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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
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)
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)
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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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Catalysis
I
Figure 1
Position in bed
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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.
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Catalysis
14
15
l6
l7
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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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Catalysis
CH4
Heluim
heating
and pump
+ HzO
u
He
3= gNaastura'
11
P
I
ADAM
CH4
Figure 2
29
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Figure 3
32
33
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Catalysis
10
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
34
3s
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11
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
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Catalysis
12
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
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
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
Co
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
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15
56
57
SA
59
60
61
62
63
64
65
66
67
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CataZy sis
16
Figure 4
69
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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
a)
'O
71
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18
Catalysis
Layer structure
3500Y
KOoc
Calcination
NiO*xA1203
+ A1203*yNi0
NiO
+ NiA1204
(x,y,z,
<< 1 )
Reduct ion
Ni
+ A1203 zNiO
Ni
+ "204
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-
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
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19
Calcination
450
600
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
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
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21
Al
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
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Catalysis
22
(a)
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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Li
75
76
77
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Catalysis
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
79
8o
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Catalysis
83
84
86
87
88
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27
I-
Inert
-a
- Catalyst
600
T/"C
500
400
30C
20c
I
I
I0
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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.
90
91
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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
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Catalysis
96
97
98
99
loo
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31
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
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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
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
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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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158
16*
16'
162
163
16'
166
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Catalysis
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
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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.
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Catalysis
without at least brief mention of some of the current ideas concerning the
mechanism of the methanation and steam reforming reactions, particularly
the former.
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)
(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:
Downloaded on 06/04/2016 16:40:57.
Published on 01 January 1985 on http://pubs.rsc.org | doi:10.1039/9781847553195-00001
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
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Catalysis
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43
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.
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Catalysis
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
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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.
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203
204
205
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