Metal Catalysed Methanation and Steam Reforming

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Published on 01 January 1985 on http://pubs.rsc.org | doi:10.1039/9781847553195-00001
Metal Catalysed Methanation and Steam Reforming

~~
BY J. R. H. ROSS
1 Introduction
The methanation and steam reforming reactions are closely inter-related and,
in general, catalysts used for one reaction will be usable, with some limitations, for the other. This similarity arises from the fact that both reactions
occur under reducing conditions over metallic (most commonly, nickel)
catalysts and, more importantly, that the types of reactive surface intermediate found during one reaction are also found during the other. Both
reactions also suffer from the same constraints, for example, carbon deposition
and susceptibility to sulphur poisoning, and hence similar approaches are
adopted in both cases in attempts to overcome these constraints. The conditions under whch the reactions are carried out depend to a large extent on
the composition of the reactant mixture and, in the case of steam reforming,
on the desired product distribution. The two reactions have another very
different factor in common: there has been a considerable resurgence of
commercial interesting variants of both processes. For example, although the
methanation reaction has been known since the beginning of the century and
it has been practiced commercially to remove traces of carbon monoxide
prior to the synthesis reactor in ammonia plants, there has recently been
considerable activity on the subject of the methanation of synthesis gas;
this activity has arisen because of a resurgence of interest (if only transient) in
coal gasification. Prior to the increase in oil prices that sparked these renewed
efforts in coal gasification, there was also an increased interest in processes
and catalysts for the production of synthetic natural gas (SNG) by the steam
reforming of the then cheap naphtha fractions of crude oil. These developments have led to considerable research on the catalysts for these processes
and also on the reactions themselves. For example, a total of 26 reviews were
published on the subject of methanation in the first six months of 1982 and
this puts the subject in the top fifteen research fronts in the physical,
chemical, and earth sciences. Under the index terms methanation and
methanation catalysts alone, there were approximately 200 articles listed in
the 1972-1976 cumulative index of Chemical Abstracts. Under the corresponding headings of the 1977-1 98 1 index, there were about 650 references
and there were 155 references in 1982 alone. Clearly, with such an enormous
literature and with such an extensive coverage by reviews, it would be
unreasonable to attempt to give a comprehensive description of all the work
in the subject area embraced by the title of this review. Instead, an attempt
E. Garfield, Current Contents, (Physical, Chemical and Earth Sciences) 1982, 2 2 (No.
39), 5
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Catalysis
will be made to draw a general picture of progress in steam reforming and

methanation, with particular emphasis on the catalysts used. Most of the
literature covered will be that from the last few years but, of necessity, some
earlier work will also receive mention. The structure of the review will be
such that a number of the processes themselves will be described in rather
general terms in order to establish the requirements for the catalysts; some of
the catalysts used for the processes themselves, particularly those based on
nickel, will then be described, with particular emphasis on improvements in
knowledge of the structure of these materials; finally, a brief description will
be given-of some of the more relevant academic publications on the steam
reforming and methanation reactions over these catalysts.
2 The Processes
Steam Reforming. - The steam reforming reaction may be described by the
general equation:
CnH2n+2 + n H 2 0
-+ nCO
+ (2n 4-
1)H2
The CO formed may take part in two further reactions, the water-gas shift
reaction:
CO + H 2 0 + C 0 2
+ H2
(2)
and the methanation reaction:
CO + 3H2 + CH4
+ H2O
(3)
Both of these reactions are exothermic and are favoured by reduction in
temperature. Hence, while the products of the steam reforming reaction at
higher temperatures (- 800 C) are CO and H2, lower temperatures are used
to produce methane-rich gases; in this case, the overall reaction can be
approximated by:
CnHZn+*+(y1-1)H20
2
-+
(3n + 1 )
~
CH4
C02
(4)
The thermodynamics of these reactions have been discussed in some detail

elsewhere .2-4
High-temperature Steam Reforming. The high-temperature steam-reforming
reaction is one of the most commonly occurring industrial processes. The
major use of steam reforming is in ammonia plants, when the feedstock is
most generally natural gas, but other feedstocks such as naphtha or LPG
(liquefied petroleum gas) may be used if there is an economic advantage to be
gained. The modern generation of ammonia plants have capacities of 1000
J. R. H. Ross in Surface and Defect Properties of Solids, ed. M. W. Roberts and J. M.

Thomas (Specialist Periodical Reports), The Chemical Society, London, 1975, Vol. 4,
p. 34.
J . R. Rostrup-Nielsen, Steam Reforming Catalysts, Teknisk Forlag A/S, Copenhagen,
1975.
G. W. Bridger and G. C . Chinchen in Catalyst Handbook, Wolfe Scientific Books,
London, 1970, p. 64.
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tons per day of ammonia and utilize some 20m3 of catalyst in the primary
steam-reformer tubes. The service life of a primary steam-reforming catalyst is
generally of the order of 2-3 years; however, the catalyst can still have
adequate activity at this stage, the replacements being timed to coincide with
routine maintenance of the plant. The secondary steam reformer contains a
similar quantity of catalyst but here the duty is somewhat less and lives of
around 5 years are normal.' The secondary reformer in an ammonia plant
brings about the complete conversion of the hydrocarbon feedstock by the
injection of air to the process-steam prior to the reactor, the amount of air
being adjusted to give the required amount of nitrogen for ammonia synthesis.
However, although undoubtedly some of the reaction occurring in this bed is
steam reforming according to equation (l), the main reaction can be thought
of as that of the oxygen of the air with some of the product H2 and CO to
form H 2 0 and C 0 2 . There are currently more than 100 plants in the world
with capacities of the order of 1000 tons per day and it has been argued that
in order to keep up with the fertiliser requirements for the production of food
for an expanding world population, a new large-scale plant will need to be
constructed each month.'
The requirements of the primary reforming catalyst are generally thought
to be greater than those of the secondary reformer. The predominant reaction
is that given by equation (l), with n = 1 or higher, depending on the availability of fuel. For any value of n, the reaction is highly endothermic and so
considerable heat has to be supplied to the reactor; this is generally achieved
by burning a proportion of the feedstock, the flame being played directly on
the exterior of the reactor tubes. However, in the steam-reforming reactor7
of the so-called Adam and Eve system' (to be discussed further below), the
heating is achieved by using a flow of preheated helium (< 950 "C). In order
to achieve the desired conversions, the exit temperature of the catalyst bed is
generally of the order of 820C. The inlet temperature achieved will depend
to a large extent on the activity of the catalyst. If the catalyst is relatively
active and the majority of the conversion occurs near the beginning of the
bed, then the inlet temperature may drop to values of the order of 450 "C, as
shown schematically in Figure 1. The function of the remainder of the bed is
then largely to shift the product distribution towards that corresponding to
the exit temperature, i.e., with reactions (2) and (3) as far as possible to the
left-hand side. In conventional hydrogen plants, it is common practice to
direct most of the heat at the beginning of the reactor tubes to encourage as
large a conversion as possible at that point. The effectiveness of the catalyst
in the primary reformer is often expressed by the approach to equizibrium of
the exit gas.4 This quantity is computed by working out the temperature
required to give an equilibrium gas mixture corresponding to the exit-gas
composition and comparing this with the measured bed temperature at the
D. R. Goodman, paper presented at Symposium o n the Science of Catalysis and its
Application, Sindri, India, 1979 (published as ICI report).
L. C. Axelrod, Catal. Rev. Sci. Eng., 1981, 2 3, 5 3.
H. Fedders, R. Harth, and B. Hohlein, Nucl. Eng. Des., 1975, 34, 119.
B. Hohlein, R. Menzer, and J . Range, A p p l . CafaL, 1 9 8 1 , 1, 125.
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I
Figure 1
Position in bed
Schematic representation of the temperature profile of a tubular steam

reformer as a function of time on stream
exit; an approach of 0C corresponds t o complete equilibration of the gas

mixture while an approach of greater than 10 "C will indicate that the catalyst
is not as effective as it should be. Operating on methane as feedstock, an
active catalyst can give an exit gas containing of the order of 0.1% CH4 at a
bed exit temperature of 850 O C , but higher proportions are ~ o m m o n As
. ~ the
catalyst ages, for example by smtering, the temperature profile will gradually
move down the bed, as is shown schematically in Figure 1, and the approach
to equilibrium will deteriorate .
In ammonia plants, the secondary reformer is included to decrease further
the proportion of methane in the final gas and also to introduce the required
amount of nitrogen for ammonia synthesis. The bed temperature is
maintained at 1000 "C and this is achieved by adding air t o the gas stream,
the oxygen of the air reacting with the hydrogen of the gas stream t o form
water. The reactor consists of a packed bed and no additional heating is
required. The exit gas contains less than 0.1%CH4. The catalyst for this
reactor does not require t o have very high activity but it must be stable under
these reaction conditions.
A variant of the continuous steam reforming process for hydrogen
production is the cyclic reforming process which is used largely for the
production of towns' gas by the steam reforming of naphtha feedstocks. In
these plants, the catalyst is maintained in a wide, relatively shallow bed which
is heated by a flame fueled by the feedstock being used. When the upper
part of the bed has reached a temperature of about 725C' the reactor is
purged with steam and then steam reforming is begun, reaction being continued until the temperature drops considerably. The system is then purged
once more and the bed is again heated with a flame. During steam reforming,
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carbon is deposited on the catalyst and this is burnt off again, exothermically,
during the heating phase. In typical plants, cycle times are of the order of
4 m i n and steam reforming occurs for approximately half of that time. A
typical exit gas contains 56% H2, 15% CO, 6% C 0 2 , 19%CH4, 4% N2, and a
trace of oxygen. The catalyst for these purposes must be mechanically very
stable and be able t o resist the stresses caused by carbon deposition and by
rapid cycles in bed temperature. As a result, the catalysts are often supported
on refractory oxides such as a-A1203 (see later section dealing with the
catalysts for these processes). Recent modifications of the cyclic reforming
process include air injection during the steam reforming process; this apparently gives an improvement in the efficiency of the process, The process has
also been used to steam reform methane t o towns' gas in situations where
conversion of gas mains and appliances is not economical.
Low-temperature Steam Reforming. The steam reforming of naphthas at

lower temperatures is used t o produce methane for use as substitute natural
gas (SNG) particularly in situations where there is a shortage of natural gas or
for supplementing supplies at peak-load periods. By operating at temperatures
of the order of 450 "C, the methanation reaction is favoured and the all-over
process can be represented by equation (3). The early developments in this
area were carried out by the British Gas Corporation: whose Catalytic Rich
Gas (CRG) process is in wide-spread use. The latest variant of the process,
entitled the CRG Hydrogasification Pvocess, has been described in some
detail by Gray." In this, several CRG reactors are used. After the first,
further naphtha is added t o the product gas and gasified in another CRG
reactor operated at lower temperature; the use of the unreacted steam from
the first reactor to convert more naphtha improves the overall efficiency
of the process. Another variant of the CRG process recirculates some of the
product gas from the first CRG reactor back t o its inlet. This is claimed to
reduce the speed of catalyst deactivation and t o enable heavier feedstocks
t o be gasified successfully."
A number of other commercial processes have been described w h c h are
similar to the CRG processes discussed above. For example, Skov12 has
claimed a process in which half the reactant stream is fed to the first reactor.
The product of this reactor is combined with the remainder of the reactant
stream and fed to a second reactor in which a methane content of greater
than 95% is achieved. Similarly, Nikki13 has claimed a process in which, after
steam reforming at 35O-55O0C, a CH4 content of 98% is achieved by
methanation at a temperature of 220 "C.
Data from British Gas Corporation published in technical literature from Dyson
Refractories Ltd., Sheffield; see also: 'Gas Making and Gas-Making Processes', BP
Publication, 1972.
10
J . A. Gray, paper presented at the International Synfuels Technology Symposium,
American Inst. Chem. Eng. Meeting, 29th Nov., 1979.
l1
C. Timmins, T. A. Yarwood, L. J . Watson, T. R. Phillips, H. J . F. Stroud, H. L.
Conway, R. L. Ensell, P. A. Borril, and R. C. Hodrien, Ger. Offen. 3 038 126, 1981.
'* A. Skov, Ger. Offen., 2 9 4 9 5 5 8 .
l 3 K. K. Nikki, Japan Kokai Tokkyo Koho, 02 9 1 9 , 1981.
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Catalysis
Methanation of Coal-derived Synthesis Gas. - The majority of the energy

requirements of the world are supplied by fossil fuels, Le., natural gas, oil,
and coal. Which is the preferred feedstock at any time and in any geographical
situation depends on a complex inter-relationship between political,
economical, and environmental factors. At the present time, oil is still the
preferred feedstock in most developed nations because of its price and
because well-developed technology exists to utilize most of the factions of
the oil. The lighter factions are used as chemical feedstocks and for petroleum
and domestic heating purposes while the heavier fractions are used, e.g., in
electricity generation. Whenever natural gas is available, it is used as an
alternative to oil, both as a fuel and as a chemical feedstock. Coal is generally,
however, used as a fuel and only in places where there is a lack of oil and gas
is it used as a chemical feedstock. The gasification of coal and the FischerTropsch process for hydrocarbon production were developed in Germany in
the period prior to the second World War.14 This technology is now practiced
in a number of plants operated by SASOL in South Africa. The gasification
in these SASOL plants is carried out in Lurgi Gasifiers. In such as gasifier, a
fixed bed of graded coal is exposed, under pressure, to a mixture of steam
and oxygen, the ash produced being discharged by a rotating grate as an
unfused granular solid. The Lurgi process was, at least until recently,, l 6 the
only commercially proven process in the world suitable for the manufacture
of SNG from coal. The greatest problem with such a gasifier is the requirements to supply sufficient excess steam to keep temperatures in the fuel bed
below that at which the ash, which forms a substantial proportion of the
coal, melts or clinkers and causes problems in the grate of the gasifier. The
addition of excess steam reduces the efficiency of the plant and also increases
the cost of treatment of the effluent from the plant. However, if only enough
steam is added to the gasifier to ensure complete reaction, bed temperatures
around 2000C are produced and this is sufficient to melt the ash which
can then be removed as a slag at the bottom of the gasifier. The so-called
Slagging Gasifier was initially developed by British Gas between 1955 and
1964, when the project was closed down. The work was recommenced in
1974 and has resulted in the British Gas High Carbon Monoxide (HCM)
process, which incorporates water-gas shift and methanation reactors and
produces methane (SNG) with good efficiency. Some of the work was
carried out in collaboration with Conoco and details of part of it have been
p~b1ished.l~~
14
15
l6
l7
H. Kolbel and M. Raleck, Catal. Rev.,-Sci.

Eng., 1981, 2 1, 225.
M. E. Dry and J. C. Hoogendoorn, Catal. Rev.,-Sci.Eng., 1981, 23, 265.
Chem. Br., 1983, 19, 896; hereit is reported that Tennessee Eastman is commissioning
a plant for the production o f acetic anhydride from coal which uses a Texaco
entrained-bed gasifier t o produce syngas.
G. F. I. Roberts, D. Hebden, C. T. Brodes, and J . D. Sudbury, I. G . U. 14th World
Gas Conference, Toronto, May, 1979.
J. D. Sudbury, B. J. Koch, and H. Yoon, Proc. 1st Int. Gas Res. Conf., 1980, p. 687;
this conference proceedings also describes a number of other coal gasification
processes.
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Metal Chtalysed Methanation and Steam Reforming
The future of coal gasification for SNG production is uncertain as it

depends upon a number of economical and political factors as much as upon
technical achievements. It is felt in some quarters that the solution t o the
current problem of Acid Rain may lie not in the use of SO2 (and NO,)
removal processes in the flue gases of oil- and coal-burning power stations but
in the prior gasification of the coal or oil, desulphurization of the syngas
produced, followed either by the combustion of the syngas or methanation to
give SNG. The SNG can then either be distributed to consumers or itself used
for electricity generation; the heat liberated in the methantion process would
also make an important contribution t o the energy balance (see also the
following section). At the time of the energy crisis, a number of government
and industrially sponsored coal-gasification projects were started18-20 but,
with the stabilization of oil prices, a proportion of these appear t o have been
cancelled.
A number of papers have described the design of reactors for methantion
of coal- and naphtha-derived synthesis gas; Frohning and Hammer2 have
reviewed some of these and Cornils22 has described research in West Germany
on methanation (and on the Fischer-Tropsch reaction) and the reactors used
in this work. A number of different conformations have been described. In
one arrangement, a high recycle ratio of product gas is passed back through
the methanator t o moderate the temperature rise.23 (A rough rule of thumb is
that there will be an 80 C temperature rise for the conversion of each 1% CO
in the feed gas). An alternative arrangement, which seems to be more generally
f a ~ o u r e d ~ ~(see
, ~ also the next section) is that using three consecutive
reactors, The inlet temperature of the first may be 400C and there may
be a temperature rise of more than 300 OC, even with control of temperature
by the injection of some steam; the inlet temperatures and temperature rises
of the subsequent beds are somewhat lower.25 A Union Carbide patent26
describes a two-bed system in which half the feed is water-gas shifted and
then combined with the remainder of the stream and fed t o the methanation
reactor, this feed-gas now having a CO content of 3-6 vol %. The Forster
Wheeler Energy Corporation has described2 the use of a reactor which
includes a twisted nickel ribbon as catalyst and which operates with an
outlet temperature of 785C and gives a gas containing 54.5% CH4, 41.1%
H 2 0 , 0.4% CO, 3.5% C 0 2 , and 0.5% N2, ie., almost complete conversion.
Pennline and his colleagues from the Pittsburg Energy Technology Center
19
22
23
24
25
26
27
F. Boegner, R. Vangala, and T. K. Subramaniam, Proc. 8th. Ann. Conf. Coal. Gasif.
Liquef. Convers. Electr., (1981), 1982, p. 141.
B. Cornils, P. Rufrecht and R. Durrfeld (Ruhrchemie AG), Proc. 16th. Intersoc.
Energy Convers. Eng. Conf., 198 1, Vol. 2 , p. 1050.
C. D. Frohning and H. Hammer, Chemierost. Kohl, 1 9 7 7 , 174.
B. Cornils, Pet. Technol., 1978, 2 5 6 , 4 4 .
K. H. Eisenlohr, F. W. Moeller and M. Dry in Methanation o f Synthesis Gas, Adv.
Chern. Ser., 1975, 146, 11 3.
G. A. White, T. R. Roszkowski, and D. W. Stanbridge in Methanation of Synthesis
Gas, Adv. Chern. Ser., 1975, 146, 138.
C. Woodward, Hydrocarbon Process., Jan. 1977; I.C.I. Catalyst Tech. Paper, N o . 4 .
H. Cheung, US P. 4 2 3 5 0 4 4 .
Forster Wheeler Energy Corporation, Jpn. Kokkai Tokkyo Koho, 78 1 4 4 5 0 5 .
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CH4
Heluim
heating
and pump
+ HzO
u
He
3= gNaastura'
11
P
I
ADAM
CH4
Schematic representation of the Eva I-Adam I pilot plant; details of heat

exchangers, etc., are omitted f o r clarity
(Reproduced by permission from Appl. Catal., 1981, 1 , 130)
Figure 2
have reviewed the use of catalyst-sprayed tube-wall reactors for

methanatioq2' while a patent t o the French Institute of Petroleum (IFP)
describes the use of slurry reactors operating at 200-350"C.29 Details of
some of the pilot methanation plants in current operation were summarized
in the review by Hohlein, Menger, and Range.'
The Adam and Eve (NFE) Project. - The long-distance energy transport
('Nukleare Fernenergie', NFE) system, generally known as the Adam and Eve
project, has been under development for a number of years in West Germany
and results from pilot-plant experiments have recently been described.' The
concept, which is shown schematically in Figure 2, depends, as discussed
briefly above, o n the supply of energy in the form of helium from a hightemperature nuclear reactor (HTR), this helium having a temperature of u p
t o 950 "C. The helium is used to heat the steam-reforming tubes of the EVA
28
29
H. W. Pennline, R. R. Schehl, W. P. Haynes, and A. J . Forney, Report 1980, DOE/

FETC/TR80/7.
Y. Chauvin, D. Commereuc, and A. Sugier, Ger. P. DE 3 138 1 2 7 , 1 9 8 2 .
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Metal Catalysed Methanation and Steam Rejorming
Catalyst bed lengthhm
Figure 3
Temperature profiles in the three reactors of Adam I; see Figure 2
(Reproduced by permission from Appl. Catal., 1981, 1,134)
(Einzelrohr-Versuchs-Anlage) reactor and bring about the steam reforming of

methane [reverse of reaction (3)] to give a synthesis-gas mixture. The Eva I
plant, which has been operation since 1972, used electrically heated helium at
950C and 40 bar press~re.~'The dried carbon oxides/hydrogen mixture is
then transported to the entrance to the three methanation tubes of the Adam
I reactor 31 where it is methanated, with the liberation of heat which is used
to produce superheated steam at about 535 "C and 110 bar pressure,
necessitating temperatures up to about 700 "C for the methanation process.
Part of the energy produced is to be used for electricity production, part for
process steam generation, and part, as low temperature heat, for heating
purposes. To ensure complete conversion to methane at the exit of the third
reactor tube of the Adam system, the exit temperature is about 300C.
Temperature profiles f o ~ n d ~ in, ~the~ three
, ~ ~reactor tubes of Adam I,
operating at -27 bar and using a 'third generation' methanation catalyst,
MCR-2X, in the first reactor and a different catalyst, MCR-4, in the second and
third reactors, are shown in Figure 3; both these catalysts are manufactured
by Haldor-Topsq5e. These temperature profiles are typical also of those found
30
32
33
C. B. von der Decken, H. Fedders, R. Harth, B. Hohlein, and E. Riensche, IAEA

Specialist Meeting o n Process Heat Application Technology, K. F. A. Julich, W.
Germany, Nov. 2 7 - 2 9 , 1 9 7 9 .
B. Hohlein, Kernforschungsanlage Jiilich, Jul. 1433, 1977.
H. G. Harms, B. Hohlein, and A. Skov, Chem. Ing. Tech., 1 9 8 0 , 5 2 , 504.
B. Hohlein, R. Menzer, M. Vorwerk and A. Skov, Kernforschungsanlage Jiilich,
Jul-Spez 9 1 , 1980.
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Table 1 Typical temperatures and gas compositions a t different positions in

the Adam I reaction system
Temperature/" C
Gas compositions/
mol %
H2 0
Synthesis
gas input
15
Input to
first bed
290
Exit of
Exit of
first bed second bed
600
43 8
Exit of Product
third bed
303
17
0.0
18.3
31.0
39.9
43.4
0.1
CH4
11.9
27.4
38.1
44.7
47.2
83.4
co
co2
8.8
4.1
1.o
0.0
0.0
0.0
10.3
7.3
5 .O
2.4
1.4
2.4
H2
65.0
38 .O
19.1
6.7
1.6
2.8
N2
4.0
4.9
5.8
6.3
6.4
11.3
in methanation reactors associated with coal gasification systems, as discussed

in the last section and, together with the temperature and gas composition
data of Table 1, illustrate clearly some of the problems to be overcome in
the design of catalysts for methanation of high concentration CO feeds. In
the Adam I system, the upper temperature of the first bed has been limited to
600C by recirculation of part of the product gas to the exit of the bed;
without this recirculation, the temperature would rise to about 800 "C. The
concentration of water throughout much of the bed is relatively high and
unreacted hydrogen is also present. Hydrogen-water mixtures are known to
be particularly detrimental to the behaviour of nickel-containing catalysts at
high t e r n p e r a t ~ r e sand
~ ~ a common method of testing the stability of catalysts
designed to withstand the conditions of the first bed of such a reactor is to
expose them for extended periods to hydrogen-steam atmospheres at high
temperatures and pressures. The catalyst must remain stable under these
conditions so that when the entrance of the bed becomes deactivated by, for
example, gradual poisoning by sulphur, the next part of the bed must still
have sufficient activity at the lower temperature to bring about the desired
conversion and temperature increase. The requirements of the second and
third beds of the Adam I system are not so great, the peak temperatures being
much lower in both cases. It is interesting to note from Table 1 that the
second reactor has brought about complete conversion of the carbon
monoxide of the feed and that the third reactor is required only to convert
the C 0 2 . This observation is compatible with the frequently encountered
selective methanation of CO in CO iCOz mixtures.35 Hohlein, Menzer, and
Range' carried out further experiments in which they tested the catalysts
from the Adam I reactors after 550h operation in an integral flow reactor
operating at 300 "C. The samples of catalyst from both the entrance and
exit of the first reactor had lost about 50% of the fresh activity and they now
only caused the methanation of the CO of the reaction mixture and had little
34
3s
A. Williams, G. A. Butler and J. Hammonds, J. Cutal., 1972, 24, 352.

T. van Herwijnen, H. van Doesberg, and W. A. de Jong, J. Cafal., 1973, 28, 391.
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11
or no remaining activity for the methanation of C02. A sample of catalyst

from the second reactor was less affected and still retained some COz
methanation activity. It is not clear that the loss of C02 methanation activity
is due to a separate poisoning of that activity, as might on first sight be
inferred from these results; it may be that loss of active area has caused a
decrease in activity to such an extent that only sufficient sites remain to bring
about conversion of the CO and that this CO precludes the adsorption and
reaction of the C02 on the same sites. A recent d e ~ e l o p r n e n tin
~ ~the NFE
project is the design and successful operation of an Inner-Cooled Reactor for
Methanation (IRMA). In this, an inner tube, through which is passed superheated steam in a direction countercurrent to the flow of synthesis gas, is
immersed in the catalyst bed. This enables the bed temperature to be
controlled without product-gas recirculation and the superheated steam
allows removal of a substantial proportion of the heat of reaction.
The Cothane Process. - This is a process for the removal of traces of CO from
waste-gas streams and its conversion to pipe-line quality SNG.37 The process
depends on the fact that carbon monoxide disproportionates at 200C
on Ni surfaces according to the Boudouard reaction:
2co
--f
C,)
+ c02
( 5 a)
and that the active carbon species formed on the nickel surface (C(s)) can
react with steam to form methane and C02 :
2C,
+ 2H20
++
CH4
+ C02
(5b)
Some reaction also occurs via non-dissociated chemisorbed CO, the all-over
reaction in either case being given by:
4CO
+ 2H20
CH4
+ 3C02
( 5 c)
The process is operated using two beds, the first of whch is being used for
adsorption of CO while the second is being regenerated. When the adsorption
and regeneration are complete, the waste-gas stream is diverted through the
second bed and the first is regenerated. It has been found that the adsorption
step can be carried out in the presence of hydrogen or water vapour without
appreciable formation and consequent loss of methane at that stage and that
hydrogen in the process stream actually raised the amount of CH4 that could
be recovered during the second step.37 The process has been tested in a small
pilot plant using gases containing 25% CO with a balance of N2 together with
up to 15% of water and/or hydrogen in some cases; there was some evidence
that the presence of hydrogen encouraged the lay-down of carbon.
36
37
B. Hohlein, Proc. Internat. Gas Research Conference, London, ed. L. H. Hirsch.

A. C. Frost, L. F. Elek, C.-L. Yang, A. P. Risch, and J. A. Rabo, AppZ, CutuZ., 1982,
2 , 347; see also Report 1980, DOE/CS/40177, T2; J. A. Rabo, L. F. Elek, and J. N.
Francis, Proc. 7th Int. Congr. Catal., Tokyo 1980; Elsevier, Amsterdam, 1981,
p. 490; US P. 4 242 103,1980
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Catalysis
12
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Steam Dealkylation. - The steam dealkylation of aromatic hydrocarbons,

such as toluene:
has been studied in some detail over the last decade as a possible process for
replacing hydrogen by water in the catalytic treatment of some petroleum
fraction^.^' The selective steam reforming of the side-chain, depicted in
equation ( 6 ) , is generally also accompanied by non-selective steam reforming
to give CO and hydrogen and, by the water-gas shift and methanation
reactions [equations (2) and (3)], C 0 2 and CH4. Hydride-alkylation can also
occur as a side-reaction:
the hydrogen being produced in the early stages of the steam dealkylation
reaction. Some work on the effect of catalyst on the selectivity will be
discussed in a Iater section. Suffice it to say here that the most effective
catalysts are the noble metals Rh, Pt, Ir and Pd.3s-40 A recent patent has
claimed that crown-impregnated Rh-A1203 catalysts (catalysts with a
predominance of rhodium in the outer layers of the pellets) are more active
than standard catalysts with a homogeneous distribution of the
This has been explained in terms of a rate determining step for the reaction
involving migration of OH groups from the support to metal through the
metal-support interface, the geometry of these catalysts being favourable for
this step.
Steam Reforming of Methanol. - The steam reforming of methanol43 has
been developed as a convenient method of producing pure hydrogen according
to the equation:
The process is generally carried out at relatively low temperature of 250350 O C , when the direct decomposition of methanol:
CH30H
CO
+ 2H2
(9)
[which is the equivalent of equation (8) combined with the reverse of the
water-gas shift reaction (2)] does not take place. The catalysts used for this
reaction are generally copper-based and so there is no tendency for the
formation of methane by the further reaction of some of the C02 and H2
formed in reaction (8). The thermodynamics of the various possible processes,
including soot formation, have been discussed by Amphlet et aZ.,44 whose
paper also gives an extensive review of the pertinent literature. The hydrogen
39
40
41
42
43
44
See, for example, D. Duprez, P. Pereira, A. Miloudi, and R. Maurel, J. Cutul., 1982,
75.151.
D. Duprez, R. Maurel, A. Miloudi, and P. Pereka, N o w . J. Chim.,1 9 8 2 , 6, 1 6 3 .
D. C. Grenoble, J. Catul., 1 9 7 8 , 5 1 , 203;ibid, 1978, 5 1 , 212;ibid, 1 9 7 9 , 5 6 , 32.
M. Grand and D. Duprez, Fr. P., 2 4 2 3 4 6 9 .
D. Duprez, A. Miloudi, J. Little, and J. Bousquet, AppZied Cutul., 1 9 8 3 , 5 , 2 1 9 .
See, for example, W. C. Pfaferte, Ger. P., 2 6 2 4 9 7 5 , 1 9 7 7 .
J. C. Amphlett, M. J . Evans, R. A. Jones, F. R. Mann, and R . P. Weir, Can. J. Chem.
Eng. 1981, 59, 7 2 0 .
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13
produced by the method may be used in fuel cells4 or for other purposes
where on-site production of hydrogen is d e ~ i r a b l e .Some
~ ~ of the recent work
on the kinetics and mechanism of the reaction will be discussed briefly in a
subsequent sect ion.
3 The Catalysts
As indicated in the Introduction, the most commonly encountered catalysts
for steam reforming and methanation are nickel-based. This is the case for a
number of reasons. First, the reaction can generally be thought of as nonselective as the products required are the most thermodynamically stable
under the conditions used (but see steam dealkylation and steam reforming of
methanol, below); hence, there is no advantage to be gained by using more
expensive metals, such as the noble metals, which wdl, like nickel, catalyse
the reactions. Secondly, nickel is among the most active metals for both the
steam reforming and methanation reactions. For example, as early as 1928,
Fischer and Tropsch4 described screening tests on many catalysts from
which they concluded that Ni and Co are among the best catalysts for the
steam reforming reaction.
Ro~trup-Nielsen~~
has given the following results for the order of specific
activities of a series of catalysts for the steam reforming of ethane:
Rh,Ru
> Ni, Pd,Pt > Re > (Ni2Cudoy) > Co
These activities were based on activities per unit metallic area rather than on
activities per gram, as in the results of Fischer and Tropsch. Rostrup-Nielsen
suggests that the low activity of the cobalt may be due to the fact that the
reaction was carried out under conditions when the cobalt can be oxidized by
the steam of the reaction mixture. For the methanation reaction, Fischer,
Tropsch, and Dilthey4 give the following order of activities for the Group
VIII metals:
Ru
> Ir > Rh > Ni > Coi > 0 s > Pt > Fe > Pd
This order of activities was again based on activities per gram of catalyst.
Vannice has determined the following order of specific activities for the
methanation of carbon monoxide at 275 C:
Ru
> Fe > Ni >
Co
> Rh > Pd > Pt > Ir
According to Vannices data, ruthenium is about six times more active than
nickel and about three times more active than iron. As ruthenium is not only
much more expensive than nickel but is also in very short supply, it is very
improbable that it will ever be used as a catalyst in any large-scale process.
Iron and cobalt (which have similar specific activities for methanation to that
45
46
47
48
49
R. F. Gould, Ed., Fuel Cell Systems-II, Adv. Chem. Ser., 1969, 90.
J. E. Philpott, Platinum Met. Rev., 1976, 2 0 , 110.
F. Fischer and H. Tropsch, Brennst. Chem., 1928, 9, 39.
J. R. Rostrup-Nielsen, J. Catal., 1973, 31, 173.
F. Fischer, H. Tropsch, and P. Dilthey, Brennst. Chem., 1925, 6 , 2 6 5 .
M. A. Vannice, J. Catal., 1975, 3 7 , 449 and 462.
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14
Catalysis
of nickel) and also to some extent ruthenium have the disadvantage that they
also produce higher hydrocarbons under methanation conditions, i.e., they
are also Fischer-Tropsch catalysts. Various aspects of the Fischer-Tropsch
and so it will not be discussed
process have been reviewed
further here.
It follows that most work reported over the last few years on steam
reforming and methanation has been concerned with nickel catalysts. The
following sections wlll therefore deal mostly with nickel-based catalysts,
particularly those which have some importance in commercial practice.
Particular stress will be laid on work, with which the author has been
associated, concerned with steam reforming and methanation catalysts but
mention will also be made of parallel studies from other laboratories. In
sections on the catalysts for steam dealkylation and steam reforming of
methanol, where catalyst selectivity is a prerequisite, other types of catalyst
will also be discussed.
Nickel Catalysts for Steam Reforming and Methanation.- The various nickelbased catalysts used for steam reforming and methanation were discussed in a
previous review by this author2 and in another by Rostrup-Niel~en.~
Most
progress in the intervening period has been made in gaining an understanding
of coprecipitated catalysts of the CRG type2 suitable for the production of
methane (SNG) from naphtha by low-temperature steam reforming, and on
catalysts for methanation, but there have also been some developments in
high-tem perat ur e st earn reforming cat a1y st s. The following sub-sect io ns
therefore deal with coprecipitated Ni-A1203 catalysts of the CRG type, then
with other Ni formulations for, in particular, methanation, and finally with
catalysts for high-temperature steam reforming.
Coprecipitated Ni-AZ203 Ciztalysts. Work by Ross and Steel on the kinetics
of the steam reforming of methane at 600C at low pressures on coprecipitated Ni-A1203 catalysts of the CRG types4 led to further work on the use of
the differential scanning calorimeter (DSC) to study the methanation activity
of a series of coprecipitated catalysts which had been prepared and pretreated
in various relatively ill-defined ways.55 It became clear that the way in which
the catalyst was prepared had an effect on its calcination, reduction, and
methanation behaviour. (The term calcination is taken here to apply to the
decomposition of the catalyst precursor at elevated temperature and does not
necessarily imply that the process had taken place in air.) This led to a
collaborative project between the authors group in Bradford and L.L. van
Reijens group in Delft, the aim being to examine more closely the factors
which control the activity and stability of such materials with the particular
aim of developing stable catalysts for the methanation of synthesis gas in the
Adam reactor of the Adam and Eve process.8 The results of this work have
51
52
53
54
55
R. B. Anderson, Cutal. Rev.-Sci. Eng., 1980, 21, 53.

A. T. Bell, Cutul. Rev.-Sci. Eng., 1 9 8 1 , 23, 2 0 3 .
D. L. King, J. A. Cusumano, and R. L. Garten, Cutul. Rev.-Sci. Eng., 1981, 2 3 , 2 3 3 .
J . R. H. Ross and M. C. F. Steel, J. Chem. SOC.,Faraduy Trans. 1, 1 9 7 3 , 69, 10.
T. Beecroft, A. W. Miller, and J . R . H. Ross, J. Cutal., 1 9 7 5 , 40, 2 8 1 ; and unpublished work.
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15
been described in a number of publication^.^^-^^ A parallel investigation was

carried out by British Gas.63
The original patent covering the preparation of the CRG-type of catalyst
described a rising-pH method of preparation.a A mixed solution of nickel
and aluminium nitrates of the appropriate composition (Ni/Al molar ratio
3) is placed in a vessel and heated to 95 C and an excess of Na2C03
solution is added slowly until the final pH is approximately 7.0. A typical
potentiometric curve for such a precipitation is shown in Figure 4 where it is
compared with the potentiometric curves for the pure component^.^^
Precipitation begins at a pH of about 4 and an aluminium hydroxide phase
separates [compare the curve for the A1(N03)3 solution]. Most of the nickel
is then precipitated at pH values lower than that (- > 5) associated with the
precipitation of the pure component (< 9, apparently by a redissolution of
the Al species and precipitation of a mixed hydroxide phase. The presence
of such a mixed hydroxide phase was first suspected from the fact that its
decomposition behaviour during calcination was very different to that of the
pure component^.^^ The actual identity of the coprecipitate was first described in a patent describing a method of preparation which was essentially
that used in the CRG method.66 The precipitate was shown to have a
composition Ni6M2(OH)16C03 4H20, which has a structure very similar to
the mineral takovite, a member of the hydrotalcite group of compounds (see
below).67 The main difference between the preparation methods described in
the two patents was that the constant pH method was used in the latter; by
adding the alkali and the mixed nitrate solutions simultaneously to a vessel
maintained at a constant pH of about 7 (see below), the mixed hydroxide
phase is formed in a single step rather than in by the redissolution of the
aluminium hydroxide precipitate, as in the rising pH method.
Kruissink, Van Reijen, and Rosss6 described the results of a detailed
investigation of the structure of the coprecipitate and the effect of pH and
Ni/Al ratio on this structure. They showed that the recipitate consists of
brucite-like layers of compositions [Ni,All -,(OH), 3
and interlayers
56
57
SA
59
60
61
62
63
64
65
66
67
E. C. Kruissink, L. L. van Reijen, and J. R. H . ROSS,J. Chern. SOC.,Faraday Trans. 1,

1981, 7 7 , 649.
L. E. Alzamora, J. R. H. ROSS,E. C. Kruissink, and L. L. van Reijen, J. Chern. SOC.,
Faraday Trans. 1, 1981, 77, 665.
E. B. M. Doesburg, S. Orr, J. R. H. ROSS,and L. L. van Reijen, J. Chem. SOC.,Chern.
Cornrnun., 1 9 7 7 , 7 3 4 .
E. C. Kruissink, L. E. Alzamora, S. Orr, E. B. M. Doesburg, L. L. van Reijen, J. R. H.
Ross, and G. van Veen, in Preparation of Catalysts II, ed. B. Delmon, P. Grange,
P. Jacobs, and G. Poncelet, Elsevier, Amsterdam, 1979, p. 143.
E. C. Kruissink, H. L. Pelt, J. R. H. ROSS,and L. L. van Reijen, Appl. Catal., 1981, 1,
23.
G. van Veen, E. C. Kruisskin, E. B. M. Doesburg, J . R. H. ROSS,and L. L. van Reijen,
React. Kinet. Catal. Lett., 1978, 9 , 143.
E. C. Kruissink, Thesis, Techn. Univ. Delft, 1981.
D.C. Puxley, I. J. Kitchener, C. Komodromos, and N. D. Parkyns, in Preparation o f
Catalysts III, ed. G. Poncelet, P. Grange, and P. A. Jacobs, Elsevier, Amsterdam,
1983, p. 237.
G. Percival and T. A. Yarwood, Br. P., 969 637, 1964.
M. R. Gelsthorpe and J. R. H. Ross, unpublished work.
Ger. Offen. 2 061 115, 1971, and 2 0 6 1 , 1 5 6 , 1971.
D. L. Bish and G. W. Brindley, A . Mineral., 1977, 6 2 , 4 5 8 ; s e e ref. 54.
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16
Typical potentiometric titration curves for the precipitation of Ni(NO,),

(l),Al(NO,), (2), anda mixtureof Ni(NO,), and Al(NO,), (3) using Na,CO,
as precipitant. The concentrations used are typical of those used in catalyst
preparation
(M. R. Gelsthorpe, Ph.D. Thesis, University of Bradford, 1983)
Figure 4
containing CO,, NOi, or OH- ions or combinations of these ions, depending

on the preparation conditions, together with molecular water. This structure
is shown schematically in Figure 5 . It was concluded that the aluminium and
nickel ions are distributed randomly in the brucite-like layer, according to the
models of Allman and Jepson68 and Ingram and Taylor6 for the minerals
68
69
R. Allmann and H. P. Jepsen, Neues Jahrb. Mineral. Monatsh., 1969, 544; R .

Allmann, A c t a Crystallogr., Sect. B, 1968,24,972.
L. Ingram and H. F. W. Taylor, J. Mineral Soc., 1967,36,465.
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Brucit e-like
layer
OHOHOHAl3+
Ni2+
OHOHOH-
H 2 0 , CO:-(NO;,
Inter layer
Brucite-like
layer
17
3 co
OH-)
OHOHOHAl3+
Ni2+
OHOHOH-
etc.
Figure 5
Schematic representation o f the structure of the Ni-A1 coprecipitate
hydrotalcite (cations Mg and Al) and pyroaurite (cations Mg and Fe),

respectively, rather than the A13+ions being found in the interlayer, as in the
models of Feitknecht7' and Ross and K ~ d a m a . ~ ~
It was found56 that the freshly prepared coprecipitate consisted of a single
phase as long as 0.5 < x 5 0.85 but that for hydrothermally aged materials,
0.66 < x < 0.75. These values correspond to 1 < Ni/AlS 6 and 2 < Ni/Al<
3, which should be compared with the fixed value of Ni/Al = 3 in the mineral
takovite. 67 Outside these ranges of composition, separate phases of either
Al(OH)3 or Ni(OH)2 form. The anion found in the coprecipitate depended
on the precipitation conditions. For example, the predominant anion in the
precipitate was found (by chemical analysis) to be nitrate if the precipitation
was carried out at a pH of 5.0 but to be carbonate if the precipitation was
carried out at pH of 7.0 or above. In order to achieve pH values much above
7.0, NaOH had t o be added to the carbonate solution and then there was an
indication that there was inclusion of OH- ions in the interlayer as well as the
COi- ions. If the precipitation was carried out a t low pH with a solution of
nickel and aluminium chlorides, the anion in the coprecipitate was found to
be chloride. The interlayer spacing, 1/3c0,(see Figure 5) depends on the
anion present, the spacing required for the nitrate anions (1/3C0 x 8.5
being higher than that for the carbonate anions (1/3C0 x 7 . 6 a ) . It would
appear that the precipitate acts as a anion exchange material and that other
anions can replace the CO",, NO;, C1-, or OH-ions of the structure.
Kruissink et aLS6 confirmed the earlier observation of Beecroft et aLS5
that the decomposition of the precipitate occurs in two steps. In the first,
between 130 and 230"C, depending on the anion, the molecular water is
removed from the interlayer and there is a slight decrease in the interlayer
spacing. The brucite layer is destroyed at a higher temperature (- 350 "C)
with the evolution of water (from the OH-ions) and for example, C 0 2 or
NO2, depending on the anions in the coprecipitate.
The nature of the anion in the coprecipitate can have a marked effect on
the behaviour of the final catalyst, particularly if the heating rate is not
carefully controlled in such a way that the gases evolved during the
a)
'O
71
W . Feitknecht, Helv. Chim, Acta, 1 9 4 2 , 2 5 , 555.

G. J. Ross a n d H . K o d a m a , A m . M i n e r d , 1 9 6 7 , 5 2 , 1 0 3 6 .
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Catalysis
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Layer structure
3500Y
KOoc
Calcination
NiO*xA1203
+ A1203*yNi0
NiO
+ NiA1204
(x,y,z,
<< 1 )
Reduct ion
Ni
+ A1203 zNiO
Ni
+ "204
Changes occurring during the calcination and reduction of Ni-A1 coprecipitates

(Modified from J. Chern. SOC.,Faraday Trans. 1, 1981, 77, 6 6 5 )
Figure 6
decomposition of the layer structure are not immediatly removed from the
system. Thus, Van Veen et aZ.61 reported that the activities of the catalyst
resulting from reduction at 500 "C of calcined samples (450 "C) derived with
precipitates with various anions decreased in the order:
COi-
> NO, > C1-
and that the stabilities of the catalysts during reaction in a CO 3H2 mixture
at 500C fell in the same order. It was concluded that the main effects of the
anions were manifested during the calcination of the coprecipitates. It was
also observed that the hydrothermally aged materials gave reduced samples
with very similar methanation activities t o those derived from the freshly
prepared materials.
The natures of the calcined and reduced samples resulting from the
coprecipitated materials were examined in some detail in a paper by
Alzamora et aZ.57 It was concluded that the X-ray data for the calcined
material were consistent with a model in w h c h two phases were formed, one
rich in NiO and containing a small proportion of A13' ions, the other rich in
alumina and containing a small proportion of Ni2+ions (see Figure 6). Calcination of the catalyst at higher temperature causes a gradual rearrangement of
the structure and, in the extreme, a t 75OoC, a nickel aluminate phase separates together with an essentially pure NiO phase. Reduction of the samples
calcined at low temperatures is much more difficult (reduction temperatures
of around 600 "C are required for complete reduction; see Figure 7) than that
of the samples calcined at high temperatures. Figure 7 shows more recent and
as yet unpublished results obtainedn using differential thermogravimetry
(DTG) which illustrate clearly this dependence of reducibility on calcination
temperature. The temperature required for the reduction of these materials is
much hlgher than that required for the reduction of pure NiO (- 350 " C ) .
Alzamora et aZ.57 explained the reduction behaviour in terms of a model,
72
M. R. Gelsthorpe and J. R . H. Ross, unpublished work.
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Calcination
450
600
Differential thermogravimetric (DTG) traces o f the reduction behaviour of a

Ni,Al, coprecipitate calcined at various temperatures
(M. R. Gelsthorpe, Ph.D. Thesis, University of Bradford, 1983)
Figure 7
shown in Figure 8, in which the reduction occurs within the separate NiO-rich
crystallites and in which the final nickel crystals are therefore approximately
the same as the original NiO-rich crystallites. The course of the reduction is
hindered by the presence of A13+ions in these crystallites and these ions tend
to segregate during the reduction. A consequence of this segregation is that if
a catalyst of this type is reduced and then fully re-oxidized, the subsequent
re-reduction occurs at a much lower temperature than did the original
reduction; hence one must conclude that the segrated alumina is in such a
position in the catalyst particles that it no longer effects the reduction in
the same way.
Puxley and his colleagues6' have carried out a parallel study to that
described above. In their published work they refer mostly to a material of
the stoichiometric nickel aluminate composition (i.e. with a Ni/Al ratio of
0.5) but they also refer in passing to the more practical composition with a
Ni/Al ratio of 3. They develop, on the basis of this and unpublished work, a
continuously variable phase model in which the precipitate [in their case,
shown as having the formula Ni2(N03)(OH)3 4A1(OH)3 4H20 when precipitated by ammonium bicarbonate] gives, on decomposition, a single phase
which changes gradually in structure as the material is calcined at higher and
higher temperatures. They suggest that the material first formed on calcination
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Catalysis
KEY
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0Ni0-xAl2O3
@ A1203
y NiO
I) Ni
Model for the calcined catalyst and its reduction. (a) Calcined catalyst; (b)
progress of reduction
(Reproduced by permission from J. Chem. Soc., Faracday Trans. I , 1981,77,665)
at around 450C is a substituted nickel oxide (SNO) in which all the A13+
ions occupy octahedral sites in the nickel oxide structures without the
formation of a separate alumina-rich phase. As the calcination temperatui-e is
raised, the aluminium ions gradually move into tetrahedral positions in the
nickel oxide lattice and finally a true nickel aluminate phase forms. Puxley
et al. call the intermediate phases disordered oxide-spinel intermediate
(DOSI) and spinel-like material (SLM). They consider that these phases also
form, but now with larger proportions of nickel, in materials with higher
nickel contents and that these materials are relatively homogeneous.
Puxley et al. argue that the reduced catalysts will be paracrystalline o n the
basis that the complete removal of the aluminate groups from the nickel
during reduction would be energetically unfavourable. Wright, Windsor, and
Puxley therefore examined the reduced catalysts by time-of-flight neutron
diffraction t e c h n i q ~ e s .They
~ ~ concluded that the crystallites were indeed
paracrystalline w h c h implies that there is within each nickel crystallite strain
introduced by the presence in the lattice of aluminate groups which occupy
more space than do the nickel atoms. This is depicted in Figure 9.63
Puxley et al. 61 have discussed their conclusions in terms of a phase distribution diagram; such diagrams, as shown in Figure 10, provide a useful
method of comparing their model with that of Alzamore et aL5' (Note that
the x-axes here are reversed compared with those of Puxley et al., whose
Ni/Al ratios read from right to left.) Figure 10a shows the behaviour for a
material with a value of xNi(= Ni/Ni + Al) of 0.33, corresponding t o the
nickel aluminate formulation. The vertical dotted line at xNi= 0.33
corresponds to the composition of the parent liquids or of a pure phase of
NiA1204. When precipitation occurs, two separate phases are formed, one
being of the approximate composition of Ni6&(OH)6C03 4 H 2 0 (i.e., the
solid envelope at xNi= 0.75) and the second being of approximate composition, A1(OH)3 (i.e., the solid curve at x N ~= 0). (It should be noted that
although Puxley et al.. claimed to have isolated a phase of composition
73
C. J. Wright, C. G. Windsor, and D. C. Puxley, J. Cutul., 1982, 78, 257.
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21
Al
m e production of local microstrains and distorted lattice cells by the

inclusion of aluminate groups in the nickel lattice
(Reproduced by permission from Preparation of Catalysts 111, 1983, p. 256
Figure 9
Ni2(N03)(OH)304A1(0H)~
* 4 H 2 0from a preparation at xNi= 0.33, they still
show the precipitate composition as consisting of two phases as in Figure
10a). Figure 10b is the corresponding figures represepting the behaviour for
preparations at XNi = 0.75. Again, the vertical dotted line at this composition
represents the composition of the solution from which the precipitate forms,
curve (i) represents the composition immediately after precipitation and curve
(ii) represents the composition after aging the precipitate; the vertical dotted
lines at xNi= 0.0 and 1.0 represent the situation which would exist if
separate phases of Ni(OH)2 and Al(OH)3 were formed. The broadness of
the curves centering at xNi= 0.75 represents the degree of non-homogeneity
of the precipitate; this will be more marked for the rising pH method, in
which Al(OH)3 is first formed, than in the constant pH method. Figures 1Oc
and 1Od illustrate what the models of Puxley et al. and of Alzamora et al.,
respectively, predict for the calcined materials. Figure 1Oc shows the
substituted nickel oxide phase of the Puxley model for xNi= 0.33 and 0.75;
broad bands of composition are shown for the single phases which are
postulated. The model of Alzamora et al., shown in Figure 10d for xNi=
0.75, is very different, as it involves the formation of two separate phases;
also shown in this diagram by dotted lines is the situation which exists after
calcination at high temperatures, when separate phases of essentially NiO and
NiA1204 are formed.
Evidence which seems to favour the original model of Alzamora et al. is
provided in a recent paper by Doesburg et al. 74 In this, samples of coprecipitated material, precipitated at pH 7 from a mixture of nitrates with a Ni/Al
ratio of 2.33 (xNi= 0.7) were examined byoscanning electron microscopy
after coprecipitation, after calcination at 600 C in air, after reduction in H2
74
E. B. M. Doesburg, G. Hakvoort, H. Schaper, and L. L. van Reijen, AppZ. CataZ., 1983,

7,85.
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Catalysis
22
(a)
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NiAlz0 4
I
I
I
I
I
I
60
0.33
oa
1.0
075 1.0
0.0
Ni/(Ni + Al)
Ni/(Ni -t Al)
(d)
(C)
(ii)
1.0
,O 0-33
Ni/(Ni
+ Al)
1.0
Figure 10 Phase distribution diagrams for various possible compositions (see text).
(a) Composition of parent solution and possible phases present in precipitate a t x N ~= 0.33; (b) as in (a) for X N ~= 0.75; (c) phases present in
calcined material with X N ~= 0.75; according to model of Puxley et a1
(Preparation of Catalysts, III, 1983, p. 237); (d) phases present in the
calcined material with X N ~= 0.75 according to the model of Alzamora
et a1 (J. Chem. SOC.,Faraday Trans. 1, 1981,11,665)
at 600 C , and after extraction of the majority of the nickel of the catalyst as
nickel carbonyl in a flow of CO at 100C; X-ray diffraction showed no
evidence for the presence of an alumina phase, as in the earlier work of
Alzamora et al., this indicating that if such a phase exists it must be X-ray
amorphous. The scanning electron micrographs of the samples at all stages
show a very porous sponge-like structure, consisting of rod-shaped particles,
even after extraction of the nickel. These rod-shaped particles must therefore
be the amorphous alumina referred to above. Doesburg etal. suggest that the
nickel-rich crystallites which make up the active phase of the catalysts are
buried within the mesopores of this alumina support. These observations help
to explain the very large difference found between the total and metal areas
of the catalysts, results which the model of Alzamora et al. (Figure 8)
attempted to explain.
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Metal Catalysed Methanation and Steam Refowning
23
Promotion of Coprecipitated MA1203 Gztalysts. Kruissink et al. have

reported on the effect of sodium ions on the behaviour of coprecipitated
nickel-alumina catalysts. Early work5' showed that sodium from the Na2C03
precipitant was commonly retained in the catalyst structure even after careful
washing of the precipitate and that the quantity of sodium retained was
rather unpredictable; samples precipitated at pH 10, especially large batches,
contained relatively large quantities of sodium but samples precipitated at pH
7 had generally almost negligible sodium contents. Kruissink et aL6" showed
that the sodium was present in the gel-like structure of the high-pH samples as
NaN03 dissolved in the gel-like water and that this sodium could be removed
completely by first drying the precipitate to destroy the gel-structure and
then washing it. The effect of sodium content on the methanation activities
of reduced samples of such a material, to whch sodium nitrate had been
added at the coprecipitate stage, were then determined. It was found that the
activity was decreased markedly by even small additions of sodium while the
metallic area decreased only slowly. This result contrasts with the observation
made by Huang and R i ~ h a r d s o nthat
~ ~ the specific methanation activity of an
8%Ni/Si02-A1203 catalyst was increased by the addition of 0.3%Na and that
it decreased to a value slightly higher than the original value at 2.4% Na.
We have recently76 carried out further work on the effect of the addition
of various promoters to a coprecipitate having a Ni/Al ratio of 2.5. We chose
to use 1.2 mol% of these additives, this quantity having given the most
significant decrease in the activity of such catalysts doped with sodium.60
It was found that the group I cations all had a detrimental effect on the
activity of the catalysts, the effect increasing in the order:
Li
< Na < K < Cs
Cs giving a decrease in activity for methanation of CO in the temperature range

200-330 "C of 80%compared with the unpromoted catalyst. The activation
energy in all cases was 100 kJ mol-l. The group I1 cations had little or no
effect on the methanation activity of the catalysts but it was found that
chromium had a slightly detrimental effect on the activity (a decrease of
10%). Finally, lanthanum and cerium were both found to be beneficial to
the activities. Work on the effect of lanthanum content and on the method of
lanthanum addition showed that the optimum lanthanum content was at
about 0.5% and that the best catalysts were obtained by including the
lanthanum in the coprecipitation mixture.76 77 The best catalysts gave
activities which were a factor of three or four greater than the unpromoted
materials.
The results for the effect of alkali are interesting in connection with the
type of catalysts which have been used commercially for the steam reforming
of hydrocarbons.2 ,64 The original commercial materials were carefully
75
76
77
C. P. Huang and J. T. Richardson, J. Catal., 1978, 51, 1 .

M. R. Gelsthorpe, K. B. Mok, J . R. H. ROSS,and R. M. Sambrook, paper presented at
the 2nd European Symposium on Catalysis by Metals, Brussels, Sept. 19-21, 1983,
t o be published in J. MoL Catal., 1984, 25, 253.
M. R. Gelsthorpe, B. G. Lippens, J. R. H. Ross, and R. M. Sambrook, 'Proc. 9th
Iberoamerican Symp. Catal.,' ed. M. F. Portela, Lisbon, 1984, p. 1082.
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24
washed until the sodium content was very low and then potassium was added
to give a content of about 1% before drying, calcining, and pelletting. The
reasoning behind this was seemingly that sodium was detrimental to the
catalyst but that the added potassium was beneficial in preventing the
deposition of carbon during low-temperature steam reforming. Our results
show that potassium is more detrimental to the activity of the catalyst than is
sodium. The poisoning effect of the alkali metals seems to increase with
increasing ionic radius. If we assume that the alkali-metal ions become
associated with the alumina species at the surface of the nickel crystallites,
then the larger is the ion, the larger is the effect on the surrounding nickel
atoms. The fact that the activition energy for the methanation reaction is not
changed argues in favour of such a geometric effect. In another investigation,
Kneale and Ross78 investigated the steam reforming of ethane over similar
catalysts; they found that potassium added to the catalyst in the same way as
described above had a detrimental effect on the activity of the catalysts, the
effect again apparently being purely geometric. The addition of potassium is
unlikely to be beneficial in the case of methanation as carbon deposition
is generally not thought to be a problem in this reaction as long as reaction
conditions are correctly chosen. It is interesting to note that ICI have
developed a methanation catalyst, which would appear to be a coprecipitated
material without alkali-metal addition, which they claim to be stable under
high-temperature methanation conditions2' Similar alkali-free materials have
also been used by others.
The slightly detrimental effect of chromium is also of some interest when
this result is contrasted with the beneficial effect on activity of such additions
claimed in a patent by British Gas.79 Here, it was suggested that the catalyst
precursor had the composition:
NiwAlxCrIn yC03(OH)16 zH20
where w = 4-6.4, x : y = 3-19.1, 2w + 3x 3y = 18 and z = 3.5-5.5. After

sintering the material in a steam-hydrogen mixture at 600 O C , the Ni particle
size was 1 5 7 8 compared with 277A for a chromium-free material tested in
the same way. Thus, it may be that the main effect of Cr is to improve the
stability of the catalysts rather than to improve the activity. Our experience
is that lanthanum additions improve not only the activity but the stability
of the catalysts. It would appear that the lanthanum enters the layer
structure of the catalyst precursors, at least at low concentration^.^^,^' We
believe77 that although the La3+ion is twice as large as the Ni2' and A13+ions,
it can fit into the structure by intruding slightly into the space normally
occupied by OH- ions; its charge is then formally balanced by one OH- and
one COi- ion rather than by two OH-ions and half a CO;-ion, as in the case
of the A13+ions depicted in Figure 5. Further work on the structure of the
lanthanum-containing precipitates is in progress.
78
79
8o
B. Kneale and J. R. H. ROSS,Faraday Discuss. Chem. SOC., 1981, 7 2 , 157;see also

J. Chem. SOC.,Chem. Commun., 1981, 751.
Br. P., 1 550 749,1979.
R. M. Sambrook and J. R . H. Ross, Br. P. Appl. 2 080 136, 1982.
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25
A recent Japanese patent by H. Futami described an alternative method of

preparing Ni-Al-La-containing catalysts.81 In this method, the aluminium is
first precipitated by adding an alkaline carbonate to a solution of A1(N03)3,
adding a solution of La(N03)3 [or Ce(N03)4] followed by further alkali, and
finally adding a solution of Ni(N03)2 at the same time as further alkali,
bringing the pH to a value in the range 6.0-10.0. The arguments behind this
procedure were based on the observations that the steam reforming activity
of a Ni-Al material prepared by sequential precipitation (first Al, then Ni)
was higher than samples prepared either by the rising pH or constant pH
methods and that La (or Ce) additions improved the activities and helped
prevent carbon deposition during steam reforming. The Ni-Al-La material
prepared by the sequential method was also claimed to be superior to a
nickel-aluminium catalyst in terms of durability. The sequential method was
also claimed to be superior to other preparation sequences (e.g., coprecipitation of all three components together by the rising pH method, addition of
La to the Ni-A1 coprecipitate, etc.). Futami argues that the sequential precipitation method gives a lower degree of 'intimacy' between the components
than does the coprecipitation method and that gives rise to higher activities.
This constrasts with our belief that a high degree of intimacy is important in
such catalysts in determining their h g h temperature activity and stability; if
the components are not completely homogeneously dispersed in the precipitate, sintering is more likely to occur during the calcination and reduction
stages than if there is a high degree of interaction between the Ni and the Al
and La. The ideas of Wright et al.73 on paracrystallinity of the Ni crystallites
also require this high degree of interaction. We have therefore recently
compared the behaviour of Ni-Al-La samples prepared by the sequential
method of Futami'' with samples prepared by the constant pH method and
have found77 that although the activity behaviour of both sorts of catalyst is
similar after reduction at 600 'C, the materials prepared sequentially show a
dramatic loss of activity after treatment in a hydrogen- water atmosphere at
800 "C for 2 h.
Schaper et al. have recently examined the effect of lanthanum additions
on the behaviour of alumina.82a They have shown that lanthanum ions
prevent the conversion of y-A1203to cu-A1203,a process which they believe
occurs by surface diffusion. They found also that the stability of the
y-Al2O3 was improved by the presence of La in steam-containing atmospheres
at high pressures and temperatures.82
Materials with High-temperature Stability. As discussed in an earlier section,
catalysts designed for methanation of synthesis gas have, in particular, to be
able to withstand the extreme conditions encountered in the first methanation
reactor (see Figures 2 and 3), i.e., they must have high activities at low
temperatures and yet also have high stabilities at higher temperatures. PreUS P. 4 215 998, 1980.
82aH. Schaper, E. B. M. Doesburg, and L. L. van Reijen, A p p l . Catal., 1983, 7 , 21 1.
%I
Schaper,
.
D. J. Arnesz, E. B. M. Doesburg, and L. L. van Reijen, A p p l . Cutul., 1984,
9 , 129.
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26
Catalysis
liminary tests on pelletted samples of coprecipitated Ni-A1 materials under

such conditions showed that while the catalysts had more than adequate
activities at low temperatures and good chemical stabilities at high temperatures, their mechanical strengths were not good; mechanical breakdown of
the pellets would lead to unacceptable pressure drops in the reactor.83
Work was therefore carried out to attempt to find ways in which
mechanically stable materials of adequate activity could be made. This was
carried out in collaboration with Dyson Refractories Ltd (Sheffield) who had
for some time manufactured a-A1203-basedcatalysts containing unpromoted
nickel for cyclic steam reforming plants and Ni-U02-a-A1203 catalystsw for
continuous steam reforming in hydrogen plants. It was found that a very
active and stable catalyst, which could be used for both steam reforming and
methanation and which had all the advantages of the strength of these a-A1203
matrices, could be prepared by a method based on the technique of urea
hydrolysis pioneered by Geus and his co-workers for, in particular, Ni-SiO2
catalysts.85 This method can give rise to very reproducible Ni crystallites of a
very narrow crystallite-size distribution86 and, in the normal method of use,
depends on a strong interaction occurring between the support and the
precipitating compound; in the case of a silica support, a nickel hydrosilicate
is formed as the catalyst precursor.85 The method developed for use with the
a-Al2O3 matrix involves impregnation of the matrix (generally in the form of
Raschig rings) with a solution containing urea and the components which are
to be precipitated.87788The excess solution is then drained off the support
and hydrolysis of the urea is brought about by heating the rings in an oven at
100C; the sample is then heated at a higher temperature to expel the
water before repeated impregnations and depositions. The sample is subsequently calcined and reduced in the usual way. It has been found that a
formulation involving nickel, aluminium, and lanthanum gives excellent
results. The solution from which the deposition of the active materials occur
is therefore made up from a mixture of Ni(N03)2, M(N03)3, and h(N03)3,
in the desired proportions, together with sufficient urea to bring about the
precipitation of these components on hydrolysis. The principal difference
between this method and that developed by Geus discussed above is that the
a-Al2O3 matrix in which deposition occurs does not act as a support for
the nickel but rather acts as host within whose pores are deposited the
coprecipitated types of material which have been discussed above.
83
84
86
87
88
B. Hohlein and R. Menzer, unpublished results.

T. Nicklin and R. J. Whittaker, Inst. Gas. Eng. J., 1968, 1 5 ; T. Nicklin and F.
Farrington, ibid., 1970, 15 1.
See, for example, L. A. M. Hermans and J. W. Geus, in Preparation of Catalysts II,
ed. B. Delmon, P. Grange, P. Jacobs, and G. Poncelet, Elsevier, Amsterdam, 1979,
p. 113.
J. T. Richardson, R. J . Dubus, J. G. Crump, P. Desai, U . Osterwalder, and T. S. Cale,
in Preparation of Catalysts 11, ed. B. Delmon, P. Grange, P. Jacobs, and G. Poncelet,
Elsevier, Amsterdam, 1979, p. 131; see also J. T. Richardson and R. J. Debus, J.
Catal., 1978, 5 4 , 207.
K. B. Mok, J. R. H. Ross, and R. M. Sambrook, in Preparation of Catalysts III, ed.
G. Poncelet, P. Grange, and P. A . Jacobs, Elsevier, Amsterdam, 1983, p. 291.
R . M. Sambrook and J. R . H. Ross, Br. P. Appl., 2 080 1 3 5 , 1982.
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27
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I-
Inert
-a
- Catalyst
600
T/"C
500
400
30C
20c
I
I
I0
Distance through bedlcm
Figure 11 Results of methanation test cam'ed out on a-Al,O,-based Ni-Al-La catalyst

in a reactor simulating the first reactor of the Adam system (Figures 2 and 3)
(B. Hohlein and R. Menzer, unpublished results)
The a-A1203-based materials described above have now been used in a

number of different types of steam-reforming plants with very encouraging
results. The addition of lanthanum t o the formulation had been shown using
small-scale continuous st eam-reforming equipment, to impart to the catalyst
an ability to resist carbon deposition; it also appeared to improve the stability
of the catalyst under operation conditions. These conclusions are borne out
by industrial experience. Experiments have also been carried out to test the
catalysts for methanation and a typical set of results will now be de~cribed.'~
A sample of a Ni-Al-La formulation containing 6.4 wt% Ni was tested in a
reactor which simulated the first catalyst bed of the Adam system (see Figures
2 and 3) and the results of the test are shown in Figure 11. In this reactor, the
catalyst bed length is 15 cm and it is preceeded by a section of inert packing
(5 cm of ar-A1203)whch serves as a preheater to a down-flow of feed gas. The
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28
Catalysis
inlet temperature is held at approximately 230 "C and the upper temperature
is limited at about 600C by some recirculation of the product gas. The
decrease in temperature after the peak maxima of the profiles shown in
Figure 11 is due to heat loss through the walls of the reactor. The temperature
profile moved slowly down the bed for the first 528 h but it then remained
relatively stable for the next 480 h. It would therefore seem that the initial
movement of the profile was due not to deactivation of the first portion of
the bed but to a gradual settling and that deactivation was very limited during
the period of the test. This was confirmed by removing samples after the
experiment and testing their activities using the DSC method (see above)
when the activities of used samples were close to those of the fresh
Hence, it is concluded that materials prepared in this way behave very well
under the conditions of the test. However, when a similar test was carried out
using a feedstock of industrial synthesis gas for a catalyst with a slightly lower
nickel content, the results were rather less satisfactory. In this case, the
temperature profile moved continuously down the bed and the test had to be
terminated after several weeks. It may be that the catalyst has insufficient
tolerance to the traces of sulphur present in such a feedstock. The problems
of sulphur tolerance will be considered further in a subsequent section.
Other Commercial Gztalyst Formulations. Many papers and patents have

recently appeared which are also addressed to the problem of maintaining
mechanical strength as well as activity and chemical stability during steam
reforming and methanation. Hence, only selected examples will be given in
the following paragraphs.
Several consider the use of suitable preformed supports. For example,
Okagami (Japan Gasoline Company) and Furata and Nakumura (Nikki
Chemical Company) have developed a materialg0 based on a refractory carrier
(e.g., ly-A1203,Sic, a-quartz, or ZrOz) in which Ni and Mg components are
precipitated by the addition of alkali in the presence of the carrier, the latter
comprising less than 70% of the final weight of the catalyst; the preferable
ratio of Ni to Mg is in the range 1.0 to 3.0. The material is claimed to have
good steam reforming activity and stability in the temperature range 300600C. As in other publications in which magnesia is included as a
component in the catalyst formulation, it is claimed to be beneficial in
maintaining activity by activating water and facilitating its reaction with the
hydrocarbon feed material. Another patent which claims the advantage of
'active magnesia' is that of Rostrup-Nielsen (Haldor Topsae A/S).9' In this
case, the importance of the formation of magnesium aluminate spinel
(MgA1204) as well as free MgO in the calcined catalyst is stressed, the former
giving considerable mechanical strength to the catalyst. The NiO and free
MgO of the calcined catalyst form a solid solution and, on reduction, this
gives small crystallites of nickel and 'active' MgO which counteracts carbon
deposition on the catalyst. Even if the nickel sinters during use, it can be
89
90
91
K. B. Mok, Thesis, University of Bradford, 1983.

A. Okagami, A. Furata, and T. Nakamura, US P., 3 992 166, 1976.
J. R. Rostrup-Nielsen, US P., 3 791 903, 1974;reissued as No. 28 655, 1975.
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29
redispersed by oxidation (hence forming the solid solution once more) and
subsequent re-reduction. The catalysts are claimed to have various possible
uses, depending on formulation, ranging from town gas production
(temperatures 350-750 "C) to hydrogen-rich synthesis gas production (6001000 "C). Some aspects of this type of catalyst were discussed previously2 in
connection with Rostrup-Nielsen's publications on the steam reforming
react ion .3
Russ and Broughton (United Catalysts Inc.) have disclosed a method of
preparing a steam reforming catalyst in which an ar-A1203material with an
area of less than 15 m2 g-' was used, in the form of rings or pellets, as
~arrier.'~The active components, Ni, Mg, and Fe, are deposited onto the
carrier by impregnation with suitable salts, usually nitrates, followed by
calcination and reduction. In the preferred embodiment, the nickel is present
in the range 8-20 wt%, magnesium 0.5-2%, and iron 1-3%. Barium may also
be added to the formulation as it has been found that it helps to prevent
carbon deposition on the catalyst, an observation also made in other work.
The catalyst was used successfully for steam reforming of hydrocarbons at
temperatures up to 780 "C.
A relatively early patent to Taylor and Sinfeltg3 (Esso Research and
Engineering Company) claims a series of formulations stable at temperatures
up to 870 "C whch have good sulphur resistance (see also following section).
These have 18-35 wt% NiO, 12-61 wt% Al2O3, 5-15 wt% CuO, 5-15 wt%
ZnO, 5-15 wt% Cr2O3, 1-15 wt% Ba, and 5-25% of other oxides including
Fe203, COO, Moo3, or W 0 3 either alone or in combination. As well as having
been tested for steam reforming, the catalysts have also been shown to have
good activities for hydrocarbon and CO conversion in automobile exhaust
gases containing thiophenic sulphur, tetraethyl lead, and organohalide
scavengers. The catalysts were prepared by a coprecipitation route involving
addition of ammonium bicarbonate to a mixture of the relevant nitrates.
R. C. Hansford (Union Oil of California) has described the preparation of
coprecipitated materials by the urea hydrolysis method;" not only the
preparation of Ni--A1203 catalysts for methanation is described but also that
of Co-Al203 and Fe-Al203 materials for Fischer-Tropsch synthesis reactions.
Hansford gives results of methanation tests similar to those described above
(Figure 11) which show that whereas such a Ni-A1203 material containing in
its calcined form 20.8 wt% NiO deactivated quite rapidly, one containing
55.9 wt% deactivated more than 20 times more slowly. (The temperature
profile moved one inch through the bed in 190 days). A material prepared by
separately precipitating the components homogeneously and then mixing
them deactivated as quickly as did materials prepared by non-homogeneous
coprecipitation. Hansford recognized that this homogeneously coprecipitated
materials contained a compound of the two components but did not establish
its composition. Undoubtedly this material is a highly dispersed form of the
92
93
94
K. J. Russ and R. Broughton, US P., 4 207 21 1,1980.

W. F. Taylor and J. H. Sinfelt, US P., 3 444 099, 1969.
R. C. Hansford, US P.,4 124 629, 1978.
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30
Catalysis
material prepared by the normal coprecipitation route whose composition

was discussed above.
Banks, Paterson, and Williams of British Gas have described" the
preparation and properties of a coprecipitated Ni-A1203 catalyst (50 wt% Ni)
to which were added 1.O wt% of an alkali metal and 0.5 wt% of ruthenium.
This material was shown to have desirable properties when used for the steam
reforming of a hydrocarbon oil in the temperature range 410-476C. It is,
however, not very likely that such a catalyst will be used commercially
because of the high cost of ruthenium and the limited supplies of t h s metal
which are available. Another British Gas patent, referred to previously,
introduces chromium into the formulation to improve the stability of the
resultant catalyst.77
Woodward (Imperial Chemical Industries) has described the formulation of
several methanation catalyst^.'^ The first is based on the hydroxycarbonate
coprecipitate Ni6A12(OH)16C03 4 H 2 0 discussed above and the second on
the same material substituted by some magnesium, Ni5MgA12(OH)16C03
4H20, sufficient to form MgA1204 or its precursors from the aluminium,
leaving the nickel free. The use of these catalysts is described in the open
~iterature.~~
In a series of papers and patents, T. Inui and his co-workers of Kyoto
University have described the use of catalysts consisting of Ni or Co supported
on various silica or silica-alumina supports of controlled g e ~ m e t r y . ' ~ - ' ~
Lanthanide oxides, such as lanthana or ceria, and platinum group metals, such
as Ru or Rh, were added to the formulation in atomic ratios of 0.2 and < 0.1,
respe~tively.'~The combined formulation had activities for methanation of
C 0 2 far in excess of single component catalyst^.'^ It was found to be
beneficial to the activities of catalysts formed on thermally resistant ceramic
silica-alumina fibres made into plates to treat them with a mixture of water
and ammonia after impregnation of the support with solutions of the active
components; in most cases, this gave improved methanation activities."' The
pore structure of the support had some effect on the activities of the final
catalyst^.'^ Another Japanese patent to Kawagoe, Matsuda, Kato, and
Kakashima (Hitachi Ltd.) describes the use of formulations containing rareearth oxides."' For example, a catalyst consisting of 7 0 wt% NiO, 10 wt%
La203and 20 wt% A1203resisted degradation after reduction and during the
methanation of carbon oxides twice as well as one containing 70 wt% COO,
10 wt% Ce02, and 20 wt% A1203.Similarly, G. B. Atkinson (US Department
of the Interior) has described catalysts derived from alloys of a Group VIII
metal (especially Ni or Co) with a rare earth metal (or Y) by reaction of the
95
96
97
98
99
loo
R . G. S. Banks, D. J . Paterson, and A. Williams, US P. 4 104 201, 1978.

C. Woodward, Ger. Offen. 2 621 314.
T. Inui, M. Funabiki, T. Iwana, and T. Sezume, Jpn. Kokai Tokkyo Koho, 79 1 1 9 385.
T. Inui, T. Sezume, K. Miyaji, and Y. Takegami, J. Chem. SOC., Chem. Commun.,
1979, 873.
T. Inui, M. Funabiki, M. Suehiro, andT. Sezume, J. Chem. SOC.,Faraday Trans. 1 ,
1979, 7 5 , 787.
T. Inui, M. Suehiro, Y. Saito, T. Miyake and Y. Takegami, A p p l . CataL, 1 9 8 2 , 2 , 389.
H. Kawagoe, S. Matsuda, A. Kato and F. Nakashima, Jpn. Kokai Tokkyo Koho,
80 31 804.
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31
alloy with a gas containing CO and H2 to form an intimate mixture of

the Group VIII metal or its carbide and the oxide of the rare earth of Y.lm
The resultant catalyst had an active area of 40 m2 g-l and had good activities
for me thanation at relatively low temperatures.
Wallace and his co-workers have studied in some detail formation of
catalysts from Ni-lanthanide metal intermetallic compounds (e.g., LaNi5)lo3
and from ThNi5, UNi5, and ZrNi5.1049105They too found that the first
component of each of these intermetallics was transferred to the oxide state
during use, the nickel remaining in the metallic state. The catalysts derived
from ThNi5 and ZrNi5 were particularly interesting, the former having a
specific activity exceeding that of a conventional Ni-Si02 catalyst by an
order of magnitude and the latter being roughly equivalent.lW It would
appear that the difference arises from the ability of the T h o 2 to resist carbon
deposition.'06 The thoria-based catalyst also had a higher resistance to H2S
poisoning than did the zirconia-based material. lo6
Nicolescu and co-workers have reported'" that a catalyst containing
15-30 wt% Ni, 2-6 wt% CO or Mo, and 1-2.5 wt% Cr supported on activated
alumina is active for the methanation of high space-velocity gases containing
up to 3% CO at temperatures in the range 180-250C with 98.5%
conversion. Surprisingly, the catalysts were reduced at temperatures as low as
200-250 "C. No data are given on the behaviour at higher temperatures.
Baird and Steffgen have reported a novel approach to the preparation of
active methanation catalysts.'08 Here, aluminium was flame-sprayed onto a
nickel surface and the two components were alloyed by heating to
temperatures close to the melting point of aluminium (660C) to form a
Raney-type alloy and then activated with caustic leach. Methanation
activities were obtained using a pulse microcatalytic reactor which does not
give results that are particularly relevant to industrial practice but they
indicated that the temperature of alloying was critical in determining the
activities of the catalysts. Little deactivation was observed during the tests.
However, an activated sample thermally treated at 500C for 8 h lost a
substantial proportion of its activity. The original activity could be restored
by flame spraying with further aluminium followed by heat treatment and
leaching. This type of catalyst-preparation process may have some importance
in reactors designed for optimum heat-transfer properties.
Bartholomew and his colleagues have conducted a large number of studies
lo'
104
105
Io6
lo8
G. B. Atkinson, US P., 4 256 653, 1981; see also G. B. Atkinson and L. J . Nicks, J.
Catal., 1977, 46, 4 1 7 .
V. T. Coon, T. Takeshito, W. E. Wallace, and R. S. Craig, J. Phys. Chern., 1976, 3 0 ,
1878.
A. Elattar, R. Takeshita, W. E. Wallace, and R. S. Craig, Science, 1977, 196, 1093.
W. E. Wallace, A. Elattar, T. Kakeshita, V. T. Coon, C. A. Bechman, and R. S. Craig,
in 'Proc. 2nd Int. Conf. on Electronic Structure o f the Actinides', ed. J. Mulck, W.
Siski, and R . Troc, Polish Acad. Sciences, Warsaw, 1977, p. 357.
A. G. Moldovan, A. Elattar, and W. E. Wallace, J. Solid State Chern., 1978, 2 5 , 23.
I. V. Nicolesen, G. Pop, A. Cobzaru, A. Nicolescu, A. Mihai, H. Florescu, G. Musca, I.
Olaru, M. Dardan, and Boteanu, Rom. P., 66 388.
M. J. Baird and F. W. Steffgen, Ind. Eng. Chem., Prod. Res. Dev., 1977, 16, 142.
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32
Catalysis
of the use of catalysts based on nickel and other metals for methanation of
carbon monoxide. Some of this work will be discussed here while discussion
of some other papers will be deferred t o a later section. Relevant to the
present discussion of catalysts claimed to have stability under the relevant
reaction conditions is the use by the Brigham Young University group of
catalysts prepared using monolith supports.lW7
These catalysts are
prepared in Cordierite (Celcor, Corning Glass Works) monolith supports by a
coating technique using a 5% Ni-AI203 catalyst.'0g The intrinsic activity of
such a catalyst, based on the content of active material, was the same as the
unsupported 5% Ni-A1203 material but it could be used at much higher space
velocities without problems of transport limitations. The catalysts have been
used in a detailed kinetic study of the methanation of CO.
Finally, the MCR-2X catalyst manufactured by Haldor Topsgje, whose
behaviour in the Adam I reactor was described above (see Figure 3 and Table
l), should be mentioned. This is almost certainly composed of nickel and
molybdenum supported on Zr02-A1203 and fired at high temperatures.'"
The other catalyst, MCR-4, used in the test discussed above for the second and
third reactors, may be a more conventional Ni-Mg0-A1203 f o r m ~ l a t i o n . ~ ~
Sulphur-resistant Gztalysts. The problem of sulphur poisoning of nickelbased catalysts is particularly serious as sulphur is rapidly and irreversibly
adsorbed by nickel under most conditions, particularly at those temperatures
encountered at the entrance to typical methanation reactors (- 300 *C).'12
Under these conditions, not only a monolayer of chemisorbed sulphur forms
but incorporation of sulphur in the nickel is also found.ll3 It is generally
considered to be most unlikely that sulphur-resistant nickel-containing
catalysts will ever be achieved as, even if an additive can be found which will
preferentially adsorb sulphur, the nickel will deactivate as soon as the additive
has reacted fully. For nickel-containing catalysts, the main hope lies in
'sulphur tolerance', Le., the use of materials with high nickel contents which
continue to function even after substantial quantities of sulphur have been
incorporated in the catalysts. Such solutions are likely to be reasonably
successful under conditions where less than parts per million (- 0.1 p.p.m.)
levels of H2S (or other sulphur-containing molecule) are present. However,
some consideration has been given to catalysts which can resist poisoning by
relatively high partial pressures of H2S such as present in untreated synthesis
gas resulting from coal gasification. Whether or not such an approach is
preferable to that involving the use of more traditional Ni-based catalysts
together with suitable desulphurization techniques prior to the catalyst bed
remains to be seen. It would seem that as the product gas will also have to be
desulphurized, it may be cheaper and easier to use prior desulphurization
109
'lo
'11
'I2
'13
G. A. Jarvi, K. B. Mayo, and C. H. Bartholomew, Chem. Eng. Commun., 1 9 8 0 , 4,

325.
E. L. Surgue and C. H. Bartholomew, A p p l . Catul., 1 9 8 2 , 2 , 239.
Br. P., 1 546 774.
See, for example, C. H. Bartholomew, P. K. Agrawal, and J. R. Katzer, Adv. Catul.
1 9 8 2 , 31, 1 3 5 .
J . H. Saleh, C. Kemball, and M. W. Roberts, Trans. Furaduy SOC.,1 9 6 1 , 5 7 , 1771.
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33
because the nickel-based catalysts are generally much more active than the
sulphur-resistant catalysts developed up till
However, t h s will
depend very much on the relative costs of desulphurization prior to or after
methanation. The cost of a unit to bring about desulphurization to the 0.1
p.p.m. H2S level required for the successful long-term operation of current
Ni-based catalysts is approximately 12% of the total initial capital requirements for a coal gasification plant.'" ,
There have been a considerable number of papers reporting the properties
of sulphur-resistant methanation catalysts, i.e., catalysts which can operate
successfully in significant partial pressures of H2S. Most of these report work
using catalysts containing vanadium, molybdenum, and such metals. However, attempts have been made to find nickel-based catalysts containing
suitable additives to allow them to operate in such atmospheres. For example,
Bartholomew and Uken"' have compared the deactivation behaviour of a
range of nickel catalysts in 10p.p.m. H2S. They found that nickel boride
catalysts and Raney nickel materials deactivated more slowly than did
unsupported nickel and alumina-supported nickel. They attributed this
improvement to two factors:
(i) lower rate constants for the deactivation process;
(ii) larger capacities for sulphur adsorption.
It should be noted that the methanation activities of all the catalysts studied
fell to 50% or less over a period of 24h. Fowler and Barth~lornew''~had
earlier reported similar results to those obtained with their boron-promoted
catalysts using Ni-Mo03 rnaterial~,''~Papers have been published on the
deactivation of Ni catalysts by H2S.A recent paper by Erekson and
Bartholomew1l8 considers in detail the complex inter-related effects of
H2S, CO, and H 2 0 partial pressures on the rate of deactivation. The authors
also discuss their results fully in relation to other investigations of this subject,
for example those by Fitzharris et al.'" Dalla Batta et al.I2' and Alstrup
et al. 12' Rostrup-Nielsen has recently reviewed the problems of sulphur
poisoning and the regeneration of sulphur-poisoned catalysts for steam
reforming and methanation.'22 A review by Kelley and Goodman123 discusses
the surface physics approach to the methanation (adsorption studies on single
crystal surfaces, etc.) and also discusses the effect of sulphur adsorption on
the methanation reaction as investigated by Auger spectroscopy, LEED, etc.
The review deals particularly with work on this subject at the National
'"
'I4
'''
'19
121
'*'
R . A. Dalla Betta and K. K. Ushiba, Hydrocarbon Process., Int. Ed., 1 9 8 0 , 59, 157.
C. H. Bartholomew and A. H. Uken, Appl. Cutal., 1982, 4, 19.
J. P. Leonard, Chem. Eng., 1979, 8 6 , 183.
R. W. Fowler and C. H. Bartholomew, Ind. Eng. Chem., Prod. Res. Dev., 1979, 18,
339.
E. J. Erekson and C. H. Bartholomew, Appl. Cutal., 1 9 8 3 , 5 , 323.
W. D. Fitzharris, J . R. Katzer, and W. H. Manogue, J. CutaL, 1 9 8 2 , 7 6 , 369.
R. A. Della Betta, A. G. Piken, and M. Shelef, J. CutuL, 1975, 40, 173.
I. Alstrup, J. R. Rostrup-Nielsen, and S. Roen, Appl. Catalysis, 1981, 1, 303.
J. R. Rostrup-Nielsen, NATO Adv. Study Inst. Ser., Ser. E, 1982, 'Progress in
Catalyst Deactivation', p. 209.
R. D. Kelley and D. W. Goodman, in 'Chemical Physics of Solid Surfaces and Heterogeneous Catalysis', ed. D. A. King and D. P. Woodruff, Elsevier, Amsterdam, Oxford
and New York, 1982, Vol. 4, p. 427.
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34
Bureau of Standards, Washington. Oudar has also reviewed work on sulphur

poisoning of single crystal surfaces.'24
A number of claims have been made for successful sulphur-resistant
catalysts. For example, Mobil have disclosed a sulphur-resistant material
based on V2O3 and Moo3 supported on alumina (approximately 5:5:90)
w h c h operated successfully in a synthesis gas feed containing 0.6% H2S at
temperatures up to about 500 OC.12' Catalysts and Chemicals (now United
Catalysts Inc,) have reported similar properties for catalysts based on nickel
and chromium and supported on magnesium silicate or magnesium aluminate.'26 These catalysts had high methanation activities before sulphidation
and much of this activity was retained afterwards. Shavloy and Reucroft have
examined the surface properties of this (or a similar) Ni-Cr-MgSi03 catalyst
using XPS.127 They found that both nickel sulphide and nickel sulphate are
present on the surface of a sulphided material which still had significant
methanation activity. Stencel and his colleagues have studied a similar catalyst
using infrared and Raman spectroscopy.'28 Happel and Hnatow (American
Gas Association) have reported the development of sulphur resistant
molybdenum-containing catalysts for methanati~n.'~' They claim that this
can be used in S-containing atmospheres with less than
3% suphur at
temperatures between 400 and 700"C, at pressures up to 65 atm. and with
hourly space velocities from 80-1 0 000. The catalyst contains an element of
the lanthanide or actinide group; this is said to improve the catalyst
performance and to obviate the need to operate at a H2 to CO ratio of 3.0 as
is required for Ni-based catalysts. Results are given in the patent for a Ce-Mo
catalyst with these elements in the ratio 9: 1; the catalyst gave a conversion of
40% with a selectivity of 50% to methane at 450C with a space velocity
of 4800 h-l. Catalysts containing Mo with La, U, or Th were also used.
Slaugh has claimed that a catalyst consisting of MoSi2 has resistance to
s u 1 p h ~ r . lT~h~s material gave 20% conversion of CO + H2 mixture (1 :3) at
500-600 "C and the conversion was > 2% after 90 min of H2S treatment.
Other transition metal silicides (e.g., ZrSi, WSi2) were tested for methanation
but had no activity
Haldor Tops$e have described a number of sulphur resistant catalyst
formulation^.'^' ,132 For example, metals of Groups VB or VIB with Fe, Co,
or Ni on a porous ceramic (A1203 or Ti02) as support can give gases
containing large amounts of hydrocarbons in addition' to methane in the
124
12'
J. Oudar, Catal. Rev.-Sci. Eng., 1980, 22, 171;Stud. Surf. Sci. Catal., 1982, 11, 2 5 5 .
Mobil, U S P., 4 1 7 7 2 0 2 , 1981.
Catalysts and Chemicals Inc., Report FE-2023-9, 1978 (Chem. Absfr., 1 9 8 0 , 9 2 , 131
676).
R. B. Shavloy and P. J . Reucroft, Univ. o f Kentucky, Inst. Min. Miner, Res., Techn.
Report, IMMR 46-PD-80.
128
J . M. Stencel, E. B. Bradley, and F. R. Brown, A p p l . Spectrosc., 1 9 8 0 , 3 4 , 319.
1 2 9 J . Happel and M. A. Hnatow, US P., 4 151 1 9 1 , 1 9 8 1 .
L. H. Slaugh, US P., 3 9 9 6 2 5 6 , 1980.
131
J . R. Rostrup-Nielsen, K. Pedersen, and I. G. H. Joergensen, Belg. P., 8 8 6 7 0 3 , 1981.
13' K. J . Andersen, K. Pedersen, I. G , H. Joergensen, and J. R. Rostrup-Nielsen, Belg. P.
8 8 6 7 0 3 . 1981.
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35
presence of 1% H2S.13' A catalyst consisting of 6.6% Mo and 4.7% Co (essentially as the sulphides) supported on alumina when tested at 300C in a gas
mixture containing 48% H2, 48% CO, 1% H2S, and 3% Ar at a pressure of
30atm. gave 16% CH4, 47% C2Hs, and 28% C3H8 with a conversion of 11%
per pass through the reactor. Catalysts with a higher selectivity to methane
under similar conditions result from the use of V or Mo supported onTi02.132
These are said to be more active than those supported on Al2O3. For
example, catalysts prepared on a high-area Ti02 support using a solution of
ammonium molybdate containing an alkanolamine and then activated in 2%
HZS in H2 at 300 "C (after calcination at 550 "C) gave high conversions at
300 "C using the gas mixture given above with 85% selectivity to methane.
Other Investigations of Nickel Catalysts. In this section a brief review will be
given of some recent academic work on supported nickel catalysts where the
main emphasis has been on the influence of the support in determining the
properties of the nickel. Some of this work was recently reviewed by
V a n n i ~ e . ' ~Unusually
~
high specific activities were first reported for the
Ni-Ti02 system by Vannice and Garten.134-136 The turnover number (TON:
the number of molecules reacting per metal site per second) for Ni-Ti02
catalysts were found to be 1-2 orders of magnitude higher than those for
conventional Ni catalysts. Similar results have since been obtained by other
workers for the Ni/Ti02 and other similar ~ y s t e m s . l ~ ~An
- l ~interesting
~
feature of these results is that whenever the so called 'Strong Metal Support
Interaction' (SMSI) occurs, the product selectivity in the reaction of CO with
H2 changes towards the production of higher hydrocarbons. There is also a
suppression of hydrogen chemisorption
There has been considerable
discussion of the nature of SMSI. It has been observed that the Ti02 is
partially reduced by spillover from the nickel during the reduction stage and
it has been suggested that the enhanced TONS are due to electron transfer
from this partially reduced support to the active metal phase." Burch and
Flambard have recently argued, however, that an alternative explanation is
that a new type of site is created at the interface between the metal and the
partially reduced
,142 Such an explanation is consistent with
results obtained on partially reduced coprecipitated Ni-A1203 catalysts which
also showed a relatively high selectivity towards higher hydrocarbons; here, a
site different to metallic nickel must also be i n ~ o l v e d . Several
~ ~ , ~ ~patents
133
M. A. Vannice, in 'Catalysis-Science and Technology', ed. J. R. Anderson and M.

Boudart, Springer-Verlag, Berlin, 1 9 8 2 , Vol. 3, p. 139.
1 3 4 M. A . Vannice and R . L. Garten, J. Catal., 1979, 56, 2 3 6 .
135
M . A. Vannice and R. L. Garten, J. Catal., 1980, 66, 2 4 2 .
1 3 6 M . A. Vannice, J. Catal., 1982, 7 4 , 199.
137
C. H. Bartholomew, R . B. Pannell, and J. L. Butler, J. Catal., 1 9 8 0 , 6 5 , 335,
1 3 8 C. H. Bartholomew, R. B. Pannel, J . L. Butler, and D. G. M. Mustard, Ind. Eng.
Chem., Prod. Res. Dev., 1 9 8 1 , 2 0 , 2 9 6 .
1 3 9 S . J. Tauster and S . C. Fung, J. Catal., 1 9 7 8 , 5 5 , 29.
140
S. J. Tauster, S. C. Fung, R. T. K. Baker, and J. A. Horsley, Science, 1 9 8 1 , 2 7 1 , 1 1 2 1 .
1 4 ' R. Burch and A. R . Flambard, J. CataE., 1 9 8 2 , 7 8 , 389.
1 4 * R. Burch and A. R. Flambard, in 'Metal-Support and Metal Additive Effects in
Catalysis', ed. B. Imelik e t al., Elsevier, Amsterdam, 1982, p. 193.
143
C.-C. Kao, S.-C. Tsai and Y.-W. Chung, J . Catal., 1 9 8 2 , 7 3 , 136.
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36
Catalysis
have been issued to Exxon for catalysts in which the SMSI effect exists:
claims for these catalysts included improved activity and life as well as
improved selectivity to higher hydrocarbons and higher resistance t o nickel
carbonyl f0rmati0n.l~~
147
Formulations covered were Ni-Ti02 ,146
Ni-Nb2O5,I4' and Ni-Ta205.147 A recent publication shows that Ni-Nb2 0 5
catalysts give high proportions of olefins among the products of the C G H 2
react ion
The Use of Other Metals for Methanation and Steam Reforming. - The review
by V a n n i ~ e 'gives
~ ~ a good description of work in the reactions of CO with
hydrogen over metals such as Fe, Ru, Co, and other Group VIII metals.
Hence, only a few selected references will be discussed here.
Iron. Iron is the catalyst used for the production of hydrocarbons by the
medium-pressure Fischer-Tropsch synthesis route. Dry has recently reviewed
the use of this process in the SASOL plants in South Africa and the nature
of the catalysts used in such ~1ants.l~'Under certain conditions, generally
low pressures and temperatures, methane is one of the predominant
p r ~ d u c t s . ~ ~ Recent
, ~ ~ ~ work
, ' ~ ~has shown the importance of SMSI effects
with supported iron catalyst^.'^^-'^^ With aluminium-supported catalysts,
there was found to be a metal-support interaction such that the least active
catalysts gave the highest selectivities to higher hydrocarbons, particularly
light 01efins;'~~
,153 similar conclusions were reached with Ti02 and MnO
supports, the latter giving particularly low selectivities to methane.154
However, a paper by van Dijk et aE.,1s5 which lists a number of other
publications which also claim that Fe-MnO catalysts have selectivities to
olefins, shows that such a catalyst prepared using pure components has a high
selectivity to methane and that selectivity to olefins results if sulphate ions
are incorporated in the catalyst formulation; other papers which show this
effect of sulphate ions are also listed. Jung, Walker, and V a n n i ~ e lhave
~~
recently reported that the support can have a major effect on the saturated
hydrocarbon/olefin ratio over supported Fe catalysts; in most cases, methane
selectivities ranged from 40-60%.
Ruthenium. V a n n i ~ e ' discusses
~~
in some detail a number of infrared studies
of ruthenium catalysts in CO + H2 atmospheres in connection with a disP. J. Reucroft, H. Parekh, P. Ganeson, S. N . Russel, and B. H. Davis, A p p l . Catal.,
1982, 3, 65.
H. Imamura and W. E. Wallace, J. Catal., 1 9 8 0 , 6 4 , 2 5 1 .
1 4 6 M. A. Vannice and R. L. Garten, J. Catal., 1980, 6 6 , 2 4 2 .
1 4 7 E. L. Kugler and S . J. Tauster, US P., 4 2 0 6 1 3 5 , 1980.
148
E. I. KO, J. M. Hupp, and N. J. Wagner, J. Chem. SOC., Chem. Comrnun., 1983, 94.
1 4 9 M. E. Dry, 'Catalysis-Science and Technology', ed. J . R. Anderson and M. Boudart,
Springer-Verlag, Berlin, 1 9 8 1 , Vol. 1 , p. 1 5 9 .
M. J . Heal, E. C. Leisegang, and R. G. Torrington, J. CutaZ., 1 9 7 8 , 5 1 , 314.
l S 1 D. J. Dwyer and G. A. Somorjai, J. Catal., 1978, 52, 2 9 1 ; 1 9 7 9 , 56, 2 4 9 .
152
V. Perrichon, P. Turlier, J. Barrault, C. Forquy, and J. C Menzo, AppZ. CutaE., 1 9 8 1 ,
1, 169.
153
J . Barrault, C. Forquy, and V. Perrichon, J. Mol. Catal., 1 9 8 2 , 17, 1 9 5 .
J. Barrault and C. Renard,Nouu. J. Chim.. 1983, 7 , 149.
155
W. L. van Dijk, J . W. Niemantsverdriet, A. M. van der Kraan, and H. S. van der Baan,
A p p l . Cutal., 1982, 2, 2 7 3 .
s6 H.-J. Jung, P. L. Walker and M. A. Vannice, J. Catal., 1982, 75, 4 1 6 .
144
145
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Metal Chtalysed Methanation and Steam Refoming
37
cussion of the mechanism of the reaction. Work reported by King157 on the

effect of the nature of the support on the activity and selectivity of Ru
catalysts shows that while the support exerts some influence on the selectivity
of the reaction, the effect of Ru crystallite size is much greater; larger Ru
crystallites have higher specific activities than do well dispersed Ru particles.
Leith"' has suggested that electronic interactions between the small metal
crystallites and the electron-donor sites in Y-zeolites enhances their selectivity
towards olefin formation. Yang and Goodwin15' have reported that the
addition of silica to Ru-A1203 and Ru-Ti02 catalysts changed their conversions and product selectivities. Kikuchi et al. 16* have examined a number
of supported Ru catalysts and showed that V2O3 supported materials had
particularly high specific activities and relatively high selectivities to
unsaturated hydrocarbon products. Bowman and Bartholomew161 have
studied the deactivation of Ru-A1203 catalysts by carbon; deactivation has a
negligible effect at low temperatures (< 570K) but becomes important at
higher temperatures.
Rhodium. It appears that the hydrogenation of CO (and C 0 2 ) over rhodium

catalysts depends to a very considerable extent on the formulation and
method of preparation. Several workers have examined the dependence of the
activity and selectivity of rhodium catalysts on the support ~ s e d . The
~ ~ ~ - ~
same type of metal-support interaction appears to occur with rhodium as
with nickel and other metals; a Rh-Si02 catalyst appears to give predominantly methane,163-166 as is the case also with Rh-A1203162166 ,167
and Rh-MgO,'@ 166 167 while Rh-Ti02 ,lW 165 Rh-Zr02 ,166 167 and
Rh-Nb205 164, 166 167 tend to give higher hydrocarbons. Solymosi et al. found
that the specific activity of a Rh-Ti02 catalysts was more than an order of
magnitude higher than that of Rh-MgO and Rh-Si02 catalyst^'^^^'^ and
that it was also rather higher than that for a Rh-Al2O3 ~ a t a l y s t . ' ~ ~To? ' ~ ~
explain the results for the Rh-Ti02 catalysts, they suggested that there was
an electronic interaction between the metal and the support,'64 a conclusion
which was also reached by Meriaudeau et all6' Izuka et al. found that
Rh-Nb205 was the most active catalyst for the reaction of CO H2 and that
Rh-Zr02 was almost as active.167 For the C 0 2 + H2 reaction, Rh-Zr02 was
the most active and reaction occurred at temperatures as low as 50C.166 In
the reaction of C 0 2 , only CH4 was formed at temperatures up to 200 oC.166
It was also found that the CO + H2reaction was faster over oxidized samples
of Rh-Zr02 and Rh-Al2O3 than over the corresponding reduced samples.f66
9
158
16*
16'
162
163
16'
166
D. L. King, J. Catal., 1 9 7 8 , 5 1 , 386.

I. R. Leith, J. Chem. SOC.,Chem. Commun., 1983, 9 3 .
C.-H. Yang and J. G. Goodwin, Can. J. Chem. Eng., 1983, 6 1 , 2 1 3 .
E. Kikuchi, H. Nomura, M. Matsumoto, and Y. Morita, Appl. Catal., 1 9 8 3 , 7 , 1.
R. M. Bowman and C. H. Bartholomew,Appl. Catal., 1 9 8 3 , 7 , 179.
F. Solymosi, A. Erdohelyi, and M. K O C SJ.
~ , Catal., 1 9 8 0 , 6 5 , 428.
F. Solymosi, A. Erdiihelyi, and T. Bansagi, J. Catal., 1981, 6 8 , 67.
F. Solymosi, I. Tomb&, and M. Kocsis, J. Catal., 1982, 7 5 , 7 8 .
P. Meriaudeau, H. Ellestad, and C. Naccache, J. Mol. Catal., 1 9 8 2 , 17, 2 1 9 .
T. Tizuka, Y. Tanaka, and K. Tanaba, J. Cutal., 1 9 8 2 , 7 6 , 1 .
T. Izuka, Y. Tanaka, and K. Tanabe, J. Mol. Catal., 1 9 8 2 , 1 7 , 381.
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Niwa and Lunsford168 studied the CO H 2 0 reaction over Rh-Al2O3,

Rh-Y zeolite, Rh-Si02, and Rh-NaY zeolite and found that methane was
formed as well as C 0 2 and H2, probably by the hydrogenation of surface
carbon by the hydrogen formed in the water-gas shift reaction; carbon was
therefore concluded to be an intermediate in the reaction over these catalysts.
The activities of the catalysts fell in the order given. Castner, Blackader, and
Somorjai studied the CO H2 reaction over Rh foil and a Rh(l,1,1) surface at
pressures of 6 atm. They found that clean surfaces gave only light hydrocarbons while a pre-oxidized surface produced predominantly oxygenated
specie^.'^' Evidence was presented which showed that the reaction mechanisms over the clean and oxidized surfaces were different, hgher oxidation
state being required to produce oxygenates. The observation of oxygenated
species as products of the reaction of CO and H2 over rhodium is in agreement
with the observation by Bhasin et all7' that acetic acid, acetaldehyde, and
ethanol could be formed over such catalysts, the balance (- 50 wt%) being
methane. Ichikawa has also reported that supported rhodium has a high
selectivity to methanol and ethan01.l~~
There is mounting evidence to support
the idea that a combination of metallic rhodium and Rh' surface sites are
necessary to bring about the production of ethanol.ln
Other Metals. Vannice has reported that SMSI effects also occur with
platinum catalysts,173 in agreement with similar observations by Sarkany and
Gonzales,174 who found that specific rates for the formation of methane over
Pt-A1203were greater than over Pt-Si02 catalysts. In contrast, Rabo et al. 17'
found that Pt, Pd, and Ir catalysts produced CH30H selectively and that
methane only formed under conditions when CH30H formation was not
thermodynamically favoured. Polazov et al. also observed methanol formation
over Pd ~ a t a 1 y s t s . l ~
~
0s-MgO
catalysts, prepared using Os3(CO)12, were
found to be selective for the formation of C I S 4 hydrocarbon^.'^' A paper
by Saito and Anderson'78 discusses the use of various molybdenum-containing
catalysts. These authors found that catalysts derived from molybdenum
carbide and molybdenum metal were less active for CO methanation than was
nickel but that their stabilities in methanation were greater than that of
nickel; materials derived from molybdenum nitride, Moo2, MoS2, and Moo3
were less active and stable. Bowman and B ~ r w e l l lfound
~ ~ that catalysts
derived from Mo(CO)~supported on alumina had relatively h g h methanation
activities.
16'
16'
170
17'
172
I73
174
17'
17'
177
17'
179
M. Niwa and J . H. Lunsford, J. Catal., 1982, 7 5 , 302.

D. G. Castner, R. L. Blackadar, and G. A. Somorjai, J. Catal., 1 9 8 0 , 6 6 , 257.
M. M. Bhasin, W. J . Bartley, P. C. Elgen, and T. P. Wilson, J. Catal., 1 9 7 8 , 5 4 , 120.
M. Ichikawa, Bull. Chem. SOC.Jpn., 1978, 5 1 , 2 2 6 8 and 2 2 7 3 .
F. H. A. van den Berg, Thesis, R. U. Leiden, 1 9 8 3 .
M , A. Vannice, J. Catal., 1 9 8 3 , 8 2 , 2 1 3 .
J. Sarkany and A. D. Gonzalez, Appl. Catal., 1982.
M . L. Poutsma, L. F. Elek, P. A. Ibarbia, A. P. Risch, and J . A. Rabo, J. Catal., 1 9 7 8 ,
52, 157.
A. Palazov, G. Kadinov, Ch. Bonev, and F. Shopov, J. Catal., 1 9 8 2 , 7 4 , 4 4 .
M. Weiba, J. P. Scott, R. Barth,and B. C. Gates, J. Catal., 1 9 8 1 , 7 1 , 373.
M. Saito and R. B. Anderson, J. Catal., 1 9 8 0 , 63, 4 3 8 .
R. G. Bowman and R. L. Burwell, J. Catal., 1 9 8 0 , 6 3 , 4 6 3 .
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Metal Catalysed Methanation and Steam Refomzing
39
The above descriptions of the behaviours of various metals is not intended

to be comprehensive but is instead intended to give some picture of the
complexity of the chemistry of such systems. It is no longer possible to
compare the behaviour of different metals without regard to the way in
whch the catalyst is prepared. The catalysts formulation (and even its pretreatment) is critical in determining its behaviour. Each study of a particular
system must be backed up by a careful characterization of the catalyst
concerned; in particular, before worthwhile comparisons can be made,
reliable determinations of metallic surface areas have to be carried out.
Catalysts for Steam Dealkylation. - Some mention has already been made of
the fact that Rh, Pt, Ir, and Pd are the most effective catalysts for reactions
such as the steam dealkylation of toluene and that a crown impregnated
Rh-A1203 catalyst is particularly active (see p. 12).3*42 Brief mention will
be made here of the role of the catalyst support in the light of the
observations summarized in the previous sections. Duprez and his colleagues
have classified the metals which will catalyse the reaction into two groups:
those with which there is a dependence on the support (Pt,Rh, and Pd) and
those which are not (Ni, Co, Ru, and to some extent Ir).38 These authors
examined the toluene dealkylation reaction over these metals supported on
alumina, silica, and titania. The nature of the support was found to affect
both the activity of a particular metal and its selectivity towards benzene. In
general, alumina-supported materials were better dispersed than silicasupported materials and gave a higher selectivity towards benzene; the
authors were unable to distinguish to what extent the selectivity was due to
dispersion or support effects. Relatively little information is given for Ti02supported materials; for Pt, the selectivities are roughly the same as for a
Si02- and A1203-supported materials but for Rh, a considerable improvement
in selectivity seems to result. The alumina-supported catalysts were considerably more active than the silica-supported ones while the titania-supported
materials had slightly lower activities than the former; again, relatively few
results are presented. The authors suggest that on Pt, Rh, and Pd catalysts,
the mechanism involves adsorption of water on the support and of the
toluene on the metal and subsequent reaction involving migration of the OH
groups to the metal. In the case of the other metals, a competitive reaction on
the metal surface is suggested to occur. The authors say that the effect of the
support is unlikely to be due to a metal-support interaction, but that the
possibility cannot be excluded. It would seem that further work using steam
dealkylation as a model reaction on other supports could be very worthwhile.
It would appear that no work has been done over the last few years on the
effect of support on other types of steam reforming reactions such as the
CH4 H 2 0 or CH30H + H 2 0 reactions. This might be a fruitful area for
research.
4 Some Mechanistic Aspects of the Methanation and Steam

Reforming Reactions.
The main intention of this review has been to discuss the process and the
catalyst used in the various reactions. However, it would not be complete
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Catalysis
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without at least brief mention of some of the current ideas concerning the
mechanism of the methanation and steam reforming reactions, particularly
the former.
Methanation. - There has been very considerable interest in the mechanism of

this reaction since it was recognized that the reaction over nickel was likely to
proceed through surface carbon species rather than through oxygenated
surface intermediates. Vannice has recently summarized the evidence for the
dissociation of carbon monoxide over nickel and other metals133 and so this
need not be repeated here, The important consequence of this conclusion
however is that kinetic expressions previously put forward cannot be valid.
Hence, a number of attempts have been made to formulate suitable equations
to explain kinetic data. In the light of the data which has been summarized
on the effect of catalyst structure on catalytic activities, it is not entirely
surprising that a number of different expressions have been derived to
explain different sets of results. It is likely, however, that a number of these
expressions will be required to distinguish between the various models. In the
following discussion, again no attempt is made to achieve a complete
coverage; rather, several examples are chosen from the experience of this
author to illustrate the problems involved.
In 1975 Vannice published a comprehensive study of the kinetics of the
methanation of carbon monoxide over various metals.45 He analysed his
results in terms of a rate-determining step for the reaction involving the
interaction of adsorbed CHOH species and adsorbed H atoms:
CHOH (ads) -I-y/2H2 (ads)
CH,(ads)
+H20
(10)
where y is between 0 and 4. He then derived a kinetic expression involving
the assumptions of the Langmuir isotherm to explain the observed kinetics.
This involves the assumption that all steps prior to this rate-determining step
are in equilibrium. The treatment was later modified to give a more satisfactory equation.'" In 1981 Ross'" derived a kinetic expression to explain the
earlier results of Vannice which involved the assumption that the ratedetermining step was the reaction of adsorbed carbon and hydrogen atoms:
-+
c(ads) -!- y H ( a d s )
CHy(ads)
(1 1)
The derivation again made use of the assumptions of the Langmuir approach,
the following equilibria being assumed to hold:
CO(g) =+ CO (ads)
CO (ads) + C (ads)
+ 0 (ads)
H2(g) + 2 H (ads)
2H (ads)
18'
+ 0 (ads)
+ H 2 0 (g)
D. F. Ollis and M. A. Vannice, J. Catal., 1975,38, 514.

J . R. H. Ross, J. Catal., 1981,71,205.
(1 2)
(1 3)
(1 4)
(1 5 )
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41
As will be seen, it is this last step whch distinguishes the mechanism from
those put forward by others. A rate expression of the following form resulted:
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P C OP H ,
y2)/PH, 0
Rate a
(16)
(1 + b c P c o P H , / ~ H , d+
where y is that shown in equation (1 1) and bc is an adsorption coefficient. By
making approximations, this equation could be transformed to a simple
power-rate expression which agreed with Vannices results with a value of
y = 2 for nickel catalysts. As Vannice did not examine the effect of water
partial pressure on the rate of reaction, the validity of the equation could not
be fully confirmed.
Van Meerten et uZ.lg2 have carried out a painstaking examination of the
kinetics of the methanation reaction over a 5% Ni-SiOz catalyst in a flow
reactor at temperatures from 460-840 K, carbon monoxide pressures from
1-650 Torr and hydrogen pressures from 55-700 Torr. They allowed for a
gradual deactivation of the catalyst by making regular measurements at a set
of standard conditions and correcting their data accordingly. Their results
represent one of the largest ranges of reaction conditions studied and are
therefore very suitable for use to distinguish various kinetic equations. Van
Meerten and his co-workers considered the following sequence of steps:
cog+2s
COa
=+
CO,
(1 7)
Ca+Oa
(18)
=+
H z g + 2 s =+ 2Ha
0, Ha =+ OH, + s
(1 9)
OH,
+ Ha
HzOg
Here, s represents a free surface site and subscripts a and g represent adsorbed
and gas-phase species, respectively. It is assumed that CO adsorbs on two sites
prior to dissociation on the same sites and that hydrogen competes for the
same sites. It is assumed that all steps prior to the rate-determining steps are
in equilibrium. Reactions (21) and (25) were assumed to occur only in one
direction and to have the same rates. The assumption that equation (21) is
not in equilibrium would appear to be the main difference between the
approach of Van Meerten et al. and that put forward by Ross.~ Van Meerten
et al. proceeded to consider a series of different equations which they then
attempt to fit to their data. They showed that the best fit to their data was
obtained if the rate determining step was the combination of CHa and Ha
lS2
R. Z. C. van Meerten, J . C. Vollenbroek, M. H. J . M. de Croon, P. F. M. T. van

Nisselrooij, and J. W. E. Coenen, Appl. Catal., 1982, 3, 29.
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42
Catalysis
species [equation (23)] concurrently with the desorption of water [equation

(2 l)] . A more recent paper by the same
describes measurements of
the hydrogen/deuterium kinetic isotope effect in the methanation reaction
over this catalyst. The results are consistent with the conclusions discussed
above.
Hakvoort and Van Reijen have p~blished''~a set of data obtained over a
coprecipitated Ni-A1203 catalyst of the type discussed in detail in an earlier
section using the differential scanning calorimeter method53 for kinetic
measurements. Although the range of data was rather less extensive than
those of Van Meerten et aZ.,182their results fitted the same rate equation in a
very satisfactory way. Gelsthorpe and Ross185 have also investigated the
methanation reaction over a rather different set of conditions using the DSC
method; a similar coprecipitated Ni-A1203 catalyst and a related material
promoted by lanthanum were used. They found that their data fitted the
equation proposed by Van Meerten et
but also gave a very reasonable
fit to the equation proposed by Ross:81 only in the extremes of partial
pressures (e.g., Pco >pH,) did the data fit the equation of Van Meerten
rather better and here the data might be expected to be rather less reliable
due, for example, to gradual carbon deposition on the catalyst.
Sugrue and Bartholomew have reported a detailed examination of the
kinetics of the methanation reaction over a nickel-alumina monolith catalyst
described earlier.'" For this work, they used a Berty internal recycle reactor
which is particularly suited for investigations of the kinetics of such an
exothermic reaction.186 Their data covered a wide range of temperatures and
pressures. They found that they were best described by a series of equations
which depended on the temperature region: between 475 and 525K, H2
adsorption was thought to be rate-determining; between 252 and 575 K, the
combination of CO dissociation and carbon hydrogenation became predominant;18' above 575 K, carbon hydrogenation alone became the slow step.
Sugrue and Bartholomew are among the few authors who have considered the
effect of water vapour pressure on the rate of the methanation reaction; they
found in all cases a decrease in rate with increasing water pressure, the effect
becoming higher with higher temperatures. They suggested several ways in
which the effect of water pressure could be included in their kinetic
expressions but none of these ways of doing so had a theoretical basis. It is
interesting to note that their data can be fitted to equation (16).
Van Ho and Harriott have postulated a different mechanism involving
intermediate adsorbed carbon atoms.188 This is based on their observation
that a larger fraction of the surface of the catalyst was covered by adsorbed
carbon monoxide during reaction. The rate determining step was assumed to
183
P. F. M. T. van Nisselrooij, J. A. M. Luttikholt, R. Z. C. van Meerten, M. H. J . M. de

Croon, and J. W. E. Coenen, A p p l . Catal., 1 9 8 3 , 6 , 2 7 1 .
G. Hakvoort and L. L. van Reijen, 'Proceedings 7th International Conference on
Thermal Analysis,'Wiley New York, 1 9 8 2 , p. 1175.
l E 5 M. R. Gelsthorpe and J. R. H. Ross, t o be published.
l E 6 J. M. Berty, Chem. Eng. Prog., 1 9 7 4 , 70, 7 8 .
D. C. Gardner and C. H. Bartholomew,Ind. Eng. Chem., Fundam., 1981, 20, 289.
S. van Ho and P. Harriott, J. CataE., 1980, 64, 2 7 2 .
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43
be that of carbon formation:
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CO,
+ 2Ha
C,
+ HzO
(26)
Chu, Bakshi, and Matthews have argued18 that such a mechanism would not
explain the deactivation of most methanation catalysts by deposited carbon;
if carbon deposition were rate-determining, the carbon would subsequently
be removed rapidly to give products. Chu et al. proposed an equation similar
to that of van Ho and Harriott in whlch the combination of hydrogen with
surface carbon was rate-determining:
This is equivalent to a combination of equations (22) and (23). Harriott and
van Ho responsed by deriving yet another equation is which both steps
[equations (26) and (27)] were rat e-det ermining .
Happel and his colleaguesp1 have investigated the methanation reaction
over a commercial catalyst, Harshaw 104T. They concluded from kinetic
measurements and from concurrent tracer measurements that the rate determining step involved the hydrogenolysis of CH, species, where x ranged from
0-3. They concluded that C02 was formed directly in the reaction and not
by the water-gas shift reaction. Happel and his co-workers have more recently
published results of multiple isotopic tracing studies, using deuteriomethanes,
of the methanation reaction.lP2 These are interpreted as indicating that the
most abundant species on the surface of the catalyst are Cads and CH,,
with
CHzadsand CH3adsbeing present in smaller proportions. A similar observation
was made earlier by Biloen and Sachtlerlg3 whose use of I3C tracing did not
furnish information on the details of the CH, species involved. Kelley and
G o ~ d m a n studied
~ ~ ~ ,the
~ ~methanation reaction over single crystal nickel
samples over a wide range of pressure (1-1 500 Ton) and temperature (450800K) and concluded that the reaction involved two slow steps, the dissociation of carbon monoxide and the hydrogenation of surface carbon with
four hydrogen atoms in a series of steps to give methane.
It can be concluded from this brief survey of some of the work in this area
that there is now some degree of agreement concerning the mechanism of the
methanation of CO over nickel catalysts although there are still some minor
differences between the conclusions reached by various authors.
Steam Reforming of Methane and Higher Hydrocarbons. - Relatively little

has been published on the mechanism of these reactions since the reviews of
Ross2 and Rostrup-Nielsen3 were written. Van Hooklg5 has recently
reviewed the literature on the steam reforming of methane, presenting a
sizeable number of previously unpublished data from Pullman Kellog. He
L. D. Chu, N. N. Bakhshi, and J . F . Mathews, J. Cutul., 1 9 8 1 , 71, 4 4 3 .
P. Harriott and S. van Ho, J. Cutul., 1981, 71, 4 4 5 .
1 9 J. Happel, I. Suzuki, P. Kokayeff, and V. Ethekanis, J. Cutal., 1980, 65, 59.
1 9 * J. Happel, H. Y. Cheh, M. Otarod, and S. Okawa, J. Catul., 1 9 8 2 , 75, 314.
1 9 3 P. Biloen and W. M. H. Sachtler, Adu. CutuL, 1981, 30, 1981.
194 R. D. Kelley and D. W . Goodman, J. Cutul., 1 9 8 0 , 63, 226.
195
J. P. van Hook, Cutal. Rev.-Sci. Eng., 1 9 8 0 , 2 1, 1 .
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44
concludes that all the data in the literature are consistent with a simple
(reversible) first-order kinetic expression; the water-gas shift reaction departs
from its equilibrium position, especially at low methane conversion level.
Munster and Grabkelg6 have studied the kinetics of the steam reforming of
methane with iron, nickel, and iron-nickel alloys. The concluded that the
steam reforming of methane is a sequence of two reactions:
They concluded that on the nickel catalysts, the rate-determining step is the
reaction of oxygen and carbon on the surface.
De Deken and his colleagues1g7 have studied the nature of the carbon
deposited on a commercial CCE catalyst (12 wt% Ni on a-A1203)and have
concluded that it has diffused into the bulk of the nickel and that some of it
is present as carbide. A more applied article from the same grouplg8 presents
intrinsic kmetic data from a tubular reactor in the temperature range
823-953 K.
Steam Reforming of Ethane.-Kneale and Ross have studied the steam
reforming of ethane over a number of coprecipitated nickel-alumina catalysts
using a low-pressure reaction system with mass-spectrometric analysis of
p r o d ~ c t s . ~They
~ ~ ,obtained
~~
data which indicated that surface carbon
species participated in the reaction in the temperature range 480-700 K,
there being a fraction of a monolayer present on the surface under steady
state conditions. This contrasted with the conclusions of earlier work on the
steam reforming of methane at 873 K over the same type of catalyst with
whch the presence of surface carbon deposited prior to reaction caused an
appreciable change in the kinetics of the r e a ~ t i o n . ~ ~The
, ~ ' nature
~
of the
carbon deposited during the reaction was examined by temperature programmed reaction experiments in which its behaviour was compared with
that of carbon deposited by CO decomposition (Boudouard carbon) and by
decomposition of C2H6 or C2H4 .200 There was little difference in properties
between the different types of carbon. It was also found that the predeposited
carbon had little effect on the rate of the C2H6 H 2 0 reaction. Carbon
deposited from benzene poisoned the reaction. The presence of potassium in
the catalyst decreased its activity but had no effect on the behaviour of the
carbon; this is surprising in the light of the frequent claim that potassium in
such a catalyst decreases carbon deposition by improving the carbongasification properties of the catalyst. It was shown that carbon predeposited
from I 3 C 0 took part in the steam reforming reaction and this was taken as
196
197
198
199
200
P. Munster and J. J . Grabke, J. Catal., 1981, 7 2 , 2 7 9 ; Ber. Bunsenges. Phys. Chem.,

1980,84,1068.
J. de Deken, P. G. Menon, G . F. Froment, and G. Haemers, J. CataL, 1 9 8 1 , 7 0 , 2 2 5 .
J. C. de Deken, E. F. Devos and G. F. Froment, in 'Chemical Reaction EngineeringBoston', ed. J. Wei and C. Georgakis, ACS Symp. Ser., 1 9 8 2 , 1 9 6 , 181.
B. Kneale and J . R. H. Ross, J. Chem. SOC.,Chem. Commun., 1 9 8 1 , 7 5 1 .
B. Kneale and J. R. H. Ross, J. Chem. Soc., Faraday Discuss., 1981, 7 2 , 158.
B. Kneale, S . H. Ali -Sobhani, M. J . Iqbal, and J. R. H. Ross, unpublished results.
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45
evidence that surface carbon species are intermediate in the steam reforming
reaction.
Higher Hydrocarbons. - A number of papers describing the steam reforming
of higher hydrocarbons are particularly concerned with the subject of
carbon deposition on the catalysts. The subject of carbon deposition on
nickel catalysts is considered to be somewhat outside the subject of this
review, especially as the subject is covered by two excellent recent discussions
of papers on carbon deposition and coking during steam reforming,
methanation, and other reactions.2o2y 2 0 3
Jackson and his colleagues2w have examined the steam reforming of a
wide range of different hydrocarbons over a coprecipitated Ni-Al2O3 similar
to that studied by Kneale and Ross.200 They identified up to four distinct
types of carbon species on the catalyst, including reactive and unreactive
types. The active area of the catalyst was markedly reduced (as measured by
CO adsorption) by the presence of this carbon. Jackson and his co-workers
suggest that the steam reforming reaction may occur on a carbonaceous overlayer on the nickel surface. In the light of the results of Kneale and Ross,200
the present author is more inclined to the view that reaction probably occurs
at exposed metal sites in close proximity to the carbon overlayer which can
be continuously replenished by the reacting hydrocarbon.
Two papers have appeared on the kinetics of the steam reforming of
heptane over nickel catalyst^.^'^ ,206 The first concerns the steam reforming
of heptane at low concentrations for injection into internal combustion
engines; the catalyst was Ni-A1203 and the reaction temperature was in the
range 360-406 0C.205 The second concerned an evaluation of the intrinsic
steam reforming kinetic parameters from rate measurements on full-size
particles of a Ni-MgO catalyst in the temperature range 450-550 oC.206
Acknowledgements. The author would like to thank Frans Feil and Peter van
der Wal for help with literature searching for parts of this review. He also
wishes to thank Anke Bakker for having critically read the manuscript and
having checked the references.
202
203
204
205
'06
C. H. Bartholomew, Catal. Rev.,-Sci. Eng., 1982,24, 67.

D. L. Trimm,AppZ. Catal., 1983,5,263.
S. D. Jackson, S. J . Thornson, and G . Webb, J. Catal., 1981,70,249.
K. Sjostrom, Ind. Eng. Chem., Proc. Des. Dev., 1980,19, 148.
P. B. T#ttrup, A p p l . Cutal., 1982,4,377.

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