in the hydrogen
reduction, and at not too high pressures (7 in the range 0 100 %) on the production ca-
12 MPa in low-pressure, 25 30 MPa in high- pacity of an ammonia catalyst has been investi-
pressure plants) to hold the exothermic forma- gated [293].
tion of ammonia under better control during the The gas/solid reaction between magnetite and
reduction. When the reduction of the oxidic hydrogen has been studied in great detail by rate
catalyst is carried out in the production plants, measurements, microscopy, and X-ray diffrac-
long reduction times are needed at low tem- tion [288291]; a summary is given in [49]. On
peratures and low pressures with a consequen- the atomic scale the reaction is controlled by two
tial loss of production. processes:
In practice, the reduction temperature is raised
stepwise by using the exothermic heat of ammo- 1. Metallic iron is formed from wustite by direct
nia formation. The progress of the reduction is chemical reaction controlled in the initial
controlled according to the catalyst temperature phase by the reaction rate (activation energy
and the water concentration by means of the ca. 65 kJ/mol) and in the final stage by diffu-
synthesis gas flow. As a rough guideline, the sion processes involving hydrogen and water
water content of the gas effluent from the catalyst on the reaction site:
should not exceed 2 3 g/m3 (STP). Under these FeOH2 !FeH2 O
conditions, depending on its size and operating
pressure, a synthesis converter with a fresh load 2. The chemical reaction creates an iron(II) ion
of oxidic catalyst attains its full production concentration gradient in the solid. This
capacity in 4 10 d. gradient leads to a rapid diffusion of iron(II)
The minimum temperatures necessary for re- ions from magnetite through wustite to the
duction are somewhat different for the various chemical reaction interface, where they are
catalyst types. Catalysts conventionally em- reduced and precipitated as iron nuclei. This
ployed in medium-pressure plants may be re- is made possible by the structural defects of
duced from about 340 to 390 C, although a slow the wustite. The precipitation of further
induction period starts somewhat lower. Gener- wustite nuclei on the magnetite/wustite re-
ally, temperatures above 440 C are required to action interface seems to be effected by ion/
complete the reduction. electron diffusion processes rather than by
The reducibility of industrial catalysts is direct contact of magnetite with hydrogen
dependent on both the combination of promo- [292]:
ters and the degree of oxidation. The FeO
(wustite) phase is reduced faster and at lower O2 H2 !H2 O2 e
temperatures than the Fe3O4 (magnetite) phase
[218]. According to [218], the rather consider- Fe3 O4 Fe2 2 e !4 FeO
able differences in the reduction rates of com-
mercial catalysts with similar compositions The topotactic reduction process leads to
may be attributed to differences in manufactur- a core and shell structure which is visible
ing methods or operating conditions. Common- under the optical microscope and is shown
Figure 18. Mechanism of catalyst reduction [42]

a) Reducibility of catalyst under standard conditions as a function of its porosity; b) Core and shell structure of catalyst;
c) Reaction interface
schematically in Figure 18 (a). Figure 18 (b) oxidized to a depth of a few atomic layers to
shows the wustite/magnetite interface as ob- make these catalysts nonpyrophoric.
served by electron microscopy [49]. This con- Reactivating such catalysts usually takes only
cept was developed for single-crystal magnetite 30 40 h. Ammonia formation begins at sub-
grains, but the shell and core model is also valid stantially lower temperatures, so that altogether
for commercial polycrystalline catalysts [294, the downtime of a production unit is reduced
49]. Information on the reduction kinetics, in- markedly. This and further advantages, such
cluding industrial catalysts, can be found in [47, as reducing the risk of damaging the catalyst
246250]. Newer findings seem to question the during activation by too high a local concentra-
shell and core model with the topotactic reaction tion of water, the quantitatively lower yield of
interface [97]. On account of the simplifications aqueous ammonia solution (which can be added
involved this model should be regarded as a to the production), as well as the roughly 20 %
formalistic approach to describe the reaction lower bulk weight (which reduces the design
kinetics rather than a mechanistic approxima- loadings and costs of the internals of large
tion. A more detailed atomistic picture leads to converter units), make using prereduced cata-
the assumption that there is no homogeneous lysts increasingly attractive, especially in
topotactic reaction interface. According to this single-train plants, in spite of higher prices.
concept the active catalyst should not grow as a The somewhat inferior mechanical strength is
shell around a precursor core but as a core within a disadvantage that requires special care when a
an oxidic matrix. charge is being loaded into the converter. When
removed from the hydrogen nitrogen atmo-
Prereduced, Stabilized Catalyst Types, intro- sphere at low to moderate pressure in the
duced on the market some years ago, have producing furnace, the prereduced catalysts are
gained a considerable market share. Prereduced pyrophoric and must be stabilized before trans-
catalysts have the full pore structure of active port and installation by passivating the surface.
catalysts, although the pore surface has been Usually, the method recommended by BURNETT
is used. The reduced charge is treated with 100 ppm of O2 or CO2 and 200 ppm CO or
nitrogen containing 100 1000 ppm oxygen at H2O, lead to the same degree of poisoning,
50 70 C (maximum 95 C) and a pressure of presumably because as soon as they enter the
0.1 0.2 MPa (1 2 bar) and up [284]. The catalyst bed they rapidly and completely trans-
reducible oxygen content of the prereduced form into H2O [1]. The damage depends approx-
catalyst ranges between 2 and 7 %. Part of this imately linearly on the quantity of adsorbed
is only loosely bound and is removed in reacti- water taken up by the catalyst
p[295], which is
p
vation even below 200 300 C. proportional to pH2 O= pH2 [296]. Corre-
Detailed data on the manufacturing steps most sponding to the adsorption equilibrium, the de-
important to the catalyst performance, reduction, gree of poisoning therefore rises with growing
prereduction, passivating, and reactivation, ap- partial pressure ratio, pH2O/pH2 and falls with
pear in [1], including a discussion of the most increasing temperature.
important literature in this field. Under the assumption of a displacement equi-
librium in accordance with
N2 ads H2 Ogas 2 H2 gas
Oads 2 NH3
5.1.5. Catalyst Poisons
The activity of an ammonia synthesis catalyst I. A. SMIRNOV et al. set up a rate equation for
may be lowered by certain substances, com- ammonia synthesis [297, 298] that takes the
monly referred to as poisons. These substances effect of water vapor into consideration over a
can be minor gaseous constituents of the syn- wide range of temperature and pressure:
thesis gas or solids introduced into the catalysts
during the manufacturing procedure, derived k1 pN2 k2p2NH =p3H2
v 3
11
from impurities in the natural magnetite from p2NH3 =p2H2 CpH2 O =pH2 1=2
which the catalyst is made. These latter should
not play a major role with catalysts from man- and found the values of C listed in Table 11.
ufacturers of repute and are not discussed in A more recent investigation [299301] pro-
detail in this section because of the proprietary posed multiplying the rate equation by a correc-
nature of the production processes. General tion factor 1 Q, where Q abTcTlnXH2 O
measures to avoid this sort of contamination and XH2 O is the molar fraction of H2O. Some
include selecting a rather pure magnetite, the authors assume a different route for the formation
application of pretreatment processes, and the of adsorbed atomic oxygen [302, 303]:
use of high-purity promoters. The melting pro- H2 Og3
2 H O
cess itself may also contribute to minimizing the
content of some minor impurities. For gaseous where * denotes a surface site.
poisons in the synthesis gas, a distinction can be The equivalence of H2O, CO, CO2 and O2
made between permanent poisons that cause [304] with respect to their poisoning effect has
irreversible damage to the catalyst and tempo- been confirmed.
rary poisons which lower the activity while The experimentally determined effect of
present in the synthesis gas. In contrast to water vapor concentrations up to about 30 ppm
temporary poisons, permanent poisons can be on the activity of a commercial catalyst
detected by chemical analysis. Oxygen-contain- (BASF S 610) at 30 MPa is evident from
ing compounds such as H2O, CO, CO2, and O2 Figure 19.
are the most common temporary poisons
encountered in ammonia synthesis.
Table 11. C values for the ammonia synthesis rate equation
Oxygen Compounds have a reversible effect
Catalyst Temperature, C
on iron catalysts at not too high temperatures.
That is, the activity of a damaged catalyst may be 400 425 450 475 500
practically completely restored by reduction
Fe Al2O3 0.63 0.39 0.24 0.17 0.12
with clean synthesis gas. Equivalent concentra- Fe Al2O3 K2O 0.74 0.46 0.28 0.20 0.14
tions of oxygen compounds, for example,
they established that above all, temperatures

above 500 520 C must be avoided in order
to achieve a converter charge operating period of
more than 2 3 years. If the temperature is kept
at this level, generally recommended for modern
plants, then even at CO concentrations of 20 ppm
in the recycle loop gas, no serious deterioration
of the catalyst performance is observed after a
month of operation. With the highly purified
synthesis gas of modern synthesis processes
(with final gas purification by methanation the
carbon monoxide level is lowered to below
5 ppm), operating periods of up to 14 years can
be achieved for a converter charge without
significant loss of activity (Fig. 20).
As already mentioned in Section 5.1.1, the
concentration and combination of promoters
affect the degree of irreversible damage. This
must be considered in the choice of catalyst for a
particular plant.
Sulfur, Phosphorus, and Arsenic Com-

pounds. Sulfur, occasionally present in synthe-
sis gases from coal or heavy fuel oil, is more
tightly bound on iron catalysts than oxygen. For
Figure 19. Reversible effect of increasing water vapor con-
example, catalysts partially poisoned with
centrations in the synthesis gas on the activity of industrial hydrogen sulfide cannot be regenerated under
ammonia catalysts the conditions of industrial ammonia synthesis.
Compounds of phosphorus and arsenic are
With continuing exposure oxygen compounds poisons but are not generally present in industrial
also cause irreversible damage to the catalyst syngas. There are indications that these perma-
activity that is causally linked with growth of the nent poisons exert the most detrimental effect
iron primary crystallite [301, 305]. This is prob- when present as hydrogen compounds and are
ably one of the main causes of the decline in less harmful in higher oxidation states [307].
converter performance over the course of the
catalyst operating life. This damage depends on
the water-vapor partial pressure and is especially
serious, in contrast to reversible poisoning, at
high temperatures. In a pilot plant, Osterrei-
chische Stickstoffwerke (OSW), Linz, estab-
lished that at 30 MPa and a water-vapor content
of 250 ppm, for example, the production de-
clined by about 15 % per month. For a carbon
monoxide content of 5 ppm, they determined
about a 4 5 % decrease in activity per year.
The influence of the operating temperature is
evident from the data. The performance of a
catalyst operated at 570 C is about 35 40 %
under that of a catalyst charge operated at
520 C. That is, the higher the temperature, Figure 20. Activity of BASF ammonia catalyst S 610 in a
the greater is the harmful effect of oxygen commercial converter after 14 years of operation
compounds [306]. Corresponding to the data, . fresh catalyst; ~ after 14 years operation
With regard to the sulfur bound on the catalyst Chlorine Compounds. The permanent poi-
surface, differences exist between the various soning effect of chlorine compounds is two
types of ammonia catalysts, especially between orders of magnitude worse than that of oxygen
those containing or free of alkali and alkaline compounds. Concentrations of about 0.1 ppm
earths. Pure iron and catalysts activated simply are viewed as the uppermost allowable limit in
with alumina chemisorb S2N2 or thiophene when order not to affect adversely the life of ammonia
treated with concentrations of H2S that lie below catalysts [310]. The deactivation effect is based
the equilibrium for the FeS bond, a maximum of at least in part on the formation of alkali chlori-
0.5 mg of sulfur per m2 of inner surface or free des that are volatile at the upper synthesis
iron surface; this corresponds to monomolecular temperatures.
coverage [308, 309]. The monolayer is also Further information on catalyst poisoning is
preserved on reduction with hydrogen at 620 C, given in [300, 301].
whereas FeS formed by treatment above 300 C
with high H2S concentrations is reducible as far
as the monolayer. For total poisoning, 0.16 5.2. Other Catalysts
0.25 mg S/m2 is sufficient. Like oxygen, sulfur
promotes recrystallization of the primary iron 5.2.1. General Aspects
particle.
Under similar poisoning conditions, alkali- For a long time efforts to improve the efficiency
and alkaline earth-containing industrial catalysts of industrial ammonia production concentrated
adsorb more H2S. In spite of this, however, in on synthesis gas production, and major progress
terms of activity, they are more stable toward the was achieved over the years. In ammonia syn-
action of sulfur and are partially regenerable thesis itself considerable progress was made in
[309]. In a catalyst bed, most of the sulfur already converter design and recovery of the reaction
has been taken up in the gas inlet layer. A catalyst energy at high temperature, but there has been
sulfur content of several 100 ppm suffices to no substantial improvement in the catalyst since
impair its activity [1]. the 1920s. The standard commercial iron cata-
In industrial plants, sulfur may reach the lyst still requires relatively high pressures (usu-
ammonia converter in various forms. In some ally in excess of 130 bar), high temperatures
plants, traces of H2S and COS may not be re- (400 500 C) and large reactor volumes
moved in the upstream purification steps and so (more than 60 m3 for a capacity of 1500 t/d) to
may enter the converter with the make-up gas. achieve good economics, although in a few
However, the sulfur contained in the compressor cases a pressure as low as 80 bar has been used.
oil constitutes the main danger. On cracking the From the vast amount of experimental and
oil to lower molecular mass hydrocarbons, sulfur theoretical studies of the iron catalyst one can
is freed as H2S. It is therefore very important to conclude that there is only limited potential for
use an oil with low sulfur content in ammonia further improvement. Substantial energy sav-
plants, especially those still using reciprocating ings would require lowering the synthesis pres-
compressors. If after mixing with the recycle gas sure considerably, down to the synthesis gas
the make-up gas first runs through an ammonia production level, say. However, to compensate
condensation stage in which the H2S and also to a for the less favorable equilibrium situation
certain extent COS are very effectively washed much lower operating temperatures would be
out by condensing ammonia, a sulfur content of necessary, because otherwise too low an ammo-
the oil of 0.1 0.2 wt % ought to be sufficiently nia concentration would result, and additional
low. Otherwise, a value under 0.1 % is recom- energy would be needed for recovery, thus
mended [310]. In modern plants designed with cancelling the energy saving from synthesis gas
centrifugal compressors and in which the sulfur compression. To reach this goal a synthesis
content of the synthesis gas is extremely low catalyst with a volumetric efficiency some two
because of very effective purification (about orders of magnitude greater than magnetite
0.5 1 mg S/m3 (STP)), sulfur poisoning is of would be necessary. Process studies show an
lesser importance than carbon monoxide and energy saving potential of about 1 GJ per tonne
chlorine poisoning. NH3 [836].
In the search for an alternative catalyst, most . Anion retention capability, which plays a role
metals have been tested, either as primary in the catalyst preparation by impregnation of a
components or as promoters. Much of this work support with metal impregnation of the
was performed in the early, pioneering studies support.
in the BASF laboratories [175, 176]. Most of
the studies in the following years concentrated 5.2.2. Metals with Catalytic Potential
on the magnetite system in the sense of more
fundamental and general catalytic research. Materials that show significant ammonia synthe-
Rising energy costs since the mid-1960s have sis activity can be divided into three categories
given a new incentive to the search for other according to their ability to form nitrides:
catalyst systems with improved performance.
The first development which found commercial 1. Platinum group metals: no stable nitrides (Ru,
application was a cobalt-modified magnetite Os, Ir, Pt)
catalyst introduced in 1984 by ICI. With similar 2. Metals forming nitrides unstable under reac-
kinetic characteristics its volumetric activity is tion conditions (Mn, Fe, Co, Ni, Tc, Re)
about twice that of the standard iron catalyst. 3. Metals likely to be present as nitrides under
The only other catalyst system which exhibits a synthesis conditions (groups 3 6 of the pe-
promising potential for industrial application is riodic table)
based on ruthenium [120]. These new efforts to
find improved catalysts could use methods and Of the platinum group metals only ruthenium and
knowledge of modern surface science as devel- osmium show an activity superior to iron, though
oped on the example of the magnetite catalyst. only in presence of alkali metal promoters, as
Structural sensitivity and nature of the nitrogen may be seen from Table 12 [311].
adsorption and dissociation steps could serve as Although osmium was the first active catalyst
guidelines [121]. used by HABER in 1909 [312] in his laboratory-
For the overall performance of potential scale unit to demonstrate the technical viability
catalysts in practical application additional of the high-pressure recycle process, this metal
factors, such as number of active sites, physi- never became an industrial catalyst because of its
cal form, and porosity must also be taken into limited availability and its dangerous properties.
account. The classical commercial iron cata- The interest therefore shifted to ruthenium. The
lyst is an unsupported catalyst. First of all iron most active ruthenium catalysts use a graphite
is a cheap material and secondly by the incor- support and alkali metal promotion, preferen-
poration of alumina a surface area similar to tially with rubidium or cesium [319, 323]. It is
that attained in highly dispersed supported unlikely that the promoter is in metallic state as
catalysts can be obtained. Of course, for an its high vapor pressure would probably lead to
expensive material such as the platinum group substantial losses under synthesis conditions. It is
metals, the use of a support material is the only assumed that a charge transfer complex MC
viable option. The properties of the supported is formed between the metal and the graphite. A
catalyst will be influenced by several factors major advantage of graphite is its ability to
[120] stabilize high loadings of alkali metals. A special
limitation until recently was the chemical reac-
. Adequate surface of the carrier to achieve a tivity of carbon supports. In a typical ammonia
reasonable metal loading. synthesis environment with high hydrogen
. Dispersion stability by using a more active partial pressure, the catalyst may also catalyze
support with strong interaction between the the methanization of carbon, which would lead to
support phase and the metal precursor. Too
strong an interaction may cause difficulties in Table 12. Ammonia synthesis activity of metals supported on carbon
with potassium metal promotion (mL NH3/ mL catalyst, 573 K,
the metal reducing. 128.313 kPa, H:N 3:1)
. Promoter localization with respect to metal
sites and support sites. Fe 0.72 Co 0.4 Ni 0.04
. Gas transport effects will be governed by pore Mo 0.6 Ru 22.2 Rh 0.52 Pd 0
Re 0.36 Os 5.6 Ir 0.68 Pt 0.008
size, pore distribution, and tortuosity.
destruction of the support. Indeed, this phenom- achieved for the magnetite system: optimization
enon has been observed [313], but it can be of manufacturing procedures, promoter concen-
avoided by careful heat treatment of the support trations, and particle size to give somewhat high-
above 1500 C [314]. With this modified carbon er activity and longer service life.
material lifetimes of at least six years are A notable development for the magnetite
expected [311]. system was the introduction of cobalt as an
The group of metals forming low-stability or additional component by ICI in 1984 [320,
unstable nitrides includes Mn, Fe, Co, Ni, Tc, and 321]. The cobalt-enhanced catalyst formula was
Re. As in the case of iron a clear structural first used in an ammonia plant in Canada using
sensitivity was found for rhenium but the role ICI Catalcos AMV process (later also in other
of promoters remains the subject of discussion. AMV license plants) and is also successfully
There are also indications of structure sensitivity applied in ICIs LCA plants in Severnside. Com-
for cobalt and nickel. It was attempted to improve mercially successful is a new type of iron-based
the activity of the classical magnetite catalyst by catalyst, the AmonMax-10 of Sudchemie which
alloying with nickel or cobalt. The only commer- uses wustite instead of magnetite. This catalyst is
cial catalyst is a cobalt containing magnetite already used in seven ammonia plants with a total
[315]. capacity of 5600 t/d [843845, 875]. Production
Of the group of metals forming stable nitrides, of synthetic wustite is described in [847], its
only molybdenum is of some interest. Under application for ammonia synthesis catalyst in
synthesis conditions it is present as a nitride with [846]. For a literature report on promoted iron
some ammonia formation activity and structural catalysts see [848].
sensitivity [316]. Molybdenum also seems to In 1979 BP disclosed to M.W. Kellogg a new
exhibit activity in biological nitrogen fixation catalyst composed of ruthenium on a graphite
[317] and is synthetically active at ambient con- support [320, 322]. In October 1990, after a ten-
ditions in the air-sensitive Glemser compounds year test program, Kellogg started the commer-
[317, 318]. cialization of the Kellogg Advanced Ammonia
The results of the intensive research in this Process (KAAP) using this catalyst [322], which
field over the last decades demonstrate that, is claimed to be 10 20 times as active as the
irrespective of the catalyst, the rate-determining traditional iron catalyst: The KAAP catalyst.
step in the ammonia synthesis reaction is the According to the patent [315] the new catalyst
dissociation of the nitrogen molecule and the is prepared by subliming ruthenium-carbonyl
catalyst effectivity is determined in the first [Ru3(CO)12] onto a carbon-containing support
instance by the activation energy of the dissoci- which is impregnated with rubidium nitrate. The
ation reaction. The other common factor for the catalyst has a considerably higher surface area
ammonia catalysis is the structure sensitivity of than the conventional catalyst and, according to
molecular nitrogen adsorption. Only if both the patent example, it should contain 5 wt % Ru
conditions are favorable, and other factors such and 10 wt % Rb. Besides having a substantially
as hydrogen and ammonia inhibition do not play higher volumetric activity, the promoted ruthe-
a major role, can a sufficient overall reaction nium catalyst works best at a lower than stoichoi-
rate be expected. The available data show that metric H/N ratio of the feed gas as shown in
these conditions are fulfilled only for a limited Figure 21. It is also less susceptible to self-
number of metals: iron, ruthenium, and osmium. inhibition by NH3 (Figure 22) and has excellent
On account of its very strong ammonia inhibi- low-pressure activity.
tion rhenium is not an option. Extensive litera- Three ammonia plants in Trinidad, each with a
ture on non-iron catalysts is given in [120, 121]; nameplate capacity of 1850 t/d, use the KAAP
kinetic investigations are reported in [121]. ruthenium catalyst [840]. The first layer of the
four-bed reactor [841, 331] is loaded with con-
ventional magnetite catalyst, the others with the
5.2.3. Commercial Ruthenium Catalysts ruthenium graphite catalyst. For the special
properties of ruthenium, which have to be con-
Since the early days of industrial ammonia syn- sidered in handling these catalysts see [331].
thesis only minor improvements have been Topse has developed a ruthenum catalyst which
whether the benefits of its use are sufficient to

compensate the higher costs. Ruthenium prices
increased by a factor of four in 2000 to 170 $/oz.
due to new applications in the electronic indus-
try. Ruthenium price development is occasionaly
published in FINDS, a Stokes Engineering
Publication.
In common with the iron catalyst ruthenium
will also be poisoned by oxygen compounds.
Even with some further potential improvements
it seems unlikely to reach an activity level which
is sufficiently high at low temperature to allow
operation of the ammonia synthesis loop at
the pressure level of the syngas generation. An
overview over ammonia synthesis catalyst
development history and newer research is
given in [849].
Figure 21. Effect of H/N ratio on activity of Ru and Fe3O4
catalysts [120]
6. Process Steps of Ammonia
uses boron nitride instead of graphite as support. Production
Boron nitride, occasionally called white graph-
ite, because of its structure similar to graphite, is The term ammonia synthesis is increasingly
completely stable towards hydrogenation under used when referring to the total ammonia pro-
all conditions relevant to technical ammonia duction process. Synthesis conditions are no
synthesis. A Ba-Ru/BN catalyst proved longer viewed in isolation. Of course, they are
completely stable in a 5000 h test at 100 bar and an important consideration in the total process
550 C using a 3:1 H2 N2 mixture [849]. There but can be determined properly only in relation to
is no industrial application so far. A discussion on the total plant integration (see ! Ammonia, 3.
ruthenium as ammonia synthesis catalyst with an Production Plants, Chapter 1). A literature sum-
extensive literature review is found in [866]. mary of ammonia production is contained in
The potential for ruthenium to displace in the [327] and [328]; the United States patent litera-
long run iron in new plants will depend on ture in the field from 1972 to 1980 is covered in
[229]. More modern and comprehensive reviews
of ammonia production technology can be found
in [329331, 841, 831]. The journal Nitrogen,
now named Nitrogen Syngas, published by
British Sulphur, presents an update of the state of
the art from time to time.
The complete process of industrial ammonia
production may be subdivided into the following
sections:
A. Synthesis gas production

1. Feedstock pretreatment and gas generation
2. Carbon monoxide conversion
3. Gas purification
B. Compression
C. Synthesis and purge gas management
Figure 22. Ammonia inhibition of Ru and Fe3O4 catalysts The most fundamental changes over the years
[120] have occurred in synthesis gas production and
Table 13. Feedstock distribution of world ammonia production capacity
1962 1972 1983 1998
103 t N % 103 t N % 103 t N % 103 t N %
Coke oven gas and coal 2800 18 4600 9 7200 8 16500 14

Natural gas 7800 50 32100 63 66850 74 94300 77
Naphtha 2050 13 10700 21 9050 10 7300 6
Other petroleum products 2950 19 3600 7 7200 8 4400 3
Total 15600 100 51000 100 90300 100 122500 100
gas compression. In the synthesis section itself, Table 13 provides an overview of the raw
some progress has been made in converter design material sources (apart from water and air) for
and optimization of heat recovery. world ammonia capacity.
Synthesis gas preparation, carbon monoxide Table 13 indicates that new ammonia plants
conversion, and gas purification for ammonia are based almost exclusively on natural gas and
synthesis are treated in detail in the article ! Gas naphtha. This trend is also expected to continue
Production, 2. Processes. Therefore, only a short in the near future. Naturally, the regional distri-
abstract is presented here. bution is diverse. In North America, for example,
natural gas dominates, with 95 % of capacity. In
the EU, 86 % of capacity is based on natural gas
6.1. Synthesis Gas Production and 8 % on naphtha [427].
The capital cost and the specific energy
The goal is preparing a pure mixture of nitro- requirement (i.e., feed and fuel, and so the
gen and hydrogen in the stoichiometric ratio of manufacturing cost) largely depend on the raw
1 : 3. The raw materials are water, air, and a material employed [339, 340]. Table 14 shows
carbon-containing reducing medium, that, for the relative capital cost and the relative energy
its part, may contain hydrogen (natural gas, requirement for a plant with a capacity of 1800 t/d
CH4 ; naphtha, CH2; petroleum, CH) and ammonia. For the natural gas based plant the
nitrogen; for example, natural gas from the current best value of 28 GJ per tonne NH3 is
Slochteren field in the Netherlands contains used. If water electrolysis (4.5 kWh/Nm3 H2) is
14 % nitrogen. used together with an air separation unit for the
Usually only the carbon-containing materials nitrogen supply the energy requirement amounts
and hydrogen from other sources are regarded as to 34 GJ per tonne NH3 when the electric energy is
raw materials in the narrow sense because of the valuated just with the caloric equivalent, which
abundance of air, which provides all of the would be only justified when electric power is
nitrogen, and water, which generally supplies generated from water power. In case of electricty
most of the hydrogen. The term feedstock is generation from fossil energy with 40 % efficien-
often applied to the total consumption of fossil cy the consumption figure is 85 GJ per tonne NH3,
fuel, although strictly speaking a distinction which is 300 % of the consumption of a modern
should be made between gasification feed and steam reforming plant [862]. The investment
fuel for energy generation. could according to a rather rough estimate be
Certain raw materials for synthesis gas pro- about three times the investment for a steam
duction that were once of primary importance reforming plant with natural gas.
currently are used only under special economic
and geographical circumstances (e.g., China,
Table 14. Relative ammonia plant investment and relative energy
where 66 % of production is based on coal). requirement for 1800 t/d NH3
These include solid fuels, coke oven gas, and
hydrogen produced by electrolysis. Reference Natural gas Naphtha Fuel oil Coal
[334] covers coke oven gas as a feedstock for Relative investment 1.0 1.15 1.5 2.5
ammonia synthesis and references [335338] Relative specific energy 1.0 1.1 1.3 1.6
describe producing hydrogen by water electrol- requirement (based on
ysis for ammonia production. lower heating values)
6.1.1. Feedstock Pretreatment and Raw steam-reforming route. In the partial-oxidation

Gas Production route less hydrogen is produced in the primary
gasification step and the raw synthesis gas has a
The chemical reaction of hydrocarbons with rather high CO content.
water, oxygen, air, or any combination of these The raw gas composition is thus strongly
is generally referred to as gasification. It yields a influenced by the feedstock and the technology
gas mixture made up of CO and H2 in various applied. But for the different feedstocks there are
proportions along with carbon dioxide and, some constraints on the applicability of the vari-
where air is used, some nitrogen. Any carbon ous gas generation processes. The catalytic steam
containing feedstock will undergo a reaction reforming technology can only be applied to light
according to Equation (5) or (6) or both simulta- hydrocarbon feedstock (up to naphtha) but not for
neously. heavy hydrocarbons such as fuel oil or vacuum
residue. These raw materials contain a substan-
CHx H2 O
COH2 x=2 H2 DH > 0 12
tial amount of sulfur and also minor quantities of
heavy metals, which would poison the sensitive
CHx 1=2 O2
COx=2 H2 DH < 0 13
reforming catalyst. In addition cracking reactions
Light hydrocarbons ranging from natural gas will occur on the catalyst, depositing carbon,
(methane) to naphtha (max. C11) undergo reac- which not only blocks the catalyst pores but also
tion with steam over a catalyst according to restricts interparticle flow. Thus for heavy feed-
Equation (5) which is usually called steam stocks the only choice is noncatalytic partial
reforming. Corresponding to Equation (6), com- oxidation, which, however, is capable of proces-
monly known as partial oxidation, all carbon- sing any type of hydrocarbon feedstock. The
containing feedstocks can be processed in a various commercial coal gasification processes
noncatalytic reaction with oxygen (together with may also be classified as partial oxidations.
a minor amount of steam for process reasons,
which gives rise to a simultaneous reaction Steam Reforming Processes (see also !
according to Eq. 5). An additional equilibrium Gas Production, 1. Introduction, Chapter 2). As
reaction involved in any gasification process is the nickel-containing catalysts are sensitive to
the water gas shift reaction (7). poisons, any sulfur compounds present in the
hydrocarbon feedstock have to be removed by
COH2 O
CO2 H2 DH 0298 41 kJ=mol 14 hydrodesulfurization, generally with a combina-
tion of cobalt molybdenum and zinc oxide
Although reaction in the right hand direction catalysts [485, 486, 564].
is favored by lower temperatures it is responsible Adsorption on activated carbon is an alterna-
for the initial carbon dioxide content of the raw tive when the feed is natural gas with a rather low
synthesis gas. To maximize the hydrogen yield, sulfur content.
this reaction is carried out in a separate step over a
RSHH2 !RHH2 S 15
different catalyst at a lower temperature than the
preceding gasification step (Section 6.1.2).
H2 SZnO!ZnSH2 O 16
From Equation (5) it can be seen that in the
steam reforming variant the proportion of hydro-
gen supplied by the feedstock itself increases The general overall reaction can be formulat-
with its hydrogen content. It attains the theoreti- ed as
cal maximum of 66 % with methane. The hydro-
Cn H2n 2 n H2 O
nCO2n1H2 17
gen oxygen bond energy in water is higher than
the hydrogen carbon bond energy in the hy- or more specifically for methane, usually the
drocarbon. The positive enthalpy per mole of major constituent of natural gas, as:
hydrogen therefore decreases as the proportion of
CH4 H2 O
CO3 H2 DH 206 kJ=mol 18
hydrogen contributed from the feedstock itself
increases. Natural gas consists predominantly of
methane and is therefore the most hydrogen-rich Simultaneously to this equilibrium the water
and energetically the best raw material for the gas shift reaction (Eq. 7) proceeds.
To introduce nitrogen to achieve the required material. Another possibility to compensate is a

stoichiometric hydrogen/nitrogen ratio for am- higher steam surplus (steam/carbon ratio), but
monia synthesis, the reforming reaction is split this is economically unfavorable. The furnace
into two sections. In the first section, the primary box usually accommodates 200 400 tubes
reformer, the reaction proceeds in indirectly (depending on plant capacity), 10 13 m long,
heated tubes filled with nickel-containing with an inner diameter of 75 140 mm and
reforming catalyst and is controlled to achieve a wall thickness of 11 18 mm. The standard
a partial conversion only [in conventional plants material for a long time was HK 40 (20 Ni/
65 % based on methane feed, leaving around 25 Cr) but for replacements and new plants, HP
14 mol % methane (dry basis) in the effluent modified (32 35 Ni/23 27 Cr stabilized
gas]. In the following secondary reformer a with about 1.5 % Nb) is being increasingly used
refractory-lined vessel filled with nickel cata- on account of its superior high-temperature
lyst the gas is mixed with a controlled amount properties [350]. With this latter tube material
of air introduced through a nozzle (burner). By a reforming pressure of 40 bar is possible at
combustion of a quantity of the gas the temper- outer tube-wall temperatures of around 900 C .
ature is raised sufficiently (to about 1200 C) A further improvement are microalloys that
that the endothermic reforming reaction is com- additionally contain Ti and Zr [331, 841, 863,
pleted with the gas adiabatically passing the 865].
catalyst layer. In this way the outlet temperature According to the disposition of the burners
is lowered to around 1000 C, and a residual primary reformers can be classified as top-fired,
methane content of 0.5 % or lower (dry basis) is side-fired, terraced-wall, or, less common,
attained in conventional plants [329, 331]. Ni- bottom-fired reformers [331, 841]. The steam/
trogen already present in the natural gas tends to carbon ratio used in modern commercial primary
cause a reduced specific air ratio in the second- reformers for natural gas is between 2.8 and 3.5,
ary reformer and a reduced secondary reformer and markedly higher for naphtha, for which an
temperature rise. Therefore, to maintain the alkalized nickel catalyst has to be used to prevent
same methane leak, the primary reformer exit carbon deposition, which causes catalyst deacti-
temperature must be increased. vation and local overheating of tubes (hot bands
The primary reformer consists of a multitude and hot spots). A special requirement for the
of reformer tubes loaded with the nickel catalyst catalyst is a low content of silica, which could
(15 25 % NiO on a-aluminum oxide, calcium be volatile under the hydrothermal conditions
aluminate, or magnesium aluminum spinel sup- and deposit downstream of the secondary
port) [841] in a furnace box in which the heat reformer at lower temperature, causing fouling
needed for the reaction is transferred to the tubes of the waste-heat recovery surfaces.
by radiation. The heat is generated in burners, When higher hydrocarbons (naphtha) are
generally gas-fired, in the furnace box. used, a so-called rich gas stage can be utilized
A special consideration is the lifetime of upstream of the primary reformer. In this, the
the expensive reformer tubes, made of highly higher hydrocarbon steam mixture is trans-
alloyed chromium-nickel steel by centrifugal formed at relatively low temperature (400
casting, because under the severe reaction con- 500 C) and steam carbon ratios less than two
ditions the material exhibits creep which finally into a methane-rich gas. This is then converted
leads to rupture [850, 867]. The time to rupture in the primary reformer under normal reforming
for a specific material depends on the tube-wall conditions. For this rich-gas stage, three pro-
temperature and on the internal pressure. This cesses are commercially available: the British
limits the reforming pressure, which to save Gas Process [351], the BASF Lurgi Process
energy in synthesis-gas compression should be [352354], and the Japan Gasoline Process
as high as possible. As the reforming reaction is [355].
endothermic and proceeds with volume in- This process has recently become the subject
crease the negative effect of a pressure increase of renewed interest for increasing the capacity of
(lower conversion) has to be compensated by a existing natural-gas-based ammonia plants in
higher reaction temperature and hence higher which the primary reformer has been identified
wall temperatures, but this is limited by the as bottle-neck. Under the name pre-reforming, it
is installed up-stream of an existing tubular instead of air [329, 371, 384, 385, 841, 877, 878].
reformer [356363, 331, 841]. The natural gas Unlike to a secondary reformer, which is fed with
enters such a pre-reformer with a temperature of partially reformed gas, having a substantial con-
530 C instead of being fed to the primary re- centration of hydrogen, the autothermal reformer
former tubes with the same temperature. A tem- (ATR) is fed directly with the hydrocarbon feed-
perature drop of about 60 70 C occurs in the stock. Because of the higher heat of reaction in
catalyst bed due to the overall endothermic reac- the internal combustion (temperature >2000 C),
tion. Medium-grade heat is used to reheat the exit the flow conditions, heat release characteristics
gas to the correct primary reformer entrance and the risk of soot formation are very different
temperature. This compensation heat may be from the situation of a normal secondary refor-
derived from a variety of sources, including flue mer. Therefore special considerations in the de-
gas, process gas, or gas turbine exhaust. sign of burner and reactor are necessary. See also
Another possibility for reducing the load on ! Gas Production, 2. Processes.
the primary reformer is to transfer part of the A recent development which avoids a fired
conversion duty to the secondary reformer with primary reformer is the exchanger reformer,
application of an super-stoichiometric amount which with some simplification may be viewed
of air. This requires removal of the surplus of as tubular heat exchanger with the catalyst inside
nitrogen from the synthesis gas either ahead the tubes, which are heated by the hot secondary
of the synthesis loop (by cryogenic methods or reformer effluent flowing on the shell-side. In
pressure swing adsorption) or by purge gas and some designs the tubes may be open at the lower
hydrogen recovery [382, 383]. In the extreme end, in which case the gas flow on the shell side
case the whole reforming reaction could be per- consists of a mixture of the off-gases from the
formed without a tubular reformer by autother- secondary reformer and from the reformer tubes.
mal catalytic reforming in a design similar to a Commercially operating designs are the GHR
secondary reformer. In this case it would be of ICI (Figure 23) [331, 386389] and the KRES
necessary to use oxygen or oxygen-enriched air of M. W. Kellogg [391395, 841843, 872]
Figure 23. ICI gas heated reformer

A) GHR; B) AGHR
a) Tubeside inlet; b) Tubeside outlet; c) Scabbard tube; d) Bayonet tube; e) Sheath tube; f) Shellside inlet; g) Shellside outlet;
h) Catalyst tube; i) Seal; j) Tail pipe; k) Catalyst; l) Refractory lining
Figure 24. Kellogg reforming exchanger System (KRES) [331]
(Fig. 24). Similar concepts are offered by other A concept developed by Uhde goes a step
licensors and contractors e.g., Braun & Root, or further in this direction: exchanger reforming and
Topse [331]. subsequent noncatalytic partial oxidation, which
ICI has come out with a modified design, the provides the reaction heat, are accommodated
AGHR, with A standing for advanced. As in a single vessel. This combined autothermal
shown in Figure 23 B, the bayonet tubes are reformer (CAR) design, shown in Figure 25 was
replaced by normal tubes attached to a bottom operated in a demonstration unit producing
tubesheet using a special seal to allow some 13 000 m3/h of synthesis gas [397400].
expansion. In this way the delicate double tube- A unique steam reforming process [364366]
sheet of the GHR is avoided. The seal which has been developed in Japan to the pilot-plant
prevents leakage of methane-rich gas to the
secondary reformer effluent flowing on the shell
side has a unique design which is subject to
patent applications of ICI. The AGHR will allow
a single-line concept for worldscale plants
whereas with the GHR several parallel units for
large plants would be necessary [331].
Because of the smaller size compared to a
conventional fired reformer considerable in-
vestment savings can be achieved. To close the
heat balance between the exchanger reformer
and secondary (autothermal) reformer, the latter
has to take on a higher reforming duty, which
may be achieved by using an over-stoichiomet-
ric amount of air or oxygen-enriched air. In
some configurations the exchanger reformer is
partially by-passed, part of the feed being fed
directly into the autothermal reformer.
Haldor Topse has developed an exchanger
reformer called HTER which may be used in
various process configurations as described in
[851]. The design may be also used as a convec- Figure 25. Uhde combined autothermal reformer (CAR)
tive reformer, called HTCR with a dedicated a) Sandwich type tubesheet; b) Enveloping tube; c) Reformer
burner. tubes; d) Tubesheet; e) Refractory lining; f) Water jacket
stage. It reportedly can operate without upstream Generation Process (TSGP) and the Shell Gasi-
desulfurization and should be able to gasify fication Process (SGP). In both the reaction is
naphtha, crude oil, and atmospheric or vacuum performed in an empty pressure vessel lined with
residues. alumina. The reactants (oil and oxygen, along
For literature on steam reforming see with a small amount of steam) are introduced
[329333, 345, 367373]; reaction kinetics and through a nozzle at the top of the generator
thermodynamics [841]; for steam reforming of vessel. The nozzle consists of concentric pipes
naphtha, [376378]; for steam reforming cata- so that the reactants are fed separately and react
lysts, [379, 380, 331, 381, 841, 852] for reformer only after mixing at the burner tip or in the space
design, [331, 374, 375, 841]. An oververview of below. The temperature in the generator is
the steam reforming technology, its historical between 1200 and 1400 C. Owing to insuffi-
development, present state of the art, newer cient mixing with oxygen, about 2 % of the
developments and future perspectives together hydrocarbon feed is transformed into soot, which
with quotation of newest literature is given in is removed from the gas by water scrubbing.
[850]. Detailed discussion on exchanger re- Depending on the process configuration the gas
forming and autothermal reforming is found in is either cooled by quenching or in a waste-heat
[851]. boiler. The TSGP and SGP are rather similar,
they mainly differ in the nozzle design, soot
Partial Oxidation. Hydrocarbons or coal removal and recirculation, and process gas
will react with an amount of oxygen insufficient cooling. The reaction pressures may be as high
for total combustion to CO2 according to: as 80 bar; there are no mechanical or material
limitations to raising the gasification pressure
Cn Hm n=2 O2 !n COm=2 H2 19
further, but with respect to the overall ammonia
process this might be beyond the energy opti-
C1=2 O2 !CO DH 123 kJ=mol 20
mum because of the increasing energy demand
for nitrogen and oxygen compression. Maximum
In practical operation some steam must raw gas generation capacity of a single generator
always be added, the quantity depending on corresponds to about 1000 t/d ammonia. World-
feedstock and process configuration, so that the scale ammonia plants based on partial oxidation
following reactions proceed in parallel: exist in Germany, India, China, and other coun-
tries [390]. Further information is found for the
Cn Hm n H2 O!n COnm=2H2 21
TSGP in [346349, 411, 412, 414416], for the
SGP in [396, 402410, 417]; see also ! Gas
CH2 O!COH2 DH 119 kJ=mol 22
Production, 2. Processes.
As the overall reaction is exothermic no Partial Oxidation of Coal. So far the

external heat supply is necessary. Since in some Koppers Totzek, Texaco and Lurgi gasifiers,
processes with coal feedstock (e.g., the Lurgi and probably the Winkler process in some smal-
Process) the reaction according to Equation (15) ler installations, have been used in ammonia
may proceed to a considerable extent, they are plants, but the successful demonstration of the
more often referred to as coal gasification rather Shell process in other applications makes it a
than as partial oxidation, but this is just a matter potential candidate for ammonia production,
of definition. too. Additional processes in different stages of
Certain processes have achieved particular technical development are the HTW and the
significance. The Texaco and Shell processes Dow process. Information on the status and the
can handle fuel oil, vacuum residues, and coal. development in the gasification of coal can be
The Lurgi process handles lump coal, operates at obtained from [418421, 423426, 428]. A
2.5 MPa, the Koppers Totzek process operates special case is China, where a number of small
on coal dust at atmospheric pressure. plants with a capacity of 30 80 t/d still pro-
duce their synthesis gas with the today largely
Partial Oxidation of Hydrocarbons. The outdated water-gas process which operates at
two dominant processes are the Texaco Syngas atmospheric pressure. Coke or anthracite is
reacted intermittently with air and steam in a carbon is removed at the bottom of the gasifier
fixed bed. The heat produced by the exothermic by a revolving grid with slots through which
reaction of coal and air in the blow phase is steam and oxygen are introduced. The tempera-
stored in the fixed bed and provides the heat ture in the lower section of the bed is around
needed for reaction of coal with steam in the 1000 C, and at the top where the raw gas exits
run phase [24, 422]. about 600 C. As a result of this lower tempera-
The Koppers Totzek Process [429, ture the raw gas has an increased content of
431435] used in several ammonia plants in impurities such as tars, phenols, and some higher
China, India, and South Africa, operates practi- hydrocarbons. In addition the methane content is
cally at atmospheric pressure. Dry coal dust is fed relatively high (up to 10 15 %), so that purifi-
to the two (sometimes four) burners of the gas- cation and conditioning of the raw gas is a rather
ifier. Oxygen, together with a small amount of elaborate task. The process actually can use any
steam, is introduced immediately at the head of sort of coal and can handle ash contents higher
the burners, and the mixture enters the reaction than 30 %. The British Gas/Lurgi Slagging
zone with high velocity. The residence time is Gasifier [420, 453, 456] operates without a grate
less than 1 s and the temperature is 1500 with withdrawal of the liquid slag.
1600 C. The gas leaving the top of the reactor The classic Winkler gasifier, which operates
vessel is cooled in a waste-heat boiler, followed at atmospheric pressure, is today still in use in
by a water scrubber to remove carbon and ash some smaller plants (e.g., in China). In a further
traces from the raw gas and to effect further development (HTW process) by Rheinbraun it
cooling. Liquid slag is withdrawn from the reac- has been tested in a demonstration plant with
tor bottom. The process can handle bituminous lignite at 10 bar [459, 460].
coal and lignite. To overcome the disadvantage The Advanced Coal Gasification Process
of atmospheric pressure operation, a version was (ACGP) [462], a new concept developed by
developed capable of operating at 25 30 bar. AECI Engineering, Kynoch Ltd and Babcock
This Prenflow (pressurized entrained flow) Wilson, is an entrained gasification process at
process [436, 831] is being tested in a 48 t/d atmospheric pressure. Pulverized coal and oxy-
pilot plant. gen are injected near the base of the gasifier
The Texaco Coal Gasification Process [420, through eight burners using a proprietary feed
443450] is rather similar to the Texaco partial technique which employs a special pump. The
oxidation process for heavy hydrocarbons. An gasifier is a slender column with a square cross-
aqueous slurry containing 60 70 % coal is fed section. The combustion area is lined with heat
by reciprocating pumps to the generator at a resistant ceramic material. The upper part is
pressure of 20 40 bar. Waste-heat boiler, made of finned tubes which are welded together
quencher, and carbon scrubber are especially and are circulated with water by thermosyphon
adapted to deal with the ash and slag introduced action. So far no commercial installation exists
with the bituminous coal feed. but it is claimed that one unit can produce the
In its coal gasification process [420, synthesis gas for 750 t/d ammonia.
437442]. Shell has completely departed from A block diagram showing steam reforming
the concept of its process for partial oxidation of and partial oxidation together with the further
heavy hydrocarbons. With reversed flow pattern steps needed to transform the raw gas into pure
in the gasifier (from bottom to top), dry coal dust make-up gas for the synthesis is shown in
is introduced via lock hoppers into the reactor Figure 26.
vessel operating at 20 40 bar.
The Lurgi Dry Gasifier [420, 451455, 457,
458] performs the reaction in a moving bed, 6.1.2. Carbon Monoxide Shift Conversion
usually operating at 25 30 bar. Crushed coal
with a particle size of 4 40 mm enters the top of As ammonia synthesis needs only nitrogen and
the gasifier through a lock hopper and is evenly hydrogen, all carbon oxides must be removed
distributed over the cross-section of the coal bed from the raw synthesis gas of the gasification
surface by a distribution disk equipped with process. Depending on feedstock and process
scraper arms. Ash with only 1 % of residual technology, this gas contains 10 50 % carbon
Figure 26. Alternative process steps for generation and purification of synthesis gas
monoxide and also varying amounts of carbon To keep the temperature low the heat of reac-
dioxide. In the water gas shift reaction, tradition- tion must be removed in appropriate way and to
ally known as carbon monoxide shift conversion achieve a sufficient reaction rate effective cata-
(Eq. 7), the carbon monoxide serves as reducing lysts have to be applied. The process is therefore
agent for water to yield hydrogen and carbon performed in steps, with intermediate heat remov-
dioxide. In this way not only is the carbon al between the individual catalyst beds in which
monoxide converted to readily removable carbon the reaction runs adiabatically. Quasi-isothermal
dioxide but also additional hydrogen is produced: reactors have been developed in which cooling
tubes run though the catalyst layers. As the pro-
COH2 O
CO2 H2 DH 41:2 kJ=mol 23
cess configuration and catalysts are to some extent
different for steam reforming and partial oxida-
As no volume change is associated with this tion, they are treated separately here.
reaction, it is practically independent of pres-
sure, but as an exothermic process, it is favored Shift Conversion in Steam Reforming
by lower temperatures, which shift the equilib- Plants. In the traditional plant concept, the gas
rium to the right-hand side. Even with a low from the secondary reformer, cooled by recover-
excess of steam in the gas, the equilibrium ing the waste-heat for raising and superheating
concentrations of CO are low; for example, steam, enters the high-temperature shift (HTS)
0.2 vol % at 220 C and 0.12 vol % at 200 C reactor loaded with an iron chromium catalyst
for a steam/gas ratio of 0.4. at 320 350 C. After a temperature increase of
around 50 70 C (depending on initial CO bulk ZnS. When the ZnO is exhausted in a given
concentration) and with a residual CO content layer of the catalyst, the H2S causes deactivation
of around 3 % the gas is then cooled to 200 of the copper by sintering. The poisoning process
210 C for the low temperature shift (LTS), moves through the catalyst as a relatively sharp
which is carried out on a copper zinc alumi- front and can be seen in the change of the catalyst
na catalyst in a downstream reaction vessel and temperature profile over time [473, 474]. The
achieves a carbon monoxide concentration of LTS catalyst is protected by a guard bed, former-
0.1 0.3 vol %. ly loaded with ZnO, but nowadays usually with
In the unreduced state the HTS catalyst is iron LTS catalyst [483]. Changing the guard bed more
(III) oxide (Fe2O3) containing additionally 5 frequently prolongs the service life of the main
10 % chromic oxide (Cr2O3). During operation, it LTS catalyst bed. Traces of chlorine compounds
is reduced more or less stoichiometrically to the [482], which may be introduced with the natural
composition of magnetite (Fe3O4). This catalyst gas or more often with the process air to the
is active in the temperature rage of 300 secondary reformer, may also deactivate the LTS
500 C. Steam surplus is not only necessary for catalyst by accelerating the sintering of the cop-
thermodynamic reasons but also to suppress per particles. Unlike sulfur poisoning, chlorine is
undesirable side reactions. Decreasing the steam more diffusely distributed over the whole cata-
surplus lowers the oxygen to carbon ratio in the lyst bed by migration as volatile zinc and copper
HTS to such an extent that the atmosphere can chlorides.
reduce magnetite partially to metallic iron. In As chemical composition and formulation of
addition the Boudouard reaction can occur under the LTS catalyst are very similar to methanol
these conditions. The resulting carbon is depos- production catalysts, small quantities of methanol
ited within the catalyst particles causing their are formed and are found in the process conden-
disintegration, and iron carbides will be formed, sate after cooling the LTS effluent. In a consecu-
which are effective Fischer Tropsch catalysts tive reaction, amines (mainly methylamine) are
that lead to the formation of some methane and formed from the methanol and traces of ammonia
higher hydrocarbons [331, 469, 470]. Newly originating from the secondary reformer and the
introduced HTS catalysts with additional copper HTS. These pollutants are removed from the
promotion suppress this side reaction [471] and process condensate by steam stripping and ion
are therefore less sensitive to lower steam-to-gas exchange. Byproduct formation is higher with
ratios. The classical HTS iron catalyst is resistant fresh catalyst and declines with operating time.
against sulfur compounds, but this is of greater New catalyst types with increased activity and
importance in partial oxidation processes and higher selectivity have reduced the problem. The
less for the practically sulfur-free steam reform- tendency for methanol formation increases with
ing gas. decreasing steam/gas ratio [477].
In some ammonia process schemes operating A relatively new process concept is the inter-
without a secondary reformer and applying pres- mediate temperature shift (ITS) [475] which
sure swing adsorption (PSA) for further purifica- performs the shift conversion in a single step.
tion (KTI PARC) only a HTS is used. The catalyst is based on a copper zinc alu-
The LTS catalyst, supplied in pellets like the mina formulation and optimized for operating in
HTS catalyst, consists of 40 55 % copper ox- a wider temperature range than the standard LTS
ide, 20 30 % zinc oxide, the balance being catalyst. The reaction heat can be removed by use
alumina. The catalyst properties are influenced of a tube-cooled reactor raising steam or heating
far more by the formulation and manufacturing water for gas saturation to supply process steam
procedure [472] than by its chemical composi- in the reforming section (Linde LAC, ICI Catalco
tion. The copper oxide is reduced in situ with LCA). In a new plant using the spiral-wound
hydrogen and a carrier gas (usually nitrogen) to Linde reactor [476], a methane slip of only
form fine copper crystallites on which the activity 0.7 mol % (dry basis) is achieved. Further puri-
depends. Sulfur, usually present as H2S, has to be fication is performed by PSA. Generally the shift
below 0.1 ppm, but even with such low concen- conversion reactors have an axial gas flow
trations, the catalyst is slowly poisoned. The ZnO pattern, but recently radial gas flow configura-
adsorbs the sulfur and it finally transforms into tions have been chosen in some instances.
Additional literature on shift conversion can upstream of gasification to avoid poisoning of the
be found in [331333, 343, 344, 461, 463468, sensitive reforming catalysts. This is usually
329, 841]. performed by hydrodesulfurization and adsorp-
tion of the H2S by ZnO. As this is an essential part
Shift Conversion in Partial Oxidation of the steam reforming process it is treated in
Plants. The raw synthesis gases from partial Section 6.1.1.
oxidation of heavy hydrocarbons and coal differ The classical method for CO2 removal is to
mainly in two aspects from that produced from scrub the CO2 containing synthesis gas under
light hydrocarbons by steam reforming. First, pressure with a solvent capable of dissolving
depending on the feedstock composition, the gas carbon dioxide in sufficient quantity and at
may contain a rather high amount of sulfur sufficient rate, usually in countercurrent in a
compounds (mainly H2S with smaller quantities column equipped with trays or packings. The
of COS); second, the CO content is much higher, CO2-laden solvent is flashed, often in steps, to
in some cases in excess of 50 %. The sulfur around atmospheric pressure, and the spent
compounds (see Section 6.1.3) can be removed scrubbing liquid is subsequently heated and
ahead of the shift conversion to give a sulfur-free regenerated in a stripping column before being
gas suitable for the classical iron HTS catalyst. In recycled to the pressurized absorption column.
another process variant the sulfur compounds are In the early days of ammonia production water,
removed after shift conversion, which thus has to often river water, served as solvent in a once-
deal with a high-sulfur gas. As the standard iron through process without regeneration and
catalyst can tolerate only a limited amount of recycling.
sulfur compounds, the so-called dirty shift cata- Today a variety of solvents are used and they
lyst is used in this case. This cobalt molybde- can be categorized as physical or chemical
num alumina catalyst [342, 343, 479481, 563] solvents. In the physical solvents the carbon
is present under reaction conditions in sulfidized dioxide dissolves without forming a chemical
form and requires for its performance a sulfur compound, and this allows recovery simply by
content in the gas in excess of 1 g S/m3. Reaction flashing. In the chemical solvents the carbon
temperatures are between 230 and 500 C. dioxide becomes fixed as a chemical compound,
Irrespective of the catalyst type used, the high which needs heat for its decomposition. At low
initial carbon monoxide concentration means carbon dioxide partial pressures, the chemical
that the reaction must generally be performed in solvents absorb substantially more carbon diox-
steps, with intermediate cooling. It has been ide than the physical solvents; at higher partial
reported that the CO content can be reduced from pressures the physical solvents (according to
50 to 0.8 % in a single step in a large hydrogen Henrys Law, the loading is approximately
plant by using a quasi-isothermal reactor (e.g., proportional to the CO2 partial pressure) have
the Linde spiral-wound reactor). a higher loading capacity than the chemical
solvents, for which the solubility approaches
a saturation value. Figure 27 shows the loading
6.1.3. Gas Purification characteristic for various solvents.
In further purification, carbon dioxide, residual

carbon monoxide, and sulfur compounds (only
present in the synthesis gas from partial oxida-
tion) have to be removed as they are not only a
useless ballast but above all poisons for the
ammonia synthesis catalyst.
The total sulfur contained in the coal and
hydrocarbon feedstock is converted in gasifica-
tion to H2S and a smaller amount of COS, which
are removed as described below. In contrast
steam reforming requires removal of sulfur from
the natural gas and light hydrocarbon feedstocks Figure 27. CO2 loading characteristics of various solvents
As both sour gases, CO2 and H2S, have good allow a higher loading of the solvent. The energy
solubility in the applied solvents, special process consumption of the modern systems, as shown in
configurations are required for partial oxidation the last two lines of Table 15 depends largely on
gases to recover separately a pure CO2 fraction process configuration and required final purity
and an H2S-rich fraction suitable for sulfur which may range from 50 to 1000 ppm in the
disposal. purified gas. There is also a trade-off between
Very suitable for the partial pressure range of energy consumption and investment costs.
CO2 in steam reforming plants (4 7 bar) are The hot potash systems, for example, the
chemical solvents based on aqueous solutions of Benfield process licensed by UOP, differ in the
potassium carbonate or alkanolamines contain- type of activator used to increase the reaction rate
ing additional activators to enhance mass transfer between the CO2 and the solvent. The activators
and, in some cases, inhibitors to limit or prevent enhance mass transfer and thus influence not only
corrosion processes. Primary and secondary the regeneration energy demand (circulation rate
amines, for example, monoethanolamine (MEA) of the solvent) but also the equipment dimen-
and diethanolamine (DEA) exhibit a high mass- sions. The following activators are used: in Ben-
transfer rate for carbon dioxide but have a high field [492495] and Carsol [496, 497] process
energy demand for regeneration. For this reason ethanolamines; in the Giammarco Vetrocoke
tertiary amines are commonly used today, for process glycine (originally arsenic oxide)
example, methyldiethanolamine together with an [500503]; in the Catacarb system [490, 491]
activator. Triethanolamine does not achieve the amine borate; in the Exxon Flexsorb HP process
required final CO2 concentration, and in the few [498, 499] a sterically hindered amine; in the
cases where it was used it was followed by Carbosolvan process [505, 509] sulfosolvan B.
additional scrubbing with monoethanolamine New activators named ACT-1 (UOP) [510, 511]
(MEA). and LRS-10 [512, 513] (British Gas) have been
The potassium carbonate processes from the introduced. All hot potash systems need corro-
various licensors differ with respect to the acti- sion inhibitors the concentration of which must
vator, corrosion inhibitor and to some extent in carefully to be monitored.
the process configuration. A typical example of an efficient modern hot
Over the years considerable progress has potash system is the Benfield LoHeat [514] sys-
been achieved in improving the efficiency of the tem of UOP. The high thermal efficiency of this
carbon dioxide removal systems. The first gen- two-stage adsorption process using lean and
eration of single-train steam reforming ammonia semi-lean solvent is achieved by recompression
plants used MEA and consumed about 5.8 GJ per of the flash steam with an injector or a mechanical
tonne NH3, which was about 14 % of the total vapor compressor. UOP has also developed a
energy consumption. Table 15 demonstrates the number of other process configurations [498,
progress made in energy consumption. 509, 515, 516, 837].
The first progress was made by addition of BASFs aMDEA [517523] process uses an
corrosion inhibitors (e.g., Amine Guard intro- aqueous solution of the tertiary amine methyl-
duced by Union Carbide) [528, 559562], which diethanolamine (MDEA) with a special amine
activator. No corrosion inhibitors are necessary,
Table 15. Heat requirements for regeneration in CO2 removal systems and unlike MEA no solvent degradation is ob-
[331, 528] served, so recovery installations are not required.
Owing to the low vapor pressure of MDEA and
Process Heat requirement,
kJ/mol CO2
the activator, there are no losses of the active
solvent components. The carbon dioxide binds
MEA (without Amine Guard) 209 much less strongly to MDEA than to MEA, and
MEA (with Amine Guard III) 116 the solvent character is more like a hybrid be-
Benfield hot potash (1-stage)a 88
BASF aMDEA process (1-stage)a 73 tween a strong chemical and a purely physical
Benfield LoHeat 28 35 solvent. On account of the relative weak binding
BASF aMDEA process (2-stage)a 28 30 forces, a substantial amount of carbon dioxide
a
Single-stage regeneration. can be recovered simply by flashing to low
b
Two-stage regeneration. pressure, and only a small amount has to be
recovered by stripping. The process is very ery in the regeneration stage is only partially
versatile: increasing the activator concentration possible (only pure CO2 can be obtained along
shifts the character of the solvent more to the with a CO2 fraction more or less rich in H2S) two
chemical side and vice versa, and process con- principal plant flowsheets are possible. In one, a
figurations include two- and single-stage first scrubbing stage, which removes the sulfur
designs, the latter allowing old MEA units to be compounds, is positioned upstream of the shift
revamped [524526] simply by swapping the conversion. The second stage, removing pure
solvent without changing the process equipment. CO2, is located downstream of the shift reactors.
Physical solvent based processes can also be This concept reduces the effort required to
applied in steam reforming ammonia plants. The receive a highly concentrated H2S fraction suit-
Selexol process (UOP) [490, 530538] uses able for further processing in a Claus plant or a
polyethylene glycol dimethyl ether, the Sepasolv sulfuric acid plant. In the other arrangement, the
MPE process (BASF) [490, 518]polyethylene sour gases are removed after shift conversion,
glycol methyl isopropyl ether, and the Fluor which in this case has to operate over dirty shift
Solvent Process [539542] polypropylene car- catalyst (see Section 6.1.2) with the consequence
bonate. These solvents are stable, noncorrosive, that the H2S is diluted by a large amount of CO2.
nontoxic, and not very volatile, but they have a In this case, too, methanol regeneration in
rather high capacity for adsorbing water. For this the Rectisol process can be tailored to achieve
reason the raw gas has to be dry, which is usually a H2S-rich fraction for downstream processing
achieved by chilling and operating at low tem- and pure CO2, a task difficult to fulfil with the
peratures. The Selexol Process for example op- other physical solvents mentioned.
erates at 5 C. The carbon dioxide is recovered Extensive surveys and additional literature of
simply by flashing; no heat is necessary. Before the CO2 removal processes are found in [489,
the solvent is recycled it has to be vacuum treated 527, 528, 548558, 853, 854, 871] a theoretical
and/or air stripped to remove traces of carbon analysis is given in [487].
dioxide. When comparing the energy consump-
tion of physical and chemical solvent based Final Purification. After bulk removal of
processes for a given application not only the the carbon oxides has been accomplished by shift
heat for solvent regeneration but also the me- reaction and CO2 removal, the typical synthesis
chanical energy for solvent circulation has to be gas still contains 0.2 0.5 vol % CO and
taken into account. 0.005 0.2 vol % CO2. These compounds and
Raw synthesis gas produced by partial oxida- any water present have to be removed down to a
tion has a carbon dioxide partial pressure be- very low ppm level, as all oxygen-containing
tween 10 and 30 bar, depending mainly on feed- substances are poisons for the ammonia synthesis
stock and gasification pressure. In the lower half catalyst [565].
of this partial pressure range chemical solvents
based on tertiary amines (e.g., MDEA) might be Methanation. Methanation is the simplest
suitable, but at higher values physical solvents method to reduce the concentrations of the car-
become increasingly preferable. Examples of bon oxides well below 10 ppm and is widely used
physical solvent processes are Selexol Process, in steam reforming plants. It is actually the
Sepasolv MPE process, Lurgi Purisol Process (N- reverse reaction of steam reforming of methane:
methylpyrrolidone) [506508], Sulfinol process
CO3 H2
CH4 H2 O DH 206 kJ=mol 24
(tetrahydrothiophene-1,1-dioxide diisopropa-
nol) [504, 529], and, probably the most important and
in this connection, the Rectisol process (Linde
CO2 4 H2
CH4 2 H2 O DH 165 kJ=mol 25
and Lurgi) [490, 543547, 871], with methanol
as solvent operating at 15 to 40 C. The advantages of simplicity and low cost
The presence of sulfur compounds, mainly more than outweigh the disadvantages of hydro-
H2S along with a minor quantity of COS, intro- gen consumption and production of additional
duces some complications for CO2 removal from inerts in the make-up gas to the synthesis loop.
partial oxidation gases. Since the sour gases are The reaction is carried out over a supported
both soluble in the solvents and a separate recov- nickel catalyst at a pressure of 25 35 bar and a
temperature of 250 350 C. The required cat- methanation unit must follow the methanolation
alyst volume is relatively small. If a breakthrough section.
of carbon monoxide from the low-temperature
shift or carbon dioxide from the absorption sys- Dryers. It is energetically advantageous to
tem occurs, the intensely exothermic methana- add the purified synthesis gas at a point in the
tion reaction can reach temperatures exceeding synthesis loop where it can flow directly to the
500 C very quickly [566]. For example, 1 % synthesis converter (see Section 6.3.1). For this
CO2 breakthrough leads to an adiabatic temper- reason water and traces of carbon dioxide must be
ature rise of 60 C. Controls should be installed removed from the make-up gas downstream of
and other security measures taken to avoid these methanation. This is accomplished by passing
high temperatures because the catalyst may be the make-up gas through molecular sieve
damaged or the maximum allowable operating adsorbers.
temperature of the pressure vessel wall
exceeded. Cryogenic Methods are usually used for final
Methanation as final purification for the raw purification of partial oxidation gases, but may be
gas from partial oxidation was proposed by also incorporated in steam reforming plants. A
Topse [567]. In this case the shift conversion prominent example is the Braun Purifier process
is carried out in two stages with a special sulfur- [382, 574580].
tolerant shift catalyst followed by removal of The purifier is a cryogenic unit placed down-
hydrogen sulfide and carbon dioxide in an acid stream of the methanator and its duty is to remove
gas removal unit. Because of the potential danger the nitrogen surplus introduced by the excess of
of a sulfur break-through causing poisoning, the air used in the secondary reformer of the Braun
normal copper zinc alumina catalyst is usu- ammonia process (! Ammonia, 3. Production
ally not applied, which is surprising as the same Plants, Section 1.1.4.2). Additionally the inert
risk exists in partial oxidation based methanol level in the synthesis loop is reduced through this
plants for the similarly composed methanol unit because methane is completely and argon is
catalyst. partially removed from the make-up gas. Anoth-
er advantage of the process is that it separates the
Selectoxo Process. The Selectoxo process front-end and the synthesis loop, permitting the
(Engelhard) reduces the hydrogen consumption H/N ratio in the synthesis loop to be set indepen-
of the methanation system, as well as the inert gas dent of the secondary reformer. The purifier is a
content of the purified synthesis gas fed to the relatively simple unit composed of feed/effluent
synthesis loop. After low-temperature shift con- exchanger, a rectifier column with an integrated
version, the cooled raw gas is mixed with the condenser and turbo-expander. At 185 C
stoichiometric quantity of air or oxygen needed methane and argon are washed out. The cooling
to convert the carbon monoxide to carbon diox- energy is supplied by expansion of the raw gas
ide. The mixture is then passed through a pre- over the turbo-expander (pressure loss about
cious-metal catalyst at 40 135 C to accom- 2 bar) and expanding the removed waste gas to
plish this selective oxidation [568571]. The the pressure level of the reformer fuel.
carbon dioxide formed by the Selectoxo reaction
adds only slightly to the load on the downstream Liquid Nitrogen Wash [581583]. Normal-
carbon dioxide absorption system. ly, for the partial oxidation processes, only a
high-temperature shift conversion is used. This
Methanolation [572, 573] has been pro- results in a carbon monoxide content of the gas
posed for partially replacing methanation. It after shift conversion in the range 3 5 vol %.
converts the residual carbon oxides to methanol, Copper liquor scrubbing for carbon monoxide
preferably at higher pressure in an intermediate removal, commonly employed in early plants,
stage of synthesis gas compression. Methanol is has become obsolete and is now operated in only
removed from the gas by water scrubbing. The a few installations. Not only does it have a high
methanol may be recycled to the steam reformer energy demand, but it is also environmentally
feed or recovered as product. As full conversion undesirable because of copper-containing waste-
of the carbon oxides is not achieved, a clean up water. Liquid nitrogen wash delivers a gas to the
synthesis loop that is free of all impurities, the excess nitrogen introduced with the process
including inert gases and is also the means for air fed to the secondary reformer, e.g. the LCA
adding some or all of the nitrogen required for Process of ICI (page 97). Since this technology
synthesis. has proven its reliability in rather large hydrogen
The nitrogen is liquefied in a refrigeration plants for refineries it is now also used for world-
cycle by compression, cooling, and expansion. scale ammonia plants, e.g., the Linde LAC
It flows to the top of a wash column, where it process (page 99).
countercurrently contacts precooled synthesis
gas from which most of the methane and hydro-
carbons have been condensed. All of the cold 6.2. Compression
equipment is installed in an insulated cold
box. The wash column temperature is about Up to the mid-1960s reciprocating compressors
190 C. Liquid nitrogen wash systems are in were used to compress the synthesis gas to the
operation at pressures up to 8 MPa correspond- level of the synthesis loop, which was around
ing to the highest gasification pressures. Careful 300 bar in the majority of the plants at that time.
surveillance of the inlet gases is required. Water Higher pressures were used in a few installations,
and carbon dioxide in the inlet gas will freeze, for example, in Claude and Casale units. Prior to
causing operating difficulties. Traces of nitric about 1950 gas generation processes and shift
oxide (NO) may react with olefinic hydrocar- conversion operated at essentially atmospheric
bons, causing explosions [584, 585]. pressure. The gas was first compressed to the
Normally, an air separation plant is installed level of the CO2 removal section (usually 25 bar)
in conjunction with liquid nitrogen wash for and afterwards to around 300 bar for final purifi-
economy in operation. In modern plants, the air cation (at that time usually copper liquor scrub-
separation and the nitrogen wash frequently are bing) and synthesis. Reciprocating compressors
closely integrated with one another so that econ- with as many as seven stages in linear arrange-
omies can be realized in the refrigeration system. ment with intermediate cooling were used,
whereby the CO2 removal section was usually
Pressure Swing Adsorption. This process installed between the 3rd and 4th stages. Ma-
can be used to replace the LT shift conversion, chines with a suction volume up to 15 000 m3
carbon dioxide removal, methanation, and even (STP) for the first stage were not uncommon.
the secondary reformer as well [331, 552, Huge flywheels were designed as the rotors of
586589]. It uses molecular sieves as adsor- synchronous motors (ca. 125 rpm) with two
bents in a series of vessels operated in a stag- crankshafts on both sides connected over cross-
gered cyclic mode changing between an adsorp- heads with the piston rod for the horizontally
tion phase and various stages of regeneration. arranged stages. In some instances gas engines
The regeneration of the loaded adsorbent is were used as drivers.
achieved by stepwise depressurization and by The rapid technical progress in the hydrocar-
using the gas from this operation to flush other bon based technologies of steam reforming and
adsorbers at a different pressure level in the partial oxidation made it possible to generate the
regeneration cycle. The hydrogen recovery may synthesis gas at a pressure level sufficient for the
be as high as 90 % depending on the number of CO2 removal operation. As gasification proceeds
adsorbers in one line, which may be as high as with a considerable volume increase and feed-
10. Very high purity can be obtained, with about stocks such as natural gas are usually already
50 ppm argon and less than 10 ppm of other available under pressure at battery limits, con-
impurities. siderable savings in compression energy are
The process scheme for the ammonia plant achieved in this way.
may consist of production of pure hydrogen Along with the introduction of pressure gasi-
followed by separate addition of pure nitrogen fication, horizontally balanced compressors in
from an air separation unit [590592]. In a spe- which the cylinders are in parallel configuration
cial version the nitrogen can be added in the PSA on both sides of a common crankshaft became
unit itself to increase hydrogen recovery the preferred design. In these machines a good
[593596]. In some processes it may also remove dynamic balance can readily be achieved, higher
speeds are possible and also the use of asynchro- sive pressure losses would occur within the pas-
nous motors is possible. The low height of the sage and in the diffusers between the impellers,
arrangement has less severe requirements for rendering the machine extremely ineffective.
foundations, allows simpler piping connections The first single-train ammonia plants with a
and facilitates maintenance. When gas engine capacity of 550 600 t/d had to lower the syn-
drivers (two-stroke type) were used instead of thesis pressure to 145 150 bar to meet the
electric motors, some designs applied a common required minimum gas flow condition. Today,
crankshaft for the piston rods of the gas machine with improved manufacturing techniques, the
cylinders and compressor cylinders. In a very few minimum gas flow from the last wheel is 350 m3
cases steam turbines with special speed reduction for synthesis gas with a molecular mass of about
gears have been used. In smaller plants, the 9 and an efficiency of around 75 %. This corre-
various compression services, e.g., natural gas, sponds to a capacity of 400 t/d at 145 bar. As
process air, and synthesis gas compression, were newer synthesis catalysts allow a pressure of
apportioned among the crankshaft throws in such 80 bar in the synthesis loop (ICIs LCA Process,
a manner that a single compressor can perform all Kelloggs KAAP) a centrifugal compressor
compression duties [597]. Further information could be used down to 220 t/d. Of course, for
on reciprocating compressors is given in [598, todays world-scale capacities of 1200
599, 602, 603]. 2000 t/d these technical limitations have no
One of the most important features of the influence on the synthesis pressure, which even
energy integrated single-stream steam reform- for plants with 1800 t/d is between 155 and
ing ammonia plant pioneered by M. W. Kellogg 190 bar [329, 331, 600, 601, 604].
in 1963 was the use of centrifugal compressors The tensile strength of the steels normally
for the compression duties of synthesis gas and used to manufacture the compressor impellers
recycle, process air, and refrigeration. From this allow a maximum wheel tip speed of about
time onwards application of centrifugal com- 330 m/s, which limits the pressure increase
pressors became standard practice in most attainable by each impeller. A pressure increase,
ammonia plants irrespective of the synthesis for example, from 25 to 200 bar would require
gas generation technology. The fundamental 18 20 impellers. However, a compressor shaft
advantage of these machines are low investment must have sufficient rigidity to avoid excessive
(single machines even for very large capacities) vibration, and this limits the possible length
and maintenance cost, less frequent shutdowns such that a compressor shaft cannot accommo-
for preventive maintenance, and high reliability date more than eight or nine impellers. It is
(low failure rate) [830]. In most cases the cen- therefore necessary to arrange several compres-
trifugal compressors in ammonia plants are sor casings in series, with compression ratios
directly driven by steam turbines. This avoids from 1.8 to 3.2.
the losses associated with generation and trans- To overcome the pressure drop (5 20 bar) in
mission of electric power. For this reason the the synthesis loop re-compression of the recycle
overall efficiency of a plant with steam-driven gas is required. In practically all modern ammo-
centrifugal compressors is superior, although nia plants, the shaft of the final casing also bears
the centrifugal compressors are inherently less the impeller for the compression of the recycle
efficient than reciprocating units. A further ad- gas. Depending on synthesis configuration, mix-
vantage is that centrifugal compressors require ing of make-up gas and recycle can be performed
only a fraction of the space needed for recipro- inside the casing or outside (three or four-nozzle
cating compressors. arrangement; Fig. 30).
Manufacturing capabilities limit the mini- In older plants which used a reciprocating
mum possible passage width (today about compressor for the recycle, a recycle cylinder
2.8 mm) at the outer circumference of a centrif- was often mounted together with the other
ugal compressor impeller and this imposes a limit cylinders on the reciprocating frame. Sometimes
on the minimum effective gas volume leaving the special rotary compressors, so-called mole pumps
last impeller. Unless the total volumetric gas flow were also used, with the unique feature that
has a reasonable relationship to the passage width compressor and electric driver were completely
of the last impeller and the pressure ratio, exces- enclosed in a common high-pressure shell. In old
Figure 28. Centrifugal compressor for make-up and recycle gas compression of an ammonia plant (courtesy of Uhde)
a) Air cooler; b) Separator; c) Silencer; d) Water cooler
Casale plants, the make-up gas was introduced tion valve. Figure 29 is a schematic diagram of a
into the high pressure recycle loop and acted as liquid film shaft seal.
the driving fluid of an injector which compressed The seal oil pressure in the floating ring cavity
the recycle gas. must always be slightly higher than the gas
Today modern plant concepts for world-scale pressure within the casing which is provided by
capacity plants tend to limit the number of
compressor casings to two. Figure 28 shows an
example of the synthesis gas compressor of a
large ammonia plant.
Geared or metal diaphragm couplings are
used to connect the shafts of the individual
casings (two in Figure 28). These flexible cou-
plings prevent possible compressor damage re-
sulting from slight misalignment and shaft
displacement.
Sealing of the rotating shaft against the atmo-
sphere is an important and demanding task. The
high pressures and the high rotational speeds
involved do not allow mechanical contact shaft
seals. Usually, liquid-film shaft seals with cylin-
drical bushings (floating rings) are applied [605].
In this concept, an oil film between the shaft and a
floating ring, capable of rotation, provides the
actual sealing. The floating ring is usually sealed
to the compressor casing by O-rings. Seal oil
flows between both halves of the floating ring. Figure 29. Liquid film shaft seal with cylindrical bushing for
Part of the oil returns to the reservoir, while the a high-pressure centrifugal compressor
a) Shaft; b) Bearing; c) Pressure side; d) Ambient side;
remainder flows against the gas pressure into a e) Floating seal rings; f) Seal oil surge vessel; g) Seal oil;
small chamber from which, together with a small h) Lube oil; i) Drain to gas oil separator; k) Drain to lube oil
quantity of gas, it is withdrawn through a reduc- tank; l) Elevation for seal oil head
static height difference of the oil level in the there is no contact between oil and gas, which
elevated oil buffer vessel. In this way normally eliminates an emission source.
no oil should enter into the synthesis gas. As the A new development, already in commercial
labyrinth section on the pressure side is con- service, but so far not used in ammonia plants, is
nected with the suction side through an equaliz- magnetic bearings [606, 609]. Magnetic bear-
ing line, it is necessary to seal the compressor ings promise a wider temperature range, are less
shaft towards the atmosphere only at suction prone to wear, are less prone to developing
pressure level. vibrations due to imbalance and require less
Often, seal oil supply is combined with the maintenance. A combination of magnetic bear-
lubricating oil system, with oil reservoir, filters ings and dry seals (dry/dry) could totally elimi-
and (in part) pumps in common. nate the oil system.
The high rotational speeds and the relatively Integrated geared centrifugal compressors
large masses of the compressor rotors place high developed by DEMAG and GHH are a new
demands on the performance of the bearings. development which might become of interest
This is especially true for the thrust bearings, for plants of smaller capacity operating at lower
which must withstand high thrust forces. The pressure. The driver (e.g., a steam turbine)
minimum clearances necessary at the labyrinths drives a common gear to which the individual
and the impellers allow practically zero wear. compression stages are connected. Each stage
Any wear resulting in friction could lead in- has a single impeller which runs with very high
stantly to severe damage. For these reasons, in speed, for example, 25 000 rpm or higher.
addition to measuring bearing temperatures, the Compressors with three or four stages are in
axial position of the rotor and the radial vibra- operation, for example, a methanol synthesis
tional deflections are continuously monitored compressor for 75 000 m3/h and a pressure of
by sensors. An increased vibrational amplitude 75 bar. It is likely that this concept can be
is often an early indication of mechanical faults, extended to a final pressure of 120 bar with
such as rotor imbalance, bearing damage, ammonia synthesis gas.
occurrence of friction, or misalignment. Compressor control is achieved basically by
An interesting concept is dry (oil-less) gas controlling the rotational speed of the driver, in
seals for centrifugal compressors. Develop- modern plants often with the help of a distributed
ment dates back to 1969 and the first commer- control system (DCS). If the volumetric flows
cial application was in a natural-gas compres- through the machine at start-up or during reduced
sor in 1973. Since then they have been widely load operation deviate too far from the design
used in off-shore service [606608]. Only re- values, it is necessary to re-circulate gas through
cently have they gained acceptance in the individual stages or through the whole machine.
ammonia industry, where several compressors Otherwise the compressor can enter a state of
for synthesis gas and refrigeration duty pulsating flow, called surge, which could cause
equipped with dry seals have been successfully damage. Anti-surge control (minimum by-pass
placed in service. Nitrogen is used as an inert control, kickback control) is designed to prevent
fluid for the seal, which is achieved at the radial this condition, as well as to minimize the inci-
interface of rotating and stationary rings. dence and degree of uneconomical re-circula-
During operation the seal is not completely tion. A point of discussion is sometimes the
tight; some of the seal gas flows back to the minimum load at which the compressor can run
suction side to be re-compressed, and a small without kickback, which means without loss of
amount from the suction side may go to the efficiency. Usually a load of 75 % is possible,
atmospheric side and is sent to the flare on and with special impeller design, the value may
account of its content of combustibles. During be lowered to 70 % but with a slight sacrifice of
stops, when the shaft is not rotating, the seal full-load efficiency.
ring is pressed tight against the seat by means Other compression duties in the plants, such
of a spring and the differential gas pressure. as process air in steam reforming plants and air,
Dry gas seals in combination with oil-lubricat- and oxygen, and nitrogen compression in partial
ed bearings (dry/wet) have the advantage that a oxidation plants, are also performed by centrif-
much smaller oil system is required and that ugal compressors. Also for the ammonia
compression in the refrigeration section centrif- synthesis gas and recycled to the converter. The
ugal compressors are normally in service. In concentration of the inert gases (methane and
some cases screw compressors have been used argon) in the synthesis loop is controlled by
for this duty on account of their good efficiency withdrawing a small continuous purge gas
and load flexibility, which is of interest in plants stream. These basic features together with the
where the ammonia product is split between properties of the synthesis catalyst and mechani-
direct users at the site and cold storage in cal restrictions govern the design of the ammonia
changing ratios. synthesis converter and the layout of the synthe-
Criteria for compressor selection and eco- sis loop. Evaluation criteria are energy consump-
nomic comparisons are discussed in [610617, tion, investment and reliability.
629]. Additional information is given in
[618628].
In modern plants the synthesis gas compres- 6.3.1. Synthesis Loop Configurations
sors, including recycle, are almost exclusively
driven by a steam turbines. These are generally A number of different configurations are possible
extraction turbines with a condensing section. for the synthesis loop. They can be classified
Steam is extracted at suitable pressure levels (e.g. according to the location of ammonia condensa-
45 55 bar) to provide, for example, the process tion and the point at which the make-up gas is
steam in steam reforming plants, and for other introduced. Figure 30 shows the principal
drivers, e.g., air compressor, ammonia compres- possibilities.
sor, boiler feed water pumps, and blowers. If the make-up gas is absolutely free of cata-
As failures and breakdowns of these large lyst poisons, such as water and carbon dioxide
rotary machines could lead to long and expensive (for example, after molecular sieve dehydration
repairs and to a corresponding loss of production or liquid nitrogen wash), it can be fed directly to
it is advisable to keep the essential spare parts, for the synthesis converter (Fig. 30 A). After the gas
example, spare rotors, in stock. In older steam leaves the synthesis converter, ammonia is con-
turbines, sometimes blade failures occurred, but densed by cooling and the recycle gas is referred
this is no longer a problem due to improved blade to the recycle compressor. This represents the
design and shroud bands, which are standard most favorable arrangement from a minimum
today. energy point of view. It results in the lowest
Gas turbines have also been used as drivers for ammonia content at the entrance to the converter
compressors in ammonia plants. The exhaust and the highest ammonia concentration for
may be used for steam production, for preheating condensation.
duties, or as combustion air in the primary re- When the make-up gas contains water or
former [630634]. carbon dioxide, advantage is taken of the fact
that these materials are absorbed completely by
condensing ammonia. This requires that the con-
6.3. Ammonia Synthesis densation stage be located partially or wholly
between the make-up gas supply point and the
Under the conditions practical for an industrial converter. This arrangement has the disadvan-
process ammonia formation from hydrogen and tage that the ammonia concentration for conden-
nitrogen sation is reduced by dilution with the make-up
gas. Also, at equal condensing temperature, a
N2 3 H2
2 NH3 DH 92:44 kJ=mol
higher ammonia concentration exists at the inlet
is limited by the unfavorable position of the to the converter. Figure 30 B shows the simplest
thermodynamic equilibrium, so that only partial such configuration. An additional drawback of
conversion of the synthesis gas (25 35 %) can this arrangement is that all the ammonia pro-
be attained on its passage through the catalyst. duced must be compressed with the recycle gas in
Ammonia is separated from the unreacted gas the recycle compressor.
by condensation, which requires relatively low The scheme shown in Figure 30 C, the fre-
temperatures for reasonable efficiency. The quently used four-nozzle compressor, avoids
unconverted gas is supplemented with fresh this waste of energy. With this arrangement,
Figure 30. Schematic flow diagrams of typical ammonia synthesis loops

A) Synthesis loop for pure and dry make-up gas; B) Product recovery after recycle compression; C) Product recovery before
recycle compression (four-nozzle compressor design); D) Two stages of product condensation
a) Ammonia converter with heat exchangers; b) Ammonia recovery by chilling and condensation; c) Ammonia recovery by
condensation at ambient temperature; d) Synthesis gas compressor; e) Recycle compressor
recycle compression follows directly after con- 6.3.2. Formation of Ammonia in the
densing and separating the ammonia. In this Converter
configuration, it is possible to cool the recycle
gas using cooling water or air immediately before The central part of the synthesis system is the
admixing the make-up gas (i.e., before diluting converter, in which the conversion of synthesis
the recycle gas) and thereby to reduce the energy gas to ammonia takes place. Converter perfor-
expenditure for refrigerated cooling. mance is determined by the reaction rate, which
Splitting the cooling step for ammonia con- depends on the operating variables (cf. Section
densation also offers advantages when the recy- 4.3). The effect of these parameters is discussed
cle gas is compressed together with the make-up briefly in the following.
gas. This applies especially at synthesis pressures With increasing pressure, ammonia forma-
above about 25 MPa (250 bar). At these pres- tion increases (Fig. 31). This results not only
sures, a greater portion of the ammonia formed from the more favorable equilibrium situation
can be liquefied by cooling with cooling water or for the reaction, but also from the effect on the
air (see Fig. 30D). reaction rate itself. In industrial practice, there
When ammonia-containing recycle gas and are plants that operate at about 8 MPa (80 bar),
carbon dioxide containing make-up gas mix to- but there are also those that operate at more than
gether under certain conditions of concentration 40 MPa (400 bar). Today, plants are built main-
and temperature, precipitation of solid ammoni- ly for synthesis pressures of 150 250 bar.
um carbamate can result. Typical operating parameters for modern
In recent years, also as a retrofit in existing synthesis loops with different pressures are
plants, molecular sieve drying of make-up gas listed in Table 16.
has increasingly been applied in order to realize Converter performance decreases with in-
the energy-saving arrangement of the synthesis creasing inert gas content (Fig. 32). The usual
loop corresponding to Figure 30 A. range is 0 15 vol %. For a secondary loop
Figure 31. Performance for a four-bed quench converter as a Figure 32. Performance of a converter as a function of inlet
function of operating pressure with space velocity (per hour) inert gas (CH4 and Ar) content with space velocity (per hour)
as parameter; 10 % inerts in the inlet synthesis gas as parameter, inlet NH3 content is 3.5 %; 30 MPa pressure;
catalyst particle size is 6 10 mm
based on purge gas, it can be 30 % or more (see
Section 6.3.5).
Converter performance also diminishes
(Fig. 33) with increasing oxygen content of the
synthesis gas. Today, a level of 10 ppm in the
make-up gas, corresponding to about 3 ppm in
the converter inlet gas, is usually, not exceeded
(cf. Section 5.1.5).
In contrast to the above-mentioned variables,
the dependence of the converter performance on
the H2 /N2 ratio shows a true maximum (Fig. 34).
The optimum conversion at high space velocity
[SV m3 (STP) gas h1 m3 catalyst] lies
close to an H2 /N2 ratio of 2 and approaches 3
at low space velocities. The reason is that equi-
librium plays a greater role at low space veloci- Figure 33. Performance of a converter as a function of
ties and has a maximum at a ratio of 3, except for oxygen content (all oxygen-containing impurities) in the inlet
synthesis gas
small corrections [1] with regard to the behavior
of real gases. Usually, the ratio is adjusted to 3,
because in most plants, conversions near equi-
librium are attained.
In practice, space velocities vary from about
12 000 h1 at about 15 MPa (150 bar) to about
35 000 h1 at about 80 MPa (800 bar). Usually,
with increasing space velocity, the ammonia
Table 16. Typical operating parameters for modern synthesis loops at

140 and 220 bar (1000 t/d NH3) [329, p. 226]
Parameters Inlet pressure, bar

140 220
Inlet flow, Nm3/h 500 000 407 000
Inlet NH3 conc., mol % 4.1 3.8
Outlet NH3 conc., mol % 17.1 19.9
Inlet inert conc., mol % 8.0 12.0
Figure 34. Ammonia conversion as a function of hydrogen/
NH3 separator temperature, C 5 5
nitrogen ratios in the inlet synthesis gas with space velocity
Relative catalyst volume 1 0.6
(per hour) as parameter; 9.7 MPa pressure [832]
concentration in the effluent synthesis gas from a section of a converter. The first models the
given converter does indeed go down (Figs. 31 concentration position relationship for trans-
32, 34). However, the operating point normally formation of the reactants to products, i.e., the
chosen means that the increase in gas flow rate reaction kinetic equation (cf. Section 4.3). The
more than compensates for the reduced ammonia second handles the temperature position
concentration. Thus, a still higher ammonia pro- behavior of the reacting synthesis gas, the cata-
duction rate is achieved. Plant operation often lyst, and the vessel internals. The form of the
takes advantage of these phenomena. For exam- latter is characteristic of the type of converter.
ple, this characteristic can be used to maintain The temperature profile depends not only on the
ammonia production rate when the synthesis rate of reaction heat evolution but also on the
catalyst ages and its activity declines. Increasing method and nature of the system for removing
converter flow rate and declining synthesis cata- heat from the catalyst bed or beds. Additional
lyst activity can reach a point, even with careful equations describe the behavior of the separate
control, where the reaction blows out and feed effluent heat exchanger system
production ceases. This occurs when the heat of [638642]. General information on converter
reaction is no longer sufficient to provide the calculations are given in [52, 641643]. Com-
temperatures necessary for operation of the puter programs and applications can be found in
feed effluent heat exchanger. The heat ex- [644647]. For a discussion of modeling of
changer then fails to heat the cold converter feed different converter types, see [638642, 648,
gas to the required reaction ignition tempera- 649]. Models for multibed quench converters are
ture. Achieving maximum ammonia production described in [648655]. Tubular reactors are
requires operating in the neighborhood of this treated in [657664]. The individual effects
blow out point, in turn requiring very careful of the operational parameters are evaluated in
control [635637]. If the synthesis converter is to [1, 55, 656].
be operated in this region, then it is advisable to The reaction temperature profile is of particu-
oversize the converter feed effluent heat ex- lar importance because the reaction rate responds
changer system to attain a higher degree of vigorously to temperature changes. Figure 35
control stability. plots lines of constant reaction rate illustrating
its dependence on temperature and ammonia
Converter Design. Design of ammonia concentration in the reacting synthesis gas. The
synthesis reactors is not just the calculation of line for zero reaction rate corresponds to the
the required catalyst volume; other parameters temperature concentration dependence of
have to be considered, too, and for some of them the chemical equilibrium. From Figure 35 it is
optimum values have to be found. This raises the apparent that there is a definite temperature at
question of the definition of optimum. In the which the rate of reaction reaches a maximum for
early days with more strict material and fabrica- any given ammonia concentration. Curve (a)
tion-related limitations the converters were represents the temperature concentration locus
usually designed for minimum high-pressure of maximum reaction rates. To maintain maxi-
volume, and this meant maximum use of the mum reaction rate, the temperature must
catalyst. Today the objective is to optimize decrease as ammonia concentration increases.
the heat recovery (at the highest possible level) If the objective in design or operation were
and to minimize the investment for the total optimizing catalyst utilization, then Figure 35
synthesis loop. shows that the converter temperature compo-
The design of an ammonia converter is a sition profile should follow curve (a), which
demanding engineering and chemical engineer- corresponds to maximum reaction rate at all
ing task. To calculate the parameters for the points. It is also obvious that in reality this
design, including dimensions and number of ideal temperature concentration profile
catalyst beds, temperature profiles, gas composi- cannot be achieved. For example, a synthesis
tions, and pressure drop, a suitable mathematical gas with about 3 % ammonia concentration
model is required. entering the converter cannot be heated to the
Two differential equations describe mathe- ideal temperature by heat exchange because
matically the steady-state behavior of the reactor the very high temperature required does not exist
tion profile was often compared to the ideal for

optimum usage of high-pressure vessel and cata-
lyst volumes [656, 665].
Commercial Ammonia Converters.

Principal Reactor Configurations. Commer-
cial converters can be classified into two main
groups:
1. Internally cooled with cooling tubes running

through the catalyst bed or with catalyst
inside the tubes and the cooling medium on
the shell side. The cooling medium is mostly
the reactor feed gas, which can flow counter-
or cocurrently to the gas flow in the synthesis
catalyst volume (tube-cooled converters).
2. The catalyst volume is divided into several
beds in which the reaction proceeds adiabati-
cally. Between the individual catalyst beds
heat is removed by injection of colder syn-
thesis gas (quench converters) or by indirect
cooling with synthesis gas or via boiler feed
water heating or raising steam (indirectly
cooled multibed converters).
Figure 35. Nitrogen reaction rate v in m3 NH3 /(m3 The gas flow can have an axial, cross-flow or
catalyst s) as a function of temperature and ammonia con- radial flow pattern. The different cooling meth-
centration at 20 MPa pressure and 11 vol % inerts in the inlet ods can be combined in the same converter.
synthesis gas
a) Locus of temperatures resulting in maximum reaction rate
The severe conditions of high pressure, high
at a given ammonia concentration temperature, and high hydrogen partial pressures
place strict requirements on the construction
materials and design for both groups. For exam-
in the converter system. To reach the ideal ple, almost all converters consist of an outer
temperature, the first portion of the catalyst must pressure vessel containing a separate inner vessel
initially operate adiabatically. Consideration of housing the catalyst and other internals, such as
the service life of the catalyst requires that this gas distributors and heat exchangers. Relatively
maximum initial temperature not exceed that cool converter feed gas flows through the annular
recommended by the manufacturer, usually space between the outer pressure shell and the
530 C (cf. Section 5.1.4). Following this initial internal basket. This shields the outer shell
adiabatic temperature rise, it is possible to mini- from the high-temperature basket, permitting
mize the required catalyst volume by cooling the use of comparatively low-alloy chromium
reacting synthesis gas such that, as ammonia molybdenum steels for its construction. Often,
formation progresses, the temperature follows part of the converter feed effluent heat-
curve (a). In the days when converters were exchange system surface is placed within the
designed to operate at very high pressures and converter pressure shell. By this means, the
temperatures and before the advent of improved nozzle penetration through the pressure shell
construction materials, the converter design for the converter effluent gas is also maintained
represented a real limitation on plant capacity. at relatively low temperature. Today, this latter
To maximize converter output and plant capacity feature is not always necessary; the state of the art
to achieve the most favorable overall manufactur- in converter construction materials now allows
ing cost, it was necessary to optimize catalyst design of exit nozzles for the maximum antici-
utilization. A converter temperature concentra- pated temperatures, i.e., up to about 530 C.
Figure 36. Countercurrent tube-cooled converter (TVA converter) [665]

A) Converter layout; a) Catalyst; b) Heat exchanger; c) Cooling tubes; d) Main gas inlet; e) Vessel wall cooling gas inlet;
f) Temperature control gas (cold-shot) inlet; g) Gas exit
B) Gas temperature profile through the converter; C) Ammonia concentration versus temperature (cf. Fig. 35)
References [670] and [671] review some litera- enters the cooling tubes that run through
ture on ammonia converters. the catalyst bed (Fig. 36 A). There it absorbs the
heat released in the reaction and reaches the
Tube-Cooled Converters. To remove the required reaction ignition temperature of about
heat evolved in the synthesis reaction, converters 400 C. The reaction begins almost adiabatically
have been designed in which cooling tubes run in the catalyst bed. As the reacting gas tempera-
through the catalyst bed. With these tubes, the ture rises, the temperature difference between the
heat is transferred to the converter feed gas to reacting gas and the cooling tubes increases,
heat it to the reaction ignition temperature or to resulting in increasing heat removal (Fig. 36 B).
an external cooling medium. The known designs As the reacting gas reaches the bottom of the
for such converters are suited only for small catalyst bed, the rate of reaction begins to de-
production capacities and therefore currently of crease sufficiently, because of high ammonia
limited interest. When designed to utilize the heat concentration, that cooling predominates and the
of reaction for heating the converter feed gas, temperature of the reacting gas begins to fall.
such converters have the further disadvantage Figure 36 C shows the converter temperature
that temperature control is sluggish and temper- concentration profile. The reaction temperature
ature oscillations dampen out very slowly, if at at first somewhat exceeds that for maximum
all, a phenomenon called hunting. reaction rate but eventually falls below curve (a).
Typical of such converters is the countercur- Cold converter feed gas can be admitted at a point
rent design of the Tennessee Valley Authority within the internal heat exchanger to control both
(TVA) [635, 662, 665, 674676, 682684]. Part the total system and reaction temperature profiles
of the feed gas to this unit enters the converter at through bypassing. Casale has employed a simi-
the top and flows down through the annular space lar converter design concept [685].
between the pressure shell and the basket. The Other tube-cooled converters with counter-
main gas flow enters the converter at the bottom current flow are the Mont Cenis reactor
and joins the shell cooling gas. The mixture is [666669], the original Haber Bosch reactors
heated to about 200 C in an internal exchanger [666], the Claude converter [484, 488], and the
located beneath the catalyst bed. The gas then older Fauser design [484]. These converters were
The Nitrogen Engineering Corporation

(NEC) converter applies cocurrent flow by
means of bayonet tubes [665, 674, 676683].
This design places maximum heat-exchange
temperature difference therefore, maximum
cooling performance at the catalyst bed inlet,
the point where maximum reaction rate there-
fore maximum rate of heat evolution is taking
place. The intent is to obtain closer approach to
curve (a) (cf. Fig. 38 C). Figure 38 A shows the
general arrangement of the converter, catalyst
bed, and heat exchanger; Figure 38 B, the tem-
perature profile of the system. Chemico, a deriv-
ative of NEC, continued to apply such converters
with only slight changes [685].
Ammonia Casale developed a new converter
concept which uses no tubes but arranged cool-
ing plates. The plates are radially immersed in
Figure 37. ICI tube-cooled ammonia converter
a) Top of catalyst bed; b) Cooling tubes; c) Catalyst;
the axial radial catalyst bed to remove the
reaction heat while it is formed. Figure 39
[879] shows the temperature profile of this pseu-
all used in relatively small plants and are now do-isothermal reactor. The profile follows the
obsolete. line of the maximum reaction rate to obtain the
An interesting rebirth of the countercurrent highest possible conversion per pass from a given
principle is the new ICI tube cooled converter catalyst volume. The use of plates allows a design
used in the LCA process (Fig. 37) [873]. without tubesheets and simplifies catalyst
Figure 38. Cocurrent-flow tube-cooled converter [665]

A) Converter; a) Catalyst; b) Heat exchanger; c) Cooling tubes; d) Gas inlet; e) Temperature control gas (cold-shot) inlet; f) Gas
exit
B) Gas temperature profile through the converter;
C) Ammonia concentration versus temperature (cf. Fig. 35)
Figure 39. Expected thermal profile of catalyst along the

converter and comparison with plant data [879]
loading and unloading and the use of small

size high active catalyst. The new Casale IAC
ammonia converter is suited for very high
capacities up to 4500 t/d for the the so-called
mega-ammonia plants presently in discussion.
The first commercial use of a converter of this
type is operating successfully in a 1050 stpd
(953 mtpd) plant in Trinidad [855]. In a recent
Casale company brochure the plate arrange-
ment is shown taking a methanol converter as
an example (Fig. 40).
Today, the great majority of synthesis con-
verters are designed with catalyst distributed in
several beds, within one or more reactor vessels.
In each bed, the synthesis gas reacts adiabati-
cally, and direct or indirect cooling is provided
between the catalyst beds for cooling the reacting Figure 40. Internals of a Casale isothermal converter (cour-
tesy of Ammonia Casale)
mixture from a temperature above to a value
below the ideal (curve (a), Fig. 41).
Multibed Reactors with Direct Cooling subsequent beds. In this way the reaction profile
(Quench Converters). In quench converters describes a zig-zag path around the maximum
cooling is effected by injection of cooler, uncon- reaction rate line. A schematic drawing of a
verted synthesis gas (cold shot) between the quench converter together with its temperature/
catalyst beds. The catalyst beds may be separated location and temperature/ammonia concentra-
by grids designed as mixing devices for main gas tion profiles is presented in Figure 41.
flow and cold shot, or be just defined by the A disadvantage is that not all of the recycle
location of cold gas injection tubes as for exam- gas passes over the entire catalyst volume so that
ple in the ICI lozenge converter. considerable ammonia formation occurs at
In this type of converter only a fraction of the higher ammonia concentration and therefore at
recycle gas enters the first catalyst layer at about lower reaction rate. Therefore a higher catalyst
400 C. The catalyst volume of the bed is chosen volume is needed compared to an indirectly
so that the gas leaves it at ca. 500 C (catalyst cooled multibed converter. However, no extra
suppliers specify a maximum catalyst tempera- space is required for interbed heat exchangers,
ture of 530 C). Before it enters the next catalyst so that the total volume of the high-pressure
bed, the gas is quenched by injection of cooler vessel will remain about the same as that for the
(125 200 C) recycle gas. The same is done in indirectly cooled variant [700].
Figure 41. Multibed converter with quench cooling [833]

A) Converter; a) Catalyst; b) Heat exchanger; c) Quench gas inlets; d) Gas inlet; e) Gas exit
As the quench concept was well suited to large divided into several zones (usually four) by
capacity converters it had a triumphant success in quench gas distributors, through which colder
the early generation of large single-train ammo- recycle gas is injected evenly across the whole
nia plants constructed in the 1960s and 1970s. cross section of the catalyst bed. For this reason
Mechanical simplicity and very good tempera- it is justifiable to classify this converter as a
ture control contributed to the widespread accep- multibed type. The distributors consist of banks
tance. For example, M. W. Kellogg alone has
installed more than 100 of its quench converters.
Though being increasingly replaced by the indi-
rect-cooling concept by revamp or substitution
they are still extensively used. Descriptions of
earlier designs of Kellogg, BASF, and Uhde can
be found in [671673, 682].
The most important example is the M. W.
Kellogg three- or four-bed converter [671,
701703] (Figure 42). In this design, the catalyst
basket is not easily removable from the pres-
sure vessel. The catalyst can be changed by
draining it at the bottom of the converter through
downcomers that connect all catalyst beds
with one another. The converter feed effluent
exchanger, attached to the top head, is designed
for disassembly.
Other designs were used by BASF [671],
Casale [671], Chemico, Grand Paroisse [670],
ICI [671], Uhde [671], and others.
An interesting variant in this group is the ICI
Figure 42. Kellogg four-bed vertical quench converter
lozenge converter [213, 666, 671, 685, 701]. This a) Gas inlet; b) Catalyst bed; c) Basket; d) Quench;
design (Fig. 43) has a single catalyst bed that is e) Interchanger; f) Gas outlet; g) Bypass
freely past them during loading and unloading.

A special version of this reactor concept is the
opposed flow design [704, 705], suggested for
very large capacities. In this configuration the
converted gas is collected and withdrawn from
the middle of the catalyst bed, with down-flow in
the upper half and up-flow in the lower half of the
catalyst bed. The uninterrupted catalyst bed is
maintained in the opposed-flow converter. A
design similar to that of ICI with direct injection
of the quench gas into the single catalyst bed has
been proposed by Chemico [706].
Converters with axial flow face a general
problem: with increasing capacity the depth of
the catalyst beds must be increased because for
technical and economic reasons it is not possible
to increase the bed diameter, and thus the pres-
sure vessel diameter, above a certain limit. To
compensate for the increasing pressure drop
conventional axial flow converters have to use
relatively large catalyst particles, which have the
disadvantage of lower activity compared to smal-
ler particles mainly on account of diffusion
restriction. Radial gas flow in the converter
avoids this dilemma, and with this concept it is
possible to design converters for very large
capacities without excessive diameters and with
low pressure drop, even with small catalyst
particle size. The advantages of radial flow are
discussed in [708711]. Radial flow has been
also applied in tube-cooled converters [712]. The
first radial flow converter introduced commer-
cially and then widely used was the Topse S 100
converter [666, 671, 701, 714719], which has
two catalyst layers with a catalyst particle size of
1.5 3 mm. Figure 44 shows a schematic of the
converter [329].
The major part of the gas enters the vessel
at the top and flows down as shell cooling gas.
It then passes through the feed effluent heat
exchanger and flows upwards through a central
pipe to the first catalyst bed, which is traversed
from the inside to the outside. After the effluent
Figure 43. ICI lozenge converter
a) Quench gas distributors; b) Heat exchanger; c) Catalyst
from the first bed has been quenched with cooler
discharge nozzle; d) Tube for thermocouples recycle gas, it enters the second bed and passes
through it in the inward direction. The cold gas
enters through the bottom of the vessel and is
of transverse sparge pipes which deliver gas at mixed with the inlet gas to the first bed for
regular intervals along their length. The spargers temperature control.
are in a void space within horizontal mesh-cov- Radial flow quench converters have also been
ered structures, whose cross section is lozenge used by Chemoproject [721], Osterreichische
shaped so that the catalyst particles can flow Stickstoffwerke [722], and Lummus [723].
Figure 45. Ammonia Casale axial radial flow pattern

a) Unperforated wall; b) Perforated wall
Figure 44. Haldor Topse S100 converter
a) Outer internal lid; b) Inner internal lid; c) First catalyst pressure shell. As the cartridge is equipped with
chamber; d) Inner annular space; e) Perforated center tube; wheels it can be moved in and out on tracks, thus
f) Catalyst support plate 1; g) Second catalyst chamber; needing no crane. The gas flows vertically from
h) Transfer tube; i) Outer annular space; j) Catalyst support
plate 2; k) Heat exchanger; l) Refractory fiber; m) Pressure the top to the bottom. The temperature difference
shell; n) Refractory cement between the top and the bottom requires special
design measures to prevent uneven circumferen-
Axial radial flow pattern was introduced by tial warming of the pressure shell and to avoid
Ammonia Casale. Converters with strictly radial bending.
gas flow require mechanical sealing of the top of
each catalyst bed and dead catalyst volume with Multibed Converters with Indirect Cooling.
little or no flow to avoid bypassing of the catalyst. In converters of this type cooling between the
In the Casale concept there is no need for a dead individual beds is effected by indirect heat
catalyst zone as the annular catalyst bed is left exchange with a cooling medium, which may
open at the top to permit a portion of the gas to be cooler synthesis gas and/or boiler feed water
flow axially through the catalyst. The remainder heating and steam raising. The heat exchanger
of the gas flows radially through the bulk of the may be installed together with the catalyst beds
catalyst bed. As shown in Figure 45 this is inside one pressure shell, but an attractive alter-
achieved by leaving the upper part of the catalyst native, especially for large capacities, is to
cartridge at outlet side unperforated so that gas accommodate the individual catalyst beds in
entering from the top is forced to undergo par- separate vessels and use separate heat exchan-
tially axial flow. gers. This approach is especially suitable when
Crossflow was chosen as a different approach using the reaction heat for raising high-pressure
by M. W. Kellogg in their horizontal quench steam. The indirect cooling principle is applied
converter to obtain low pressure drop even with today in most large new ammonia plants, and
small catalyst particles [670, 695, 715, 716, 725, also in revamps an increasing number of quench
726, 835]. The catalyst beds are arranged side by converters are modified to the indirect cooling
side in a removable cartridge which can be mode. Figure 46 shows a schematic of the prin-
removed for catalyst loading and unloading ciple together with temperature/location and
through a full-bore closure of the horizontal temperature/ammonia concentration profile.
Figure 46. Multibed converter with indirect cooling

A) Converter; a) Catalyst; b) Heat exchanger; c) Cooling section; d) Gas inlet; e) Temperature control gas (cold-shot) inlet;
f) Gas exit
Converters with indirect cooling have been Further development of the radial flow con-
known since the early days of ammonia produc- cept used in the quench converter Topse Series
tion, for example, the Fauser Montecatini re- 100 has led to the successful launch of the Topse
actor [666, 670, 671, 682, 728730]. In this Series 200 converter [477, 690, 691, 708,
converter, tube coils between catalyst beds trans- 732736], designed for indirect cooling. Two
fer the reaction heat to a closed hot water cycle versions are shown in Figure 47, with and with-
under pressure, operating by natural draft. The out a lower internal heat exchanger. A cold
hot water releases the absorbed heat in an exter- shot ahead of the first catalyst bed is installed
nal steam boiler generating about 0.8 t of steam for temperature adjustment.
per tonne of ammonia at about 45 bar (ca. In the converter without a lower exchanger the
250 C). feed gas enters at the bottom and flows as pres-
In the well-known Uhde Chemie Linz sure wall cooling gas to the top of the converter.
converter with three catalyst beds described After passing the centrally installed interbed
in various versions [656, 670, 671, 686689, exchanger on the tube side, the gas is mixed with
701] the indirect cooling is provided by con- cold gas for temperature adjustment and passes
verter feed gas. Feed gas enters at the top, passes through the first catalyst bed radially from the
down the annulus between basket and shell to outside to the inside. The exit gas flows through
cool the pressure wall, flows through the shell the shell side of the interbed exchanger before it
side of the lower feed effluent heat exchanger, enters the second bed, which is crossed in the
and then via the center pipe and interbed ex- same direction as the first one. The Topse Series
changers to the top of the first catalyst bed. The 300 converter contains three catalyst beds and
gas passes downwards through the catalyst beds two central interbed exchangers in a single pres-
and the tube side of the interbed exchangers and sure shell.
the lower heat exchanger to leave the reactor Casale [738743] has also successfully com-
vessel. For trimming purposes a quench is mercialized converters based on the axial
foreseen. radial flow concept with indirect cooling.
Figure 48. Kellogg horizontal intercooled ammonia

converter
a) Inlet; b) Interbed heat exchanger; c) Bypass; d) Bed 1;
e) Bed 2; f) Outlet
located between first and second bed. A cold shot

is installed for adjusting the inlet temperature of
the first catalyst bed. A horizontal design with
indirect cooling is also proposed in [754].
In the C. F. Braun ammonia synthesis concept
[697, 698, 744747], separate vessels were used
for the two catalyst beds in the original version.
The feed effluent heat exchanger was located
between the first and second reactor vessels, and
the second catalyst vessel was followed by a
waste-heat boiler for high pressure steam. This
basic concept was already introduced in the hey-
day of the quench converters and prior to the first
energy crisis. In a later version three catalyst
vessels [747751] with boilers after the second
and the third were used. The gas flow is axial and
the mechanical design rather simple. Contrary to
most converter designs, in which the pressure
shell is kept below 250 C by means of insulation
or by flushing with cooler gas, the pressure vessel
wall of the C. F. Braun reactors is at 400 C,
which is possible with modern steels in compli-
ance with the Nelson diagram (see ! Ammonia,
3. Production Plants, Chapter 1). Figure 49 shows
the two-bed version of the C. F. Braun converter.
To withstand the high outlet temperature level
(450 500 C) needed for the high-pressure
Figure 47. Topse Series 200 converter
a) Pressure shell; b) Interbed heat exchanger; c) 1st Catalyst boilers, a special design is employed to keep the
bed; d) Annulus around catalyst bed; e) 2nd Catalyst bed; outlet nozzle cool. C. F. Braun has devised a
f) Lower heat exchanger; g) Cold bypass; h) Cold bypass pipe good solution by direct coupling the boilers and
the exchanger to the converter.
Kellogg has re-engineered its horizontal cross- Uhde has used three catalyst beds for capaci-
flow quench converter for indirect cooling [670, ties up to 2300 t/d (Fig. 50). The first two are
695, 696, 752, 753]. (Fig. 48) As in the quench accommodated in a single pressure vessel to-
version the pressure shell has a full-bore closure to gether with an inlet outlet exchanger. Then a
remove the catalyst cartridge for loading and waste-heat boiler generating high-pressure
unloading. The reactor contains two catalyst beds, steam cools the gas before it enters the second
with the second one split into two parallel vessel containing the third bed, which dis-
sections. Reactor feed gas passing between car- charges through a second external high-pressure
tridge and shell is used to keep the pressure wall boiler. The gas flow is in radial mode in all three
cool, and an inlet outlet heat exchanger is catalyst beds.
Figure 49. C. F. Braun converters with interbed heat exchanger and waste-heat boiler
a) Gas inlet; b) Feed first bed effluent exchanger; c) Bypass for temperature control; d) First bed; e) Line to second bed;
f) Second bed; g) waste-heat boiler (Borsig); h) Steam drum; i) Steam outlet; k) Gas outlet
A new development is the Uhde dual pressure Al-Jubail, Saudi Arabia (Safco IV). This is so far
process [856861], suited for very large capaci- world-wide the largest capacity in a single
ties. The syngas with 110 bar from the low- synthesis (see also ! Ammonia, 3. Production
pressure casing of the compressor is fed to a Plants, Section 1.4).
three-bed, intercooled, once-through converter Topse has now introduced a hot-wall con-
which can produce a third of the total ammonia verter with only one catalyst bed and no internal
yield. From the effluent about 85 % of the am- heat-exchange equipment, similar to C.F. Braun,
monia produced is removed from the gas before but with radial flow. Three of these converters
it is compressed in the high presure casing to 210 can be combined with an external heat exchanger
bar to enter the well-known Uhde two-vessel- and two high-pressure boilers to give an arrange-
three-bed combination as described above. ment as described for Braun. This Topse Series
Figure 51 shows the Uhde dual pressure con- 50 converter, can also be combined with the
cept. The first plant based on this concept with a Series 200 reactor and two external high-pressure
capacity of 3300 t/d will come on stream 2006 in boilers to attain the configuration as described for
Uhde (Topse Series 250).
Kellogg has developed for its ruthenium
catalyst based KAAP ammonia process [331,
394] a special converter design. Four radial flow
beds are accommodated in a single pressure
shell with intermediate heat exchangers after
the first, second and third bed. The first bed
is loaded with conventional iron catalyst, the
following ones with the new ruthenium catalyst.
Figure 52 is a simplified sketch of the synthesis
loop of the KAAP Figure 53 shows the internals
of the KAAP converter [864].
For revamps Kellogg has also proposed a two-
Figure 50. Uhdes standard synloop configuration
bed version completely loaded with ruthenium
a) Ammonia converter; b) Syngas compressor; catalyst to be placed downstream of a conven-
c) Refrigeration tional converter [395].
Figure 51. Uhde dual pressure ammonia synthesis concept

a) First ammonia converter; b) Second ammnia converter; c) Purge gas recovery unit; d) LP casing; e) HP casing; f) Once-
through ammonia converter
Optimizing the Temperature Profile and 6.3.3. Waste-Heat Utilization and Cooling
Bed Dimensions in Multibed Converters.
With closer approach to equilibrium, the volume The reaction heat of ammonia synthesis is
of catalyst required in the individual beds in- 46.22 kJ/mol at STP, which corresponds to
creases, requiring greater total catalyst volume 2.72 GJ per tonne NH3. Utilization of this heat
and appropriate changes in the catalyst bed di- at the highest possible temperature for generating
mensions. The literature has frequently treated high-pressure steam is a major contribution to the
the problem of optimizing both the distribution of high total energy efficiency of modern ammonia
catalyst volume between a given number of beds plants [755]. Early converters, operating at about
and the bed inlet temperatures [638, 640, 665, 300 bar, equipped with a lower heat exchanger
720, 724, 727, 731]. Reference [737] examines for raising the inlet temperature for the (first)
optimizing the temperature profile in a given catalyst bed to the ignition temperature (ca.
four-bed quench converter. For additional litera- 400 C) , received the converter feed at about
ture on this important issue in converter layout ambient temperature and therefore had outlet
and design, see also page 65.
Figure 52. Kellogg advanced ammonia process (KAAP)

a) Compressor; b) Purge gas recovery unit; c) Refrigeration
stalled to use this heat in other plants or produc-

tion steps. As for any type of converter the outlet
temperature rises with increasing inlet temper-
ature (DT is determined by the degree of con-
version), in further developments an additional
heat exchanger for converter feed versus the
converted gas was installed, downstream of
the above-mentioned heat recovery. In this way
the temperature level at which heat could be
recovered was increased, ultimately to the point
where the inlet temperature to waste-heat
recovery is equal to the outlet temperature of
the last catalyst bed. In practice this corresponds
to moving the lower heat exchanger (which in
multibed converters exchanges feed to the first
catalyst bed against effluent from the last bed)
partially or completely to a position outside of
the converter and downstream of the waste-heat
recovery installation. In this way the waste-heat
downstream of the synthesis converter in
modern plants is available in the temperature
range around 480 to 290 C. The steam pres-
sure, formerly 100 bar, has now been raised to
125 bar, which means that the gas can be cooled
in the boiler to ca. 350 C ; the remaining
recoverable heat is used for boiler feed water
heating.
The trend followed in newer plants is to
increase conversion per pass with the result of
higher ammonia outlet concentrations and lower
outlet temperatures from the last bed. However,
as optimum energy efficiency of the whole am-
monia plant requires maximum high-pressure
steam generation, part of the heat must be recov-
ered before the reaction is completed in the
reactor system. This can be accomplished
[732, 733, 755, 756] by using three catalyst beds
Figure 53. KAAP four bed ammonia converter
a) Bed no. 1 magnetite catalyst; b) Bed no. 2 KAAP catalyst; in separate pressure vessels with boilers after the
c) Bed no. 3 KAAP catalyst; d) Bed no. 4 KAAP catalyst second and the third vessel and an inlet outlet
heat exchanger for the first catalyst bed.
Advanced ammonia concepts produce as
temperatures of ca. 250 C (ca. 15.5 C per much as 1.5 t of high-pressure steam per tonne
mol % of ammonia formed). of ammonia, which correspond roughly to 90 %
Initially there was practically no heat recov- of the standard reaction enthalpy. Figure 54 is a
ery, and nearly the total heat content of the temperature enthalpy diagram for a converter
gas down to ambient temperature and thus the system corresponding to the original C. F. Braun
reaction heat was transferred to cooling water. arrangement. High-pressure steam (113 bar,
Subsequently plants were modified to use this 320 C) is generated after the second catalyst
heat to some extent, but the low temperature bed.
level allowed only boiler feed water heating and Appropriate designs of waste-heat boilers are
generation of low-pressure steam (ca. 20 bar). described in ! Ammonia, 3. Production Plants,
In some instances, water circulation was in- Section 1.3.
ly reliquefied by compression and water or air

cooling) can be substantial. At a loop pressure in
the range 100 to 150 bar the quantity of relique-
fied ammonia may be twice the ammonia product
flow.
The liquid ammonia of the high-pressure
separator is flashed to about 20 bar, whereby the
majority of the dissolved gases are released in the
let-down vessel. This gas is normally used as a
fuel, preferably after removal of ammonia vapor
to avoid NOx formation in the combustion
furnace.
The ammonia from the let-down vessel may
be sent directly to downstream users or flashed
further to atmospheric pressure for storage in a
cold tank. All ammonia vapors removed from
flash gases and from purge gas by water scrub-
bing can be recovered as pure liquid product by
distillation if there is no direct use for the aqueous
Figure 54. Temperature versus enthalpy diagram for a two- ammonia.
bed system with steam generation
a) Heating in main feed effluent exchanger; b) Further heating
Absorption refrigeration with aqueous ammo-
in feed first bed effluent exchanger; c) Temperature rise in nia instead of a mechanical refrigeration system
first bed; d) Cooling in feed first bed effluent exchanger; [757, 764, 770, 772, 778, 780] did not find
e) Temperature rise in second bed; f) Cooling by steam widespread application.
generation; g) Temperature level of waste-heat boiler;
h) Cooling in main feed effluent exchanger
Although ammonia condensation was already
used in HABERs lab-scale ammonia plant and in
early pilot plants of BOSCH, the first commercial
6.3.4. Ammonia Recovery from the units of BASF used ammonia absorption in water
Ammonia Synthesis Loop to remove the product from the cool synthesis
loop gas, because various technical problems
In all commercial plants ammonia is recovered were encountered with refrigeration at that time.
from the synthesis loop by cooling the synthesis It was only in 1926 that ammonia condensation
gas to condense the ammonia under synthesis was introduced in the Haber Bosch plants. In
pressure. The liquid ammonia product is separat- the early 1920s LUIGI CASALE successfully used
ed from the gas, which is recycled. Arrangement condensation for his first plant. Water cooling
and location of the ammonia separator(s), recir- was sufficient on account of the very high syn-
culation compression, addition of make-up gas thesis pressure.
and extraction of purge gas are discussed in Recovery of ammonia by water scrubbing
Section 6.3.1; see also Figure 30). offers the advantage of achieving a very low
In older high-pressure synthesis loops (> 450 residual ammonia content, but the drawback is
bar) cooling by water and or air is sufficient to that the whole recycle gas has to be dried after-
obtain the required low residual ammonia con- wards and in addition distillation of aqueous
centration in the gas. In modern plants, which ammonia is necessary to yield liquid ammonia.
operate at moderate pressures, the cooling has to Nevertheless the scrubbing route was again pro-
be supplemented by refrigeration, for which a posed for a synthesis loop to be operated under
mechanical ammonia refrigeration cycle, with extremely low pressure (around 40 bar) [787].
one or more temperature levels is generally used. Snam Progetti [213, 791, 792] has proposed
Refrigeration down to 25 C is used, which removing the ammonia from the loop gas at
with inclusion of the necessary temperature ambient temperature down to 0.5 mol % by
difference in the chiller requires ammonia evap- absorption in dilute aqueous ammonia.
oration at about atmospheric pressure. The The extent to which the ammonia concentra-
amount of ammonia vaporized (and consequent- tion in the gas can deviate from that expected
for ideal behavior can be seen from ! Ammo- by reducing the hydrogen and nitrogen partial
nia, 1. Introduction, Table 4 and ! Ammonia, 1. pressures. The gas recycle flow is increased by
Introduction, Table 5. For example, at 30 bar the amount of inert gas. Piping and equipment
the ammonia vapor pressure according to ! must correspondingly be increased in size, and
Ammonia, 1. Introduction, Table 4 is 1.167 bar, the associated power consumption for recycle
corresponding to 5.84 mol % at the total pressure gas increases. Moreover, there is an unfavorable
of 20 bar. In contrast, ! Ammonia, 1. Introduc- effect on condensation of the ammonia product.
tion, Table 5 gives the ammonia concentration in Because of the dilution, less ammonia can be
a 1/3 nitrogen/hydrogen mixture at 20 bar total condensed from the recycle synthesis gas by less
pressure as 9.8 mol %. expensive air or water cooling or higher temper-
ature level refrigeration.
There are several possibilities for reducing the
6.3.5. Inert-Gas and Purge-Gas losses associated with the purge gas. The most
Management capital-intensive method consists of feeding the
purge gas to a second synthesis loop operating at
Apart from nitrogen and hydrogen, the fresh a slightly lower pressure [794, 795]. As this loop
make-up gas supplied to the synthesis loop can operate at a very high inert level (40 % or
usually contains small quantities of inert gases. more), only a very small final purge stream is
These include methane (from gas generation), necessary and no recompression is needed. Up to
argon (from the process air), and helium (from 75 % of the hydrogen from the first-loop purge
the natural gas). Because they are inert, they stream can be recovered. This system has the
tend to concentrate in the synthesis loop and advantage that nitrogen is also recovered, but it is
must be removed to maintain the loop material too expensive for use in modern plants and
balance. A portion of the inert gases dissolves in revamps. For this reason other methods have
the liquid produced in the ammonia separator. been developed.
! Ammonia, 1. Introduction, Table 6 gives a
rough approximation of the extent to which these Hydrogen Recovery by Cryogenic Units
inerts are dissolved. ! Ammonia, 1. Introduc- [773]. Ammonia is first removed from the
tion, Figure 2 gives vapor liquid equilibrium purge gas by cooling or in a water wash operating
ratios for use in making precise calculations of the at 7.5 MPa (75 bar). Molecular sieve adsorbers
dissolved quantities of inerts. If the synthesis gas then eliminate moisture and traces of ammonia
pressure is high, for example, 300 bar), and the (Fig. 55). The dry, ammonia-free purge gas from
inert gas concentration in the synthesis loop
make-up gas low enough, for example, under
0.2 vol % [793], then dissolution in the product
ammonia suffices to remove the inerts from the
synthesis loop.
With a higher inert gas content in the make-up
gas this method is not applicable, because the
required partial pressure of the inert gas at equi-
librium in the loop gas would become so high
that a synthesis under moderate pressure would be
virtually impossible. So, in addition to removal as
dissolved gases (flash gas), inerts have also to be
removed from the gas phase by withdrawing a
small purge-gas stream from the loop. At the same
time expensive synthesis gas is also lost from the
loop, which lowers the ammonia yield. Therefore, Figure 55. Simplified flow diagram of cryogenic hydrogen
determining the appropriate inert gas concentra- recovery unit
a) Molecular sieve adsorbers; b) Heater; c) Plate-fin exchang-
tion requires a precise economic calculation. er; d) Separator; e) Ammonia-free purge gas; f) Fuel gas to
A high inert gas level has various drawbacks. reformer burners; g) Hydrogen product to syngas compressor;
It decreases the specific converter performance h) NH3 refrigerant
the adsorbers next enters the cold box. Heat

exchange with cold product hydrogen fraction
and with gas rejected to fuel cools the purge
gas to a temperature of about 188 C (85 K).
Partial condensation liquefies methane and argon
as well as some of the nitrogen and helium. These
are removed in a separator, leaving a hydrogen-
rich gas.
The liquid flows through a control valve,
reducing its pressure, and into a brazed alumi-
num (plate-fin or core-type) heat exchanger. The
hydrogen-rich gas also flows into the same ex-
changer (in separate passages) where the vapor-
izing liquid and the hydrogen are warmed by
cooling the entering purge gas. Liquid ammonia
from the ammonia plant may be used to provide
additional refrigeration, especially at plant
startup.
The warm hydrogen-rich gas flows back to the
suction side of the second stage of the synthesis
gas compressor (6.5 7 MPa). About 90
95 % of the hydrogen and 30 % of the nitrogen
in the purge gas can be recovered.
The remaining gas, with a high concentration
of inerts, serves as fuel for the primary reformer.
After heating in a preheater, a portion serves to
regenerate the molecular sieves and then like-
wise flows to reformer fuel.
Cryogenic hydrogen recovery units are sup- Figure 56. Gas separator module
a) Nonpermeate gas outlet; b) Fiber bundle plug; c) Hollow
plied by firms such as Costain Engineering (for- fiber; d) Separator (length, diameter, and number of separa-
merly Petrocarbon Development) [707, tors determined by ammonia process); e) Coated carbon steel
774776, 796, 808813], Linde [777], and LAir shell; f) Feed stream of mixed gases; g) Permeate gas outlet
Liquide, among others. Reference [713] reports
on the changes in operating conditions of an in a tubesheet at the other. The entire bundle is
ammonia plant resulting from the operation of encased in a vertical shell (Fig. 56).
a cryogenic hydrogen recovery unit. The purge gas is water scrubbed at 135
145 bar, reducing the ammonia concentration to
Hydrogen Recovery by Membrane Sepa- less than 200 ppm. The scrubbed purge gas is
ration. The Monsanto Prism membrane sepa- heated to 35 C and sent directly to the Prism
rator system uses selective gas permeation separators. Trace concentrations of ammonia and
through membranes to separate gases. This prin- water vapor in the gas stream pose no problem to
ciple has been applied to separating hydrogen the membrane. Therefore, a dryer system is not
from other gases [814817] (! Membranes: required.
Gas-Separation Applications). The membranes The gas stream enters the separator on the
are hollow fibers with diameters of about shell side, i.e., the outside of the hollow fibers.
0.5 mm. The fiber is a composite membrane Hydrogen permeates through the wall of the
consisting of an asymmetric polymer substrate fibers. Hydrogen-rich permeate gas flows down
and a polymer coating. The design of a single the bore of the fiber and through the tubesheet and
separator module (length, 3 6 m; diameter, is delivered at the bottom of the separator. The
0.1 0.2 m) resembles a shell and tube heat remaining (nonpermeating) gases, nitrogen,
exchanger. A bundle with many thousands of methane, and argon, are concentrated on the shell
hollow fibers is sealed at one end and embedded side, recovered through the top and pass to the
next separator module. Several separators oper- and a process developed by Bergbau-Forschung
ate in series. The rate of permeation decreases [825] is offered by Costain.
across a bank of separators as the hydrogen
partial pressure differential across the membrane Hydrogen Recovery Using Mixed Metal
approaches zero. Therefore, a second bank of Hydrides. A proprietary hydrogen separation
separators with lower pressure on the tube side is process utilizing the reversible and selective
used to increase the hydrogen recovery. Of the adsorption capability of mixed metal hydrides
recovered hydrogen, 40 70 % leaves the first has been proposed. The hydride, such as LaNi5,
bank of separators at 7 MPa (70 bar) and is FeTi, or Mg2Cu, is in the form of ballasted
returned to the second-stage suction of the syngas pellets. The ballast material serves as a heat sink
compressor. The second bank permeate hydro- to store the heat of adsorption. Subsequently, this
gen is recovered at 2.5 2.8 MPa (25 28 bar) is used to supply the heat of desorption. The
and returned to the first-stage suction of the ballast also is the binder for the pellets, prevent-
syngas compressor. Overall hydrogen recovery ing attrition. Each type of metal hydride is sus-
is 90 95 %. The remaining nonpermeate gas ceptible to certain contaminants. Therefore,
stream normally flows to primary reformer fuel. selection of the metal hydride must be based on
The main advantages of the Prism separator the analysis of the gas to be treated. No ammonia
system are simplicity, ease of operation, and low removal step is required upstream of the unit. The
maintenance. Reference [818] compares mem- system yields 99 mol % hydrogen product at a
brane and cryogenic separation units for a large recovery efficiency of 90 93 % [826, 785, 786].
ammonia plant. No commercial installations are known to be in
For further literature on gas separation by operation in ammonia production processes.
membranes, see [779, 781, 782, 819822].
Membrane technology is also offered by other Argon Recovery from Ammonia Purge
licensors; an example is the Polysep Membrane Gas. The waste gas from hydrogen recovery
System of UOP [783]. In addition to the systems plants is more highly enriched in argon than the
based on hollow fibers, membrane modules have purge gas. If potential markets for argon exist,
been developed in which the membrane is in the then it may be possible to supplement the hydro-
form of a sheet wrapped around a perforated gen recovery plant with one for recovering argon.
center tube using spacers to separate the layers. Cryogenic argon recovery from ammonia purge
The raw gas flows in axial direction in the high gas is discussed in [827829]. Typical argon
pressure spacer and the permeate is withdrawn in recoveries are in excess of 90 %, with a purity
the low pressure spacer. Linde, for example, of 99.999 %.
offers such a module under the name Serarex
[784, 785].
6.3.6. Influence of Pressure and other
Hydrogen Recovery by Pressure Swing Variables of the Synthesis Loop
Adsorption. Pressure swing adsorption on ze-
olite molecular sieves (PSA) (see Section 6.1.3) The influences of individual parameters can be
may be also used for hydrogen recovery from summarized as given in [771, p. 231]:
purge gas [588]. The process, originally devel-
oped by Union Carbide under the name HYSIV, . Pressure: increasing pressure will increase
is now marketed as Polybed PSA by UOP [783, conversion due to higher reaction rate and
823825]. PSA technology is also offered by more favorable ammonia equilibrium.
Linde and other companies. If required, the . Inlet temperature: there are two opposed ef-
process also offers the possibility to supply pure fects as increasing temperature enhances reac-
hydrogen from the purge gas for other uses. PSA tion rate but decreases the adiabatic equilibri-
units usually operate at adsorption pressures of um concentration.
20 30 bar and achieve recovery rates higher . Space velocity: increasing the space velocity
than 82 % for hydrogen and 20 % for nitrogen. normally lowers the outlet ammonia concen-
Carbon-based adsorbents for pressure swing ad- tration, but increases total ammonia pro-
sorption have also been investigated [823, 824] duction.
. Inert level: increasing the inert level lowers the and minimum possible temperature for the first
reaction rate for kinetic and thermodynamic bed, and especially the equilibrium temperature
reasons (Section 4.3). of the last bed [790]. Second, this approach
. Hydrogen/nitrogen ratio: a true maximum re- considers only the mechanical energy and
action rate for a certain H/N ratio; at lower ignores completely the recovered energy of re-
temperatures the maximum lies at lower H/N action, its energy level, and its impact on the
ratios (Section 4.3). Position of the maximum energy balance of the complete ammonia plant.
also depends on the space velocity values Third, the temperature attainable at a given site
(Section 6.3.2). by air- or water cooling will affect the refrigera-
. Recycle rate: at constant pressure and production duty. And fourth, the type of front end can
tion rate, the consequence of higher recycle profoundly alter the result. The front-end pres-
rate is a lower ammonia concentration. In this sure determines the suction pressure of the syn-
case the difference to the equilibrium concen- thesis gas machine. In a plant based on partial
tration and thus the reaction rate increases with oxidation with an operating pressure of 80 bar,
the result that less catalyst is required. How- less than half as much energy is needed to
ever, the temperature level for waste-heat compress the make-up gas to 180 bar, for exam-
recovery decreases and with lower temperature ple, as in a steam reforming plant with a suction
differences, larger heat exchanger surface pressure of only 25 bar.
areas become necessary and the cross sections Thus the problem of choosing the best syn-
of piping and equipment have to be enlarged on thesis pressure is complex because not only does
account of the higher gas flow. the entire energy balance have to be examined,
. Separator temperature: together with pressure but also the mechanical design and the associated
and location of make-up gas addition, the investment costs. For an actual project, the costs
temperature of the ammonia separator deter- for energy (i.e., the feedstock) have to be
mines the ammonia concentration at the con- weighed against investment. With the exception
verter inlet. A lower temperature means lower of some older processes which used extremely
ammonia concentration, which translates into high pressures (Casale, Claude) a pressure of
either a lower catalyst volume or a higher around 300 bar was common for the old multi-
conversion. stream plants operated with reciprocating com-
. Catalyst particle size (Section 5.1.2): smaller pressors. The centrifugal compressor is one of the
catalyst particles give higher conversion most important features of single-train ammonia
because of lower diffusion restrictions (higher plants. The first of these plants, with a capacity of
pore efficiency) 600 t/d, were built in the mid-1960s and the
maximum attainable synthesis pressure was
The question of the best synthesis pressure is restricted to ca. 150 bar by technical limitations
rather a difficult one and the answer is extremely of the centrifugal compressor, which needed
dependent on optimization parameters such as a minimum gas flow (see also Section 6.2).
feedstock price, required return on investment, Of course, at current plant sizes of 1200
and site requirements. In principle it is possible to 2000 t/d this constraint is no longer of impor-
calculate the minimum amount of mechanical tance. These plants usually operate in the pres-
work needed in the synthesis loop. If plots of sure range of 170 190 bar and it is a confirma-
kilowatt hours versus synthesis pressure for tion of the argumentation presented above that
make-up gas compression, recycle, and refriger- the different pressures are not reflected in the
ation are superimposed the result will be a mini- overall energy consumption of the complete
mum, for which a value of 155 bar is reported in ammonia plant. Analysis of the effects of various
[788, 789]. The result is strongly dependent on parameters on the energy consumption of the
assumed boundary conditions, and other studies synthesis loop are also reported in [732, 733].
came to higher values in the range 180 At constant equilibrium temperature for the
220 bar. However, such diagrams should be effluent from the last bed (constant ammonia
interpreted with care. First, this type of plot is concentration) energy consumption of the loop
strongly influenced by the catalyst activity, and was found to be almost independent of pressure
thus by any factors that affect it, such as grain size in the range of 80 220 bar [790].
Figure 57. Example of a synthesis loop for 1500 t/d NH3 (Krupp Uhde)
a) Converter with two radial beds and internal heat exchange; b) Converter with one radial bed; c) Waste-heat recovery; d) Heat
exchanger; e) Water cooling; f) Heat exchanger; g) No. 1 separator; h) Refrigerated cooling; i) No. 2 separator; j) NH3 recovery;
k) H2 recovery
No. Flow rate, T, C p, MPa Gas composition, mol % Production of

kmol/h NH3 liquid, t/h
N2 H2 CH4 Ar NH3
1 28344 295 18.80 23.53 61.20 8.20 2.89 4.18

2 25368 469 18.48 20.43 50.79 9.15 3.23 16.40
3 25368 401 18.38 20.43 50.79 9.15 3.23 16.40
4 24672 336 18.26 19.60 47.99 9.43 3.31 19.67
5 21613 21 18.02 22.33 54.71 10.67 3.78 8.51
6 28344 0 17.88 23.54 61.20 8.20 2.88 4.18
7 3060 21 18.02 0.30 0.55 0.50 0.09 98.55 51.36
8 3678 20 2.50 0.02 0.03 0.12 0.01 99.82 62.51
9 320 38 0.25 46.55 21.72 24.34 7.21 0.18 0.01
10 7667 35 3.23 25.89 72.73 1.07 0.31 0.00
11 374 38 3.25 5.22 90.20 2.86 1.72 0.00
12 8041 35 18.20 24.93 73.54 1.16 0.37 0.00
6.3.7. Example of an Industrial Synthesis inlet gas of the second vessel, which accommo-
Loop dates the third catalyst bed, has a temperature of
401 C and the outlet enters a further waste-heat
Figure 57 is an example of modern ammonia boiler generating 125 bar steam.
synthesis loop (Krupp Uhde) with two con-
verter vessels and three indirectly cooled catalyst
beds producing 1500 t/d NH3 at 188 bar.
The gas enters the converter (a) at 295 C and
is subsequently heated in the internal heat ex- References
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347 R. Lohm uller, Chem. Ing. Tech. 56 (1984) no. 3, 203. 380 D. P. Rounthwaite, Plant Oper. Prog. 2 (1983) no. 2,
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350 J. Thuillier, F. Pons, Ammonia Plant Saf. 20 (1978) 89. 384 Chem. Eng. (N.Y.) 73 (1966) 24.
351 R. G. Cockerham, G. Percival, Trans. Inst. Gas. Eng. 107 385 Hydrocarbon Process. 63 (1984) no. 4, 103.
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352 H. Jockel, B. E. Triebskorn, Hydrocarbon Process. 52 387 K. J. Elkins, I. C. Jeffery, D. Kitchen, A. Pinto, Nitro-
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355 T. Ishiguro, Hydrocarbon Process. 47 (1968) no. 2, 87. 389 D. Kitchen, K. Mansfield, Eurogas 92, Trondheim 1992.
356 N N. Clark., W. G. S. Henson, 33rd AIChE Ammonia 390 G. E. Weismantel, L. Ricci, Chem. Eng. (N.Y.) 86 (1979)
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357 B. J. Cromarty, Nitrogen 191 (1991) 30 34. 391 R. Schneider, Kellogg Ammonia Club Meeting, San
358 R. Vannby, S. Winter-Madsen, 36th AIChE Ammonia Diego 1990.
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359 B. J. Cromarty, B. J. Crewdson, The Application of Pre- Conf., Singapore 1996.
reforming in the Ammonia and Hydrogen Industries, ICI 393 Ammonia, Kellogg brochure, HG 1/96.
Catalco Tech. Paper, 59W/0590/0/CAT2. 394 J. R. LeBlanc, R. Schneider, K. W. Wright, 40th AIChE
360 K. Elkins, Feedstock Flexibility Options, ICI Catalco Ammonia Safety Symp., Tucson 1985.
Tech. Paper, 313/035/0REF. 395 T. A. Czuppon, S. A. Knez, 41th AIChE Ammonia
361 P. W. Farnell, Pre-Reforming a Retrofit Case Study, Safety Symp., Boston 1996.
ICI Catalco Tech. Paper, 291W/025/0/IMTOF. 396 G. J. van den Berg et al., Hydrocarbon Process. 45
362 W. D. Verduijn, 37th AIChE Ammonia Safety Symp., (1966) no. 5, 193.
San Antonio 1992. 397 H. D. Marsch, N. Thiagarajan, 33rd AIChE Ammonia
363 S. E. Nielsen, I. Dybkaer, 41th AIChE Ammonia Safety Safety Symp., Denver 1988.
Symp., Boston 1996. 398 H. J. Herbort, Uhde Ammonia Symp., Dortmund 1992.
364 T. Tomita, M. Kitugawa, Chem. Ing. Tech. 49 (1977) 399 N. Thiagarajan, Uhde Ammonia Symp., Dortmund
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365 Nitrogen 144 (1983) 33. 400 H. D. Marsch, N. Thiagarajan, 37th AIChE Ammonia
366 T. Tomita et al., Special Paper 9, 11th World Petroleum Safety Symp., San Antonio 1992.
Congress, London 1983. 401 Nitrogen 214 (1996) 46.
402 L. W. ter Haar, Ind. Chim. Belge 33 (1968) 655. 439 C. A. Bayens, 36th AIChE Ammonia Safety Sympo-
403 P. D. Becker et al., Chem. Process Eng. (London) 52 sium, Los Angeles 1991.
(1971) no. 11, 59. 440 Clean Coal Technology, International Power Genera-
404 C. L. Reed, C. J. Kuhre, Hydrocarbon Process. 58 (1979) tion, 1990.
no. 9, 191. 441 M. J. van der Burgt, J. E. Naber, Ind. Chem. Bull. (1983)
405 Lurgi Gas Production Technology: The Shell Process 104 105.
Lurgi comp. brochure 189e/6.92/2.20. 442 J. N. Mahagaokar, J. N. Phillips, A. Kreweinghaus, 10th
406 C. Higmann, Perspectives and Experience with Partial ERPI Conf. on Coal Gasification, 1986.
Oxidation of Heavy Residues, Lurgi company brochure. 443 T. W. Nurse, 5th International Symposium Large Chem-
407 Integrated Gasification Combined Cycle Process, Lurgi ical Plants, Antwerpen 1982.
information paper, 1995. 444 E. T. Child, Tennessee Valley Authority Symposium in
408 W. Liebner, N. Hauser, ERPI Conference on Power Muscle Shoals, Alabama 1979.
Generation and the Environment, London 1990. 445 B. Cornils et al., Hydrocarbon Process. 60 (1981) no. 1,
409 C. Higmann, G. Grunfelder, Conference on Gasification 149.
Power Plants, San Francisco 1984. 446 B. Cornils et al., Chem. Ing. Tech. 52 (1980) no. 1, 12.
410 W. Soyez, 33rd AIChE Ammonia Safety Symp., Denver 447 Hydrocarbon Process. 63 (1984) no. 4, 97.
1988. 448 W. Konkol et al., Hydrocarbon Process. 61 (1982) no. 3,
411 Nitrogen 83 (1973) 40. 97.
412 C. P. Marion, J. R. Muenger, Energy Prog. 1 (1981) 449 D. E. Nichols, P. C.Williamson in A. I. More (ed.), Proc.
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414 H. J. Madsack, Hydrocarbon Process. 61 (1982) no. 7, no. 6 7, 7.
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415 S. Strelzoff, Hydrocarbon Process. 53 (1974) no. 12, 79. 452 Hydrocarbon Process. 60 (1980) no. 11, 130.
416 Hydrocarbon Process. 58 (1979) no. 4, 168. 453 M. K. Schad, C. F. Hafke, Chem. Eng. Prog. 79 (1983)
417 Hydrocarbon Process. 63 (1984) no. 4, 90. no. 5, 45.
418 Nitrogen 126 (1980) 32. 454 H. Hiller, Erd ol Kohle Erdgas Petrochem. 28 (1975)
419 Nitrogen 161 (1986) 23 27. no. 2, 74.
420 E. Supp: How to Produce Methanol from Coal, Springer- 455 P. D. Becker, Tennessee Valley Authority Symposium in
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421 Ammonia from Coal, Tennessee Valley Authority, Mus- 456 Hydrocarbon Process. 61 (1982) no. 4, 133.
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422 Nitrogen 226 (1997) 47 56. (1983) no. 12, 557.
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425 D. A. Waitzman, Chem. Eng. (N.Y.) 85 (1978) 69. 460 P. Speich, H. Teggers, Erd ol Kohle Erdgas Petrochem.
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432 H. J. Michaels, H. F. Leonard, Chem. Eng. Prog. 74 no. 11, 185.
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433 H. Staege, Hydrocarbon Process. 61 (1982) no. 3, 92. 111.
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435 A. D. Engelbrecht, Tennessee Valley Authority Sympo- 468 P. N. Hawker, Hydrocarbon Process. 61 (1982) no. 4,
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436 Nitrogen 1985, no. 156, 35. 469 P. S. Pedersen, J. H. Carstensen, J. Boghild-Hansen,
437 Hydrocarbon Process. 63 (1984) no. 4, 96. 34th AIChE Ammonia Safety Symp., San Francisco
438 M. J. van der Burgt, Hydrocarbon Process. 58 (1979) 1989.
no. 1, 161. 470 R. E. Stockwell, FINDS V (1990) .
471 S. J. Catchpole et al., Modern Catalyst Systems for 502 G. Giammarco, in A. V. Slack (ed.): Ammonia, vol. 12,
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472 H. Roos, H. Wanjek, 34th AIChE Ammonia Safety 504 K. E. Zarker in A. V. Slack, G. J. James (eds.): Ammonia,
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473 J. R. Rostrup-Nielsen et al., 37th AIChE Ammonia 505 S. Linsmayer, Chem. Tech. (Leipzig) 24 (1972) no. 2, 74.
Safety Symp., San Antonio 1992. 506 G. Hochgesand, Ind. Eng. Chem. 62 (1970) 7 37.
474 J. B. Hansen, P. S. Pedersen, J. H. Carstensen, 33rd 507 L. Dailey, in A. V. Slack, G. J. James (eds.): Ammonia,
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475 J. M. Stell et al., The Operation of High, Low and 508 W. V. Korf, K. Thormann, K. Braler, Erd ol Kohle
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476 J. Ilg, B. Kandziora, 41st AIChE Ammonia Safety (1977) no. 1, 43.
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477 I. Dybkjaer in A. I. More (ed.), Proc. Br. Sulphur Corp. Vancouver 1994.
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478 J. D. Rankin, J. G. Livingstone, Ammonia Plant Saf. 23 UOP Hydrogen Plant Seminar, Chicago 1995.
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479 Hydrocarbon Process. 61 (1982) no. 4, 154. 1994, Proceedings of the Conf., p. 191 193.
480 I. Dybkjaer, H. Bohlbro, Ammonia Plant Saf. 21 (1979) 513 J. N. Iyengar, D. E. Keene, 38th AIChE Ammonia Safety
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481 I. Dybkjaer, in: Ammonia from Coal Symposium, TVA 514 US 4702 898 (B. S. Grover).
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482 P. W. Young, B. C. Clark, Ammonia Plant Saf. 15 (1973) Sulphur Conf., Copenhagen 1991, Proceedings of the
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483 W. C. Lundberg, Ammonia Plant Saf. 21 (1979) 105. 516 R. K. Bartoo, Removing Acid Gas by the Benfield Pro-
484 Nitrogen 72 (1971) 34. cess, UOP Comp brochure, GP 51321M-11/93.
485 J. Y. Livingston, Hydrocarbon Process. 50 (Jan. 1971) 517 R. E. Meissner, U. Wagner, Oil Gas J. 81 (Feb. 7, 1983)
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486 H. W. Neukermans, J. P. Schurmans, AIChE Symp. Saf. 518 K. Volkamer, E. Wagner, F. Schubert, Plant Oper. Prog.
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487 H. W. Schmidt, Chem. Ing. Tech. 40 (1968) 425. 519 K. Volkamer, U. Wagner: Fertilizer 83, Br. Sulphur
488 C. A. Vancini: Synthesis of Ammonia, Macmillian, Corp. 7th Int. Conf., London 1983, Proceedings of the
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489 H. W. Schmidt, H. J. Henrici, Chem. Ztg. 96 (1972) 520 W. Gerhard, W. Hefner, 33rd AIChE Ammonia Safety
no. 3, 154. Symp., Denver 1988.
490 Hydrocarbon Process. 63 (1984) no. 4, 57 64. 521 D. W. Stanbridge, Y. Ide, W. Hefner, AIChE Ammonia
491 A. G. Eickmeyer in A. V. Slack, G. J. James Safety Symp., Anaheim 1984.
(eds.): Ammonia, vol. 2, Marcel Dekker, New York 522 R. Welker, R. Hugo, R. Meissner, 41st AIChE Ammonia
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492 H. E. Benson, R. W. Parrish, Hydrocarbon Process. 53 523 R. Welker, R. Hugo, B. Buchele: Asia Nitrogen 96,
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493 H. E. Benson in A. V. Slack, G. J. James (eds.): Ammo- 524 G. Ripperger, J. C. Stover, AIChE Spring National
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498 Nitrogen 180 (1989) 20 30. no. 2, 84.
499 C. C. Song et al., 36th AIChE Ammonia Safety Symp., 530 D. K. Judd, Hydrocarbon Process. 57 (1978) no. 4, 122.
Los Angeles 1991. 531 C. G. Swanson, Ammonia Plant Saf. 21 (1979) 152.
500 Hydrocarbon Process. 61 (1982) no. 4, 95 102. 532 C. G. Swanson, F. C. Burkhard, Ammonia Plant Saf. 24
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535 T. L. Huurdemann, V. A. Shah, 34th AIChE Ammonia 569 Nitrogen 123 (1980) 39.
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536 V. A. Shah, Hydrocarbon Process. 67 (1988) . (1978) 165.
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538 Fertilizer Focos 5 (1988) 27. 572 Nitrogen 197 (1992) 18 25.
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559 K. F. Butwell et al., Chem. Eng. Prog. 69 (1973) no. 2, 598 Compressors in Encyclopedia of Chemical Engineer-
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560 Nitrogen 96 (1975) 33. 599 E. E. Ludwig, Compressors in Applied Design for
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563 BASF, DE-AS 1250792, 1959. 602 C. A. Vancini: La Sintesi dell Amoniaca, Hoepli, Milano
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96. 604 Chem. Eng. (N.Y.) 73 (1966) no. 9, 126.
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607 C. Dickinson, Why Dry Running Gas Seals? J. Crane Inc. 648 C. P. P. Singh, D. N. Saraf, Ind. Eng. Chem. Process Des.
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608 W. Koch, Dry Gas Seal Principles Capabilities 649 J. Simiceanu, C. Petrila, A. Pop, Chem. Tech. (Leipzig)
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609 S. Gray, B. Baxter, G. Jones, Magnetic Bearings can 650 K. Lukas, D. Gelbin, Chem. Eng. (London) 7 (1962) 336.
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610 R. R. Poricha, D. G. Rao, Technology (Sindri, India) 3 (1979) no. 3, 381.
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611 H. Forster, Chem. Tech. (Leipzig) 23 (1971) 157. 654 K. V. Reddy, A. Husain, Ind. Eng. Chem. Process Des.
612 Hydrocarbon Process. Pet. Refiner 45 (1966) no. 5, 179. Dev. 21 (1982) no. 3, 359.
613 Eur. Chem. News 11 (1967) no. 270, 26. 655 L. M. Shipman, J. B. Hickman, Chem Eng. Progr. 64
614 W. Pl otner, Chem. Tech. (Leipzig) 24 (1972) 324. (1968) 59.
615 A. F. Wilck, Energy Tech. 23 (1971) no. 5, 161. 656 H. Hinrichs, J. Niedetzky, Chem. Ing. Tech. 34 (1962)
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617 W. L. Luther, Ingenieur Digest 10 (1971) no. 1, 60. 657 R. F. Baddour et al., Chem. Eng. Sci. 20 (1965) 281.
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620 A. Vitti, Het Ingenieursblad 40 (1971) 619. 660 I. Porubsky, E. Simonyi, G. Ladanyi, Chem. Eng.
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628 Nitrogen 181 (1981) 23. 666 J. B. Allen, Chem. Proc. Eng. (London) 46 (1965) 473.
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634 W. Rall, 35th AIChE Ammonia Safety Symp., San 672 C. A. Vancini: Synthesis of Ammonia, Macmillan, Lon-
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635 R. F. Baddour et al., Chem. Eng. Sci. 20 (1965) 281. 673 A. V. Slack, G. J. James, Ammonia, Marcel Dekker,
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688 H. Hinrichs, H. Lehner, Chem. Anlagen Verfahren 723 US 3918 918, 1975 (H. B. Kohn, G. Friedman).
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690 Nitrogen 101 (1976) 42. 726 G. P. Eschenbrenner, G. A. Wagner, 16th AIChE
691 Topse Topics, June 1976. Ammonia Safety Symp., Atlantic City 1971.
692 U. Zardi, E. Commandini, C. Gallazzi in A. I. More (ed.), 727 R. Jackson, Chem. Eng. Sci. 19 (1964) 19, 253.
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695 O. J. Quartulli, G. A. Wagner, Hydrocarbon Process. 57 732 I. Dybkjaer, E. A. Gam, 29th AIChE Ammonia Safety
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696 S. E. Handman, J. R. LeBlanc, Chem. Eng. Prog. 79 733 I. Dybkjaer, E. A. Gam, CEER Chem. Econ. Eng. Rev. 16
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700 P. Lesur, Nitrogen 108 (1977) 29. (1977) no. 3, 381.
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703 S. Strelzow: Technology and Manufacture of Ammonia, 740 L. Sutherland, B. Wallace, 33rd AIChE Ammonia Safety
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704 US 3694 169, 1972 (R. Fawcett, A. W. Smith, D. 741 G. Pagani, U. Zardi, FAI Seminar 1988, The Fertilizer
Westwood). Society of India, New Dehli, S II/119.
705 D. E. Riddler, 16th AIChE Ammonia Safety Symp., 742 K. A. Clayton, N. Shannahan, B. Wallace, 35th AIChE
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706 US 3633 179, 1972 (D. D. Metha, E. J. Miller). 743 N. Shannahan, Hydrocarbon Process 68 (1989) 60.
707 R. Harmon, W. H. Isalski, Ammonia Plant Saf. 23 (1981) 744 GB 1134 621, 1989 (D. R. Twist, D. W. Stanbridge).
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708 I. Dybkaer in H. I. Lasa (ed.): Chemical Reactor Design (1973) 165.
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709 V. Vek, 7th Int. Symp. Large Chem. Plants, Brugge 748 US 4 744 966, 1988 (B. J. Grotz).
1988, p. 77. 749 EP 268 469, 1988 (B. J. Grotz).
710 V. Vek, Chem. Ing. Tech. 45 (1973) 608. 750 K. C. Wilson, B. J. Grotz, J. Tech. Dev. 14 (1990) 54.
711 V. Vek, Ind Eng. Chem. Process Des. Dev. 16 (1977) 751 B. J. Grotz, L. Grisolia, Nitrogen 199 (1992) 39.
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721 A. V. Slack in A. V. Slack, G. J. James (eds.): Ammonia, 759 NH3GasSynthesis, Balke-Durr comp. brochure,
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760 M. Podhorsky et al., 40th AIChE Ammonia Safety 794 H. Neth et al., Chem. Eng. Prog. 78 (1982) no. 7, 69.
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761 Synloop Wast Heat Boiler in Ammonia Plants Unique Process. 55 (1976) no. 1, 103.
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brochure. Ammonia Safety Symp., Denver 1988.
762 K. Nassauer, M. Fix, AFA/Abu Qir Ammonia/Urea 798 M. Appl et al., 34th AIChE Ammonia Safety Symp., San
Technol. Symp., 1996. Francisco 1989.
763 T. Timbres et al., 34th AIChE Ammonia Safety Symp, 799 R. A. Selva, A. H. Heuser, 21st AIChE Ammonia Safety
San Francisco 1989. Symp.,
764 M. J. P. Bogart, Plant Oper. Prog. 1 (1982) no. 3, 147. 800 K. A. van Krieken, 16th AIChE Ammonia Safety Symp.,
765 H. W. Graewe, 25th AIChE Ammonia Safety Symp., Atlantic City 1976.
Portland 1980. 801 A. Cracknell, 24th AIChE Ammonia Safety Symp., San
766 H. W. Graewe, Chem. Eng. Progr. 77 (1981) no. 10, 54. Francisco 1979.
767 H. Lachmann, D. Fromm, 32nd AIChE Ammonia Safety 802 R. S. Brown, Plant/Oper. Progr. 1 (1982) 97.
Symp., Minneapolis 1987. 803 D. C. Guth, D. A. Clark, 29th AIChE Ammonia Safety
768 D. L. Johnson, T. M. OConnor, 31st AIChE Ammonia Symp., San Francisco 1994.
Safety Symp., Boston 1986. 804 D. C. Guth, D. A. Clark, Plant/Oper. Progr. 4 (1985)
769 Nitrogen 176 (1988) 25. 16.
770 M. J. P. Bogart, Hydrocarbon Process. 57 (1978) no. 4, 805 S. Hewerdine, The Fertilizer Society, London 1991,
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771 I. Dybkjaer in A. Nielsen: Ammonia Catalysis and 806 B. G. Burke, D. E. Moore, 21st AIChE Ammonia Safety
Manufacture, Springer-Verlag, New York 1995, p. 231. Symp., San Francisco 1989.
772 W. Malewski, Chem. Ztg. 95 (1971) 186. 807 M. J. Conley, S. Angelsen, D. Williams, 35th AIChE
773 A. Finn, Nitrogen 175 (1988) 25 32. Ammonia Safety Symp., San Diego 1990.
774 W. H. Isalski, Nitrogen 152 (1984) 100. 808 Nitrogen 102 (1976) 35.
775 R. Harmon, W. H. Isalski, 25th AIChE Ammonia Safety 809 R. Banks, Chem. Eng. (N.Y.) 84 (1977) no. 21, 90.
Symp., Portland 1980. 810 A. A. Haslam, W. H. Isalski, Ammonia Plant Saf. 17
776 C. A. Combs, 25th AIChE Ammonia Safety Symp., (1975) 80.
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778 K. Bohlscheid, Chem. Prod. 8 (1979) no. 3. 813 Oil Gas J. 77 (March 5, 1979) 182.
779 A. K. Fritzsche, R. A. Narayan, CEER Chem. Econ. Eng. 814 D. L. MacLean, C. E. Prince, Y. C. Chae, Chem. Eng.
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782 Hyrocarbon Process. 62 (1983) 43 62. Technol. 4th 1981 1982, 457.
783 G. Q. Miller, M. J. Mitariten, ICI Catalco/KTI/UOP 816 Nitrogen 130 (1981) 40.
Hydrogen Plant Seminar, Chicago 1995. 817 Nitrogen 136 (1982) 29.
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785 G. Low, Nitrogen 147 (1984) . Process. 62 (1983) no. 8, 58.
786 J. J. Sheridan, III, et al., Less Common Met. 89 (1983) . 819 D. L. MacLean, D. J. Stockey, T. R. Metzger, Hydro-
447. carbon Process. 62 (1983) no. 8, 47.
787 Pullman Inc., DE-OS 2741851, 1978 (C. L. Becker). 820 H. Knieriem, Jr., Hydrocarbon Process. 59 (1980)
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792 F. Saviano, V. Lagana, P. Bisi, Hydrocarbon Process. 60 826 J. G. Santangelo, G. T. Chen, Chemtech 13 (1983)
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793 H. Hinrichs, Chem. Ztg. Chem. Appar. 86 (1962) 223. 827 R. J. Berry, Chem. Eng. (N.Y.) 86 (1979) no. 15, 62.
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829 S. Lynn, C. Alesandrini, Ammonia Plant Saf. 16 (1974) 856 Ammonia, Uhde company brochure F 110e/2000 09/
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830 G. P. Williams, W. W. Hoehing, Chem. Eng. Prog. 79 857 Nitrogen & Methanol, 258 (2002) 4748.
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833 H. Hinrichs et al., DECHEMA Monogr. 68 (1971) 493 sented at 50th AIChE Symposium on Safety in Ammonia
500. Plants and Related Facilities, Toronto 2005.
834 M. Appl: Ammonia, Methanol, Hydrogen, Carbon 861 J. S. Larsen, D. Lippman, paper presented at 46th AIChE
Monoxide Modern production Technologies CRU Symposium on Safety in Ammonia Plants and Related
Publ., London 1997, p. 44, 45. Facilities, San Diego, 2002.
835 M. W. Kellogg, EP-A 106076, 1983 (C. van Dijk et al.) 862 J. Gosnell, paper presented at Hydrogen Conference,
836 I. Dybkjaer, E. A. Gam, AIChE Symposium on Safety in Argonne National Laboratory, 13 October 2005.
Ammonia Plants, San Francisco, Calif., 1984. 863 Ch. J. Muhlenforth, FINDS, A Stokes Engineering
837 R. K. Bartoo, Chem. Eng. Prog. 80 (1984) no. 10, 35 Publication Volume XVII, Number 4, Fourth Quarter
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839 G. Ertl et al., Surface Science 114 (1982) 527. 864 K. Blanchard, St. Noe, E. Plaxco, FINDS, A Stokes
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KBR Indonesian Ammonia Seminar, 20-23 February Quarter 2000.
2005, Jakarta, Indonesia. 865 Ch. J. Muhlenforth, FINDS, A Stokes Engineering
841 M. Appl: Ammonia, Principles and Industrial Practice, Publication, Volume XV, Number 3, Third Quarter
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842 Syngas Technologies Supplement to Nitrogen & 866 Is there any real competition for iron, Nitrogen &
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845 N. Ringer, paper presented at 50th AIChE Symposium on 869 R. Strait, paper presented at Nitrogen 99, Caracas,
Safety in Ammonia Plants and Related Facilities, Tor- Venezuela (March 1999) International Conference &
onto 2005. Exhibition, British Sulphur Publishing.
846 L. Huazhang et al., US 5,846 507 (1998) Zhejiang 870 Maximising output from a single train, Nitrogen &
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847 J.-C. Park, D. Kim, C.-S. Lee, D.-K. Kim, Bull. Korean 871 By no means a foregone conclusion, Nitrogen &
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catalysts, Literature report, Michigan State University 48th AIChE Symposium on Safety in Ammonia Plants
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Chemical Technology, 5th edition, vol. 2, p. 678710,

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What are the main steps involved in the production of ammonia?

What are the main steps involved in the production of ammonia?

What catalysts are commonly used for ammonia synthesis and what are their properties?

What catalysts are commonly used for ammonia synthesis and what are their properties?

Article No : o02_o11

Ammonia, 2. Production Processes

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . 139 6.1. Synthesis Gas Production . . . . . . . . . . . . . 173

1. Introduction slightly lower synthesis pressure and is used in

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

Table 1. Thermodynamic data for the reaction 0.5 N21.5 H2

300 400 500 600 700 800 900 1000

DH, kJ 46.35 48.48 50.58 52.04 53.26 54.28 55.06 55.68

Table 2. Ammonia content (in mol %) in equilibrium synthesis gas; N2 :H21 : 3

4. Ammonia Synthesis Reaction reasonable pressures, the theoretically achiev-

simulations based on the results of surface sci-

Ammonia synthesis activity:

Reaction Mechanism on Non-Iron Cata-

. Platinum group metals such as Ru, Os Ir, Pt (no

In the non-iron systems the rate-determining

Knowledge of the reaction kinetics is important

or from empirical evaluations. A critical review

Experimental Measurements of Reaction

on an energetically inhomogeneous surface. For thermodynamical equilibrium, Equation (3)

An important modification was made by detailed microscopic model of the reaction

passing through the converter creates sufficient

Position in catalyst bed, NH3 concentration NH3 concentration at Temperature in Temperature at

0 2.500 2.592 400.0 401.4

catalyst life was a big issue; because the

The ammonia synthesis catalyst problem has

Table 7. Effect of various elements or their oxides on the activity of

oxides [176] (Table 7). The iron catalysts pro-

1 68.6 36.07 57.85 3.30 0.09 0.75 2.13 1.13 2 4 2.37

The free iron surface of the reduced BASF cata-

Figure 12. Dependence of the catalyst activity on various factors

decrease in the work function upon potassium

5.1.2. Particle Size and Shape

The choice of particle size and shape of com-

Figure 16. Ammonia catalyst manufacture

Figure 18. Mechanism of catalyst reduction [42]

they established that above all, temperatures

Sulfur, Phosphorus, and Arsenic Com-

whether the benefits of its use are sufficient to

A. Synthesis gas production

Table 13. Feedstock distribution of world ammonia production capacity

1962 1972 1983 1998

103 t N % 103 t N % 103 t N % 103 t N %

Coke oven gas and coal 2800 18 4600 9 7200 8 16500 14

6.1.1. Feedstock Pretreatment and Raw steam-reforming route. In the partial-oxidation

To introduce nitrogen to achieve the required material. Another possibility to compensate is a

Figure 23. ICI gas heated reformer

Figure 24. Kellogg reforming exchanger System (KRES) [331]

As the overall reaction is exothermic no Partial Oxidation of Coal. So far the

In further purification, carbon dioxide, residual

Figure 30. Schematic flow diagrams of typical ammonia synthesis loops

Table 16. Typical operating parameters for modern synthesis loops at

Parameters Inlet pressure, bar

tion profile was often compared to the ideal for

Commercial Ammonia Converters.

1. Internally cooled with cooling tubes running