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Chapter 10
Ammonia crackers
V. Hacker and K. Kordesch
Graz University of Technology, Graz, Austria
1 INTRODUCTION
Anhydrous ammonia is a widely used commodity and is
available worldwide in liquid form in low pressure tanks.
Procedures for safe handling have been developed in every
country. Facilities for storage and transport by barges,
trucks and pipelines from producer to ultimate consumer are
available throughout the world. Therefore liquid anhydrous
ammonia is an excellent storage medium for hydrogen.
Ammonia and its compounds are mainly used in agricultural
as fertilizers, especially in the USA and China. Ammonia
is also used in large amounts in the Ostwald process
(Wilhelm Ostwald) for the synthesis of nitric acid, the
Solvay process for the synthesis of sodium carbonate, the
synthesis of numerous organic compounds used as dyes,
drugs, in plastics and in various metallurgical processes.
Important aspects of ammonia as a fuel include its low
toxicity, low flammability and its assured purity which
results from the method of manufacturing. The major contaminant is water, which has no adverse effect on the fuel
cell operation. From a technical point of view, ammonia
offers, in comparison to hydrogen, significant advantages
in cost and convenience as a fuel due to its higher density
and its easier storage and distribution. The heating value
of liquid ammonia is similar to that of methanol. Ammonia
contains 1.7 times as much hydrogen as liquid hydrogen per
volume. Ammonia dissociates into its constituents hydrogen
and nitrogen according to the reaction:
2NH3 N2 + 3H2 ,
H = 46.22 kJ mol1
(1)
2 AMMONIA PRODUCTION
At the end of the 19th century great efforts in research
on ammonia production were a response to the social
requirements of fixed nitrogen for nitrogen-containing fertilizer due to the fast increase in the world population.
Many famous scientists were involved in the work to overcome this challenge, which was finally solved by Carl
Bosch and Fritz Haber. The HaberBosch process was
one of the most important factors to increase crop yields
two to three times over that which existed prior to the
introduction of fertilizer so perhaps as much as half of
the biomass in our foods today is derived from the use
of anhydrous ammonia which is produced directly from
natural gas.[10]
There are literally dozens of chemical plants that produce
anhydrous ammonia. The worldwide ammonia production
capacity in 1998 was approximately 151 Mt. The typical
Handbook of Fuel Cells Fundamentals, Technology and Applications, Edited by Wolf Vielstich, Hubert A. Gasteiger, Arnold Lamm.
Volume 3: Fuel Cell Technology and Applications. 2003 John Wiley & Sons, Ltd. ISBN: 0-471-49926-9.
17.0312
22.08 l mol1
0.48818 kPa m3 kg1 K1
0.6386 g cm3
0.7714 g l1
0.682 g cm3
0.888 g l1
11.28 Mpa
132.4 C
0.235 g cm3
4.225 cm3 g1
0.242
0.522 kJ K1 h1 m1
23.90 103 mPa s
77.71 C
332.3 kJ kg1
6.077 kPa
33.43 C
1370 kJ kg1
46.22 kJ mol1
192.731 J mol1 K1
16.391 kJ mol1
18.577 kJ g1
22.543 kJ g1
1 1011 1 cm1
3 105 1 cm1
651 C
579 vol% NH3
1627 vol% NH3
15.528 vol% NH3
a Reproduced
b LHV,
3 AMMONIA DISSOCIATION
System studies demonstrate that hydrogen derived from
anhydrous liquid ammonia, via a dissociator and following a hydrogen purifier, offers an alternative to conventional methods of obtaining pure hydrogen for small-scale
use. Hydrogen from ammonia dissociation would be the
preferred option for the smallest plant sizes where it is
projected to be competitive with hydrogen via natural gas
of comparable purity.[13] The dissociation rate depends on
temperature, pressure and the catalysts being used. The theoretical limitation for the lowest working temperature possible is given by the chemical equilibrium for the dissociation
reaction. Figure 4 shows that a nearly complete conversion
from ammonia to hydrogen and nitrogen at higher temperatures and atmospheric pressure is possible. For an almost
H2
Primary
reforming
Steam
O2
Primary
reforming
Partial
oxidation
Steam
Air
Off-gas (fuel)
LT shift
conversion
O2
Partial
oxidation
Steam
Secondary
reforming
Purification
HT shift
conversion
Shift conversion
Gas generation
Hydrotreating
Sulfur removal
Steam
Final purification
HT shift
conversion
Shift conversion
(CoMo cat.)
HT shift
conversion
CO2
removal
Off-gas (fuel)
Purification by
(hydro)desulfurization
CO2
removal
Sulfur
removal
Methanation
Pressure swing
adsorption
Molecular
sieves
Liquid nitrogen
scrubbing
Liquid nitrogen
scrubbing
Sulfur
recovery
N2
N2
N2
Purifier
CO2
CO2
CO2
Ammonia synthesis
Ammonia
Figure 1. Options for generating and purifying ammonia synthesis gas. (Reproduced from Appl (1999)[11] by permission of Wiley
VCH.)
as ammonia catalysts, especially those from the transitionmetal group. Catalyst systems currently used for ammonia
synthesis have emerged from extensive research efforts
to select catalysts that are active for the forward reaction of nitrogen hydrogenation, least active for ammonia
2.5
US ammonia
US natural gas
18
Natural gas
Coke oven gas and coal
16
20
2
1.5
1
0.5
14
12
10
8
6
4
2
1962
1972
1983
1998
0
19
67
19
70
19
73
19
76
19
79
19
82
19
85
19
88
19
91
19
94
19
97
1
0.9
0.8
15 bar
5 bar
1 bar
NH3
0.7
1 bar
H2
5 bar
0.6
0.5
15 bar
0.4
N2
0.3
1 bar
5 bar
0.2
0.1
15 bar
0
300
400
500
600
700
800
900
Temperature (K)
1000
1100
1200
1300
0.9
Conversion rate
0.8
0.7
0.6
0.5
Temperature (C)
1
Ni
Ni + Pt
Ni + Pd
Ni + La2O3
Ni + Ru
800
700
600
500
400
0
100
200
300
400
500
0.4
0.3
0.2
0.1
0
350
400
450
500
550
600
650
700
Temperature (K)
4 CONCLUSIONS
By using materials which are more or less commercially
available, it is possible to construct a hydrogen generating plant using ammonia as the fuel, thus eliminating the
problems of hydrogen storage and transport. At the high
cracking efficiency of the developed catalyst, the ammonia
cracker could be constructed at modest mass and volume. The system using ammonia feedstock is technically
simple, no recycle loops are required. With alkaline fuel
cells especially high efficiency systems are possible as
small amounts of ammonia in the cracked gas are permitted and can be burned in an anode off-gas heated
cracker device.
Air inlet
Burner
Catalyst
H3
Thermocouple
H2
H1
Hydrogen/nitrogen
outlet
(a)
(b)
Figure 7. Anode off-gas heated tube type cracker prototype (a) with a plate type ammonia cracker (b) heated with six burner tubes.
Graz University of Technology with the courtesy of Apollo Energy Systems, USA.
Temperature (C)
700
625
Th1
Th3
Th10
Th9
Th7
550
Th5
Th7
475
Th6
Th8
Th5
Th3
Th4
Th9
Th2
Th1
400
320:00
(a)
330:00
340:00
(min:s)
(b)
Figure 8. The temperature distribution during start-up period inside plate type cracker (a) and the position of thermocouples inside
cracker (b).
REFERENCES
1. G. Faleschini, V. Hacker, M. Muhr, K. Kordesch and
R. Aronsson, Ammonia for High Density Hydrogen Storage, presented at the Fuel Cell Seminar 2000, Portland, OR,
Oct. 30Nov. 2, pp. 336339 (2000).
2. V. Hacker, G. Faleschini, K. Kordesch, R. Aronsson et al.,
Alkaline Fuel Cells for Electric Vehicles, presented at
8. I. W. Kaye and D. P. Bloomfield, Portable Ammonia Powered Fuel Cell, presented at the Conference of Power
Sources, Cherry Hill, pp. 408409 (1998).
17. R. Dong, Y. Dong and Z. Xu, Cracking Process for Producing Hydrogen and Special Equipment for Producing Hydrogen, CN 1,134,912, Jun. 11 (1996).
10. R. D. Schwartz, Population, Fossil Fuel, and Food, Newsletter, The American Physical Society, Vol. 31, No. 1, January
(2002).
21. T. Shikada, M. Asanuma and T. Ikariya, Method of Decomposing Ammonia using a Ruthenium Catalyst, US patent
5,055,282, Oct. 8 (1991).