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Ammonia crackers

V. Hacker and K. Kordesch


Volume 3, Part 2, pp 121127
in
Handbook of Fuel Cells Fundamentals, Technology and Applications
(ISBN: 0-471-49926-9)
Edited by
Wolf Vielstich
Arnold Lamm
Hubert A. Gasteiger
John Wiley & Sons, Ltd, Chichester, 2003

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)

The cracking process is thermally efficient and simple.[15]


A fine purification step after ammonia cracking is usually
unnecessary and further co-reactants such as water are not
required. The nitrogen generated can be released to the
atmosphere without significant local environmental impact.
Therefore, an important reason for using ammonia as fuel
is that dissociation of ammonia offers by far the simplest
approach to produce hydrogen on-site or on-board. It allows
a single feed stream, simplicity of start-up and low overall equipment weight.[69] The properties of ammonia are
shown in Table 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.

122 Part 2: Hydrogen storage and hydrogen generation


Table 1. Properties of ammonia.a
Molecular mass
Molecular volume (at 0 C, 101.3 kPa)
Gas constant (R)
Liquid density (at 0 C, 101.3 kPa)
Gas density (at 0 C, 101.3 kPa)
Liquid density (at 33.43 C, 101.3 kPa)
Gas density (at 33.43 C, 101.3 kPa)
Critical pressure
Critical temperature
Critical density
Critical volume
Critical compressibility
Critical thermal conductivity
Critical viscosity
Melting point (triple point)
Heat of fusion (at 101.3 kPa)
Vapor pressure (triple point)
Boiling point (at 101.3 kPa)
Heat of vaporization (at 101.3 kPa)
Standard enthalpy of formation (gas at 25 C)
Standard entropy (gas at 25 C, 101.3 kPa)
Free enthalpy of formation (gas at 25 C, 101.3 kPa)
Net heating value (LHV)b
Gross heating value (HHV)b
Electrical conductivity (at 35 C), very pure
Electrical conductivity (at 35 C), commercial
Ignition temperature according to DIN 51794
Explosive limits:
NH3 /O2 mixture at 20 C, 101.3 kPa
NH3 /air mixture at 0 C, 101.3 kPa
NH3 /air mixture at 100 C, 101.3 kPa

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,

from Schwartz (2002)[10] by permission of The American Physical Society.


lower heating value; HHV, higher heating value.

ammonia-producing plant first converts natural gas (i.e.,


methane) or liquefied petroleum gases, such as propane and
butane, or petroleum naphtha into gaseous hydrogen. The
driving force for the production of ammonia is nitrogen fixation. When ammonia is considered as a fuel, the reason
for ammonia production changes from nitrogen to hydrogen fixation but the method of production stays the same
and is shown in Figure 1.
Figure 2 provides an overview of the raw material
sources (apart from water and air) for the world ammonia capacity. New plants are based almost exclusively on
natural gas and naphtha. The capital cost and the relative
energy requirements for a plant depends on the raw material employed. The relative investment for naphtha is 1.15
times, for oil 1.5 times and for coal 2.5 times that of natural gas. Natural gas has also the lowest specific energy
requirement.
The significant changes in energy prices from 1973
onwards were a strong incentive to obtain better energy
efficiency. The overall energy consumption was reduced
from around 40 GJ t1 NH3 to 29 GJ t1 NH3 (the lower

heating value (LHV) of ammonia is 18.577 GJ t1 ) which


equals an efficiency of 64% (see Figure 3).

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

Ammonia crackers 123

H2

Primary
reforming

Steam

O2

Primary
reforming

Partial
oxidation

Steam
Air

Off-gas (fuel)

LT shift
conversion

O2

Partial
oxidation

Steam

Secondary
reforming

H2S and COS


removal

Purification

HT shift
conversion

Shift conversion

Gas generation

Hydrotreating

Sulfur removal

Steam

Final purification

Fuel oil, coal

HT shift
conversion

Shift conversion
(CoMo cat.)

HT shift
conversion

CO2 and H2S


removal

CO2
removal

Off-gas (fuel)

Purification by
(hydro)desulfurization

Natural gas, naphtha

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.)

complete decomposition of ammonia this temperature is


approximately 430 C at atmospheric pressure.
The ammonia synthesis catalyst problem has been more
intensively studied than the catalysis of any other industrial
reaction. In principle, metals or metal alloys are suitable

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

124 Part 2: Hydrogen storage and hydrogen generation

2.5

US ammonia
US natural gas

18

Natural gas
Coke oven gas and coal

16

Price (US$ GJ1)

World ammonia production capacity


LHV (EJ year 1)

20

Other petroleum products


Naphtha

2
1.5
1
0.5

14
12
10
8
6
4
2

1962

1972

1983

1998
0

decomposition and reasonably resistant to poisoning. A


typical chemical analysis of the catalyst precursor yields
following values: Fe3 O4 94.3 wt%; K2 O 0.8 wt%; Al2 O3
2.3 wt%; CaO 1.7 wt%, MgO 0.5 wt%; SiO2 0.4 wt%.[14]
The influence and kinetic data of materials like porcelain or silica glass, metals like iron, tungsten, molybdenum,
nickel, etc., especially noble metals and metal oxides, have
been investigated for the dissociation of ammonia. The
temperatures for a sufficient catalytic acceleration of ammonia cracking in most of the investigations is between 700
and 1100 C, and therefore too high for a mobile ammonia dissociator. Studies with commercially available simple

19
67
19
70
19
73
19
76
19
79
19
82
19
85
19
88
19
91
19
94
19
97

Figure 2. Feedstock distribution of world ammonia production


capacity, based on LHV of ammonia. Compare worldwide electricity production: 50.2 EJ a1 in 1997.

Figure 3. US natural gas and ammonia price trends. Calculated


with an average heat content of natural gas of 38 MJ m3 . (Reproduced from Ref. [12].)

catalyst materials such as nickel oxide or iron oxide on


aluminum and the influence of the addition of noble metals have been carried out with lab scale reactors (see
Figure 5).[1]
Catalysts based on nickel on aluminum oxide in the form
of small pellets with a diameter of approximately 5 mm
at a length of 3 mm have been investigated. The catalysts were tested with the addition of different amounts of
platinum and with platinum/lanthanum oxide combinations.

1
0.9
0.8

15 bar
5 bar
1 bar
NH3

Parts per volume

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)

Figure 4. Chemical equilibrium: 2NH3 N2 + 3H2 .

1000

1100

1200

1300

Ammonia crackers 125

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

Ammonia flow (l h1)

0.4
0.3

Figure 6. Reactor temperature as a function of ammonia flow


(conversion > 99.99%, standard liters per hour) with a Ni/Ru
catalyst and tube type cracker.

0.2
0.1
0
350

400

450

500

550

600

650

700

Temperature (K)

Figure 5. Conversion rate as function of reactor temperature


using different catalysts.

The catalysts were prepared with the addition of an aqueous


solution of dihydrogen hexachloroplatinate, the addition
of lanthanum nitrate to the activated catalyst (nickel on
aluminum oxide), the addition of an aqueous solution of
dihydrogen hexachloroplatinate, and then the addition of
ruthenium chloride to the inactivated catalyst (nickel oxide
on aluminum oxide).
Ammonia cracking devices for small transportable
applications have been investigated with different system
designs.[1517] Portable ammonia dissociators with small
residual amounts in the ppm-range of ammonia for low
power applications up to a 200 W electrical output at the
added fuel cell are described in a volume range of less than
6 l. Studies with commercially available catalyst materials
like nickel oxide or iron oxide on aluminum and the
influence of the addition of noble metals were done with lab
scale reactors.[18] Dissociation rates of ammonia on noble
metal wires were examined and compared at temperatures
from 500 to 1900 K.[19] New catalytic investigations have
obtained better cracking efficiencies with new catalyst
materials based on Zr, Mn, Fe and Al/alloy catalysts.[2022]
At Graz University of Technology in co-operation with
Apollo Energy Systems (USA), catalysts have been investigated with and without the addition of noble metals like
platinum, rhodium, palladium, lanthanum oxide and ruthenium, including combinations of these additives (Figure 5).
The catalyst test reformer unit was a tube (inner diameter =
12 mm, heated length = 130 mm). The unit was insulated
and heated electrically. The temperature was measured
inside the catalyst with thermocouples. Ammonia was preheated to obtain a constant temperature over the full catalyst length. The temperature of the reactor is shown in
Figure 6 as a function of ammonia flow at a conversion rate higher than 99.99%. The pressure drop in the

reactor was dependant on the ammonia flow being up


to 70 hPa.
Based on the results of the catalyst research, the design
and development of a lab-scale ammonia cracking reactor was done (Figure 7). In laboratory studies the ammonia
used is preheated to about the catalyst temperature. Preheating has been found to improve the efficiency of the cracking
reaction, and therefore provides higher flow rates. In further
applications this preheating will be done by heat exchangers
to use the heat released from the cracked hydrogen/nitrogen
mixture. In combination with fuel cells the hydrogen containing anode off-gas will be used as fuel for the burner to
heat the cracker.
The plate type cracker was filled with 320 ml of catalyst,
heated by six burner tubes and isolated with 8 cm rock
wool. The gases were not preheated. Figure 8 shows
the temperature distribution by four vertically positioned
thermocouples at an ammonia flow of 300 l h1 . The
temperature at the ammonia inlet is reduced from 660 to
480 C, whereas the temperature in the middle zone remains
almost constant.

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.

126 Part 2: Hydrogen storage and hydrogen generation

Air inlet

Anode off gas inlet


Ammonia 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

the 3rd International Fuel Cell Conference, Nagoya, Japan,


Nov. 30Dec. 3 (1999).
3. K. Kordesch, Brennstoffbatterien, SpringerVerlag, Wien,
p. 64 (1984).
4. M. F. Collins, Life Test of a 200 W Ammonia/Air Fuel Cell
System, presented at the 25th Power Sources Symposium,
pp. 162165 (1972).

Ammonia crackers 127


5. O. J. Adlhart and P. Terry, Ammonia/Air Fuel Cell System,
presented at the Intersociety Energy Conversion Engineering
Conference, Washington DC, September (1969).

14. J. R. Jenning, Catalytic Ammonia Synthesis, Plenum Press,


New York, p. 20 (1991).

6. A. J. Appleby and F. R. Foulkes, Fuel Cell Handbook, Van


Nostrand Reinhold, New York, p. 238 (1989).

15. H. H. Geissler, Compact H2 Generators for Fuel Cells,


presented at the 17th Power Source Conference, pp. 7577
(1993).

7. R. Metkemeijer and P. Achard, Int. J. Hydrogen Energy,


19(6), 535 (1994).

16. DiMartino, Production of Hydrogen from Ammonia, US


patent 4,704,267, Nov. 3 (1987).

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).

9. R. Metkemeijer and P. Achard, J. Power Sources, 271


(1994).

18. P. N. Ross, Jr, Characteristics of an NH3 /Air Fuel Cell


System for Vehicular Applications, in Proc. 16th Intersoc.
Eng. Conf., pp. 726733 (1981).

10. R. D. Schwartz, Population, Fossil Fuel, and Food, Newsletter, The American Physical Society, Vol. 31, No. 1, January
(2002).

19. G. Papapolymerou and V. Bontozoglou, J. Mol. Catal. A:


Chem., 120, 165 (1997).

11. M. Appl, Ammonia, Principles and Industrial Practice,


WileyVCH, New York, p. 66 (1999).

20. G. Boffito, Better Materials for Cracking Ammonia, US


patent 5,976,723, Nov. 2 (1999).

12. Compare www.dasnr.okstate.edu (Gordon Johnson); Gas


prices from US DOE Website: www.eia.doe.gov; NH3 prices
from www.tfi.org/Statistics/pricespaidbyfarmers, March
(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).

13. G. Strickland, Int. J. Hydrogen Energy, 9(9), 759


(1984).

22. E. Rosenblatt and J. Cohn, Dissociation of Ammonia, US


patent 2,601,221, Jun. 17 (1952).