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Abstract
A brief review on the recent developments of alternative routes for synthesis gas production, namely catalytic methane partial
oxidation and methane reforming with carbon dioxide, is presented. Particular attention is given to reaction thermodynamics,
catalyst formulation, reaction mechanism and problems of carbon deposition.
in the product gas and thirdly, the Hz-to-CO ratio industrial and academic interest in the catalytic
is higher than the optimum required for the down- partial oxidation of methane to synthesis gas. The
stream synthesis gas conversion to methanol, ace- recent developments in the catalytic partial oxi-
tic acid or hydrocarbons. In the case of Fischer- dation of methane and the closely related methane
Tropsch synthesis, high Hz/CO ratios limit the dry reforming reaction are discussed below.
carbon chain growth.
The alternative reactions for synthesis gas pro-
duction, namely partial oxidation using oxygen
2. Methane partial oxidation: reaction
(2) and dry reforming with carbon dioxide (3))
thermodynamics
both give lower Hz/CO ratios but they have
received much less attention. The mildly exother-
mic partial oxidation of methane to synthesis gas Reaction of CH, with O2 at high temperatures
was first investigated in the 30s and 40s [ 5-71 gives principally CO, COz, Hz0 and HZ.The com-
position of the product gas depends on tempera-
but, at the stoichiometric methane-to-oxygen ratio
ture, pressure, input gas composition, and also on
used, carbon formation occurred on the metal cat-
kinetic factors. The important reactions occurring
alysts. Such undesirable carbon formation cannot
in partial oxidation are:
be avoided by increasing the oxygen-to-methane
ratio or by increasing the operating temperature CH4 + 202 = CO2 + 2Hz0 (4)
without also increasing the potential explosion
CH4+ 1$02=CO+2Hz0 (5)
hazards, separation problems, gas phase reactions
and decreased synthesis gas selectivities. Cata- CH4+02=COz+2H2 (6)
lytic partial oxidation has thus been virtually
CH4 + Hz0 = CO + 3Hz (7)
ignored for the last 50 years. It was not until the
recent oil crisis that there was renewed interest in CH4 + CO2 = 2C0 + 2Hz (8)
the conversion of methane, which is the principal
CO+HzO=COz+H2 (9)
component of natural gas. Green and co-workers
reported in 1990 that some noble metals could, on The calculated thermodynamic gas composi-
a laboratory scale, catalyse methane partial oxi- tions at various temperatures, based on the above
dation to the thermodynamic equilibrium com- reactions, at 1 atmosphere pressure and with an
position of product gases with little or no carbon input methane-to-oxygen (air) ratio of 2:l are
deposition [ 8,9]. This observation reawakened shown in Fig. 1. It can be seen that as the temper-
0.5
0.35
7m~~(K)
Table 1
Table 1 Effect of flow-rate on the catalyst-bed temperature
F/W (ml g- h-) CH4 conv. (%) CO sel. (% ) HJCO CO yield (o/o) Catalyst bed temp. (K)
Catalyst = Ni/MgO (3: 1 Ni:Mg), CH,/OZ = 2, furnace temperature = 723 K. A further thermocouple is inserted directly into the catalyst bed.
aRef. [ 111.
ature increases so also does the selectivity to CO carbon formation is thermodynamically favoura-
and HZ,for example, at 773 K, the equilibrium gas ble below about 1200 K.
composition is calculated to be 0.032 bar CO; Recently, Choudhary and co-workers have
0.078 bar CO*, 0.149 bar CH, and 0.151 bar Hz. reported that high yields and selectivities to syn-
At 1023 K, this changes to values of 0.1830 bar thesis gas ( > 85% selectivity) can be obtained
CO, 0.006 bar CO,; 0.017 bar CH4 and 0.369 bar over nickel [ 11-141 and cobalt [ 15,161 sup-
Hz. Therefore, very high methane conversion ported on various oxides under conditions of
( > 90%) and selectivity ( > 90%) to synthesis apparently low temperature, (723-773 K) and
gas can be obtained above 1000 K. very short residence times. The thermodynamic
Lunsford and co-workers [lo] have also cal- calculations at these temperatures predict that CO
culated the equilibrium concentrations of product selectivity would be much lower than their results
gases at various pressures. Their data indicate that (Fig. 1) . They also observed low conversions for
methane, carbon dioxide and water concentrations steam and dry reforming of methane over the same
increase at high pressures. However, increasing catalysts at the same reaction conditions. They
the reaction temperature can compensate for the suggested that a process giving high selectivity to
effect of pressure. For example, methane conver- synthesis gas is occurring under non-equilibrium
sions greater than 80% with more than 90% selec- conditions and there is a reaction path completely
tivity to CO are predicted above 1173 K at total different from that of the equilibrium processes.
pressures of 10 bar. Thus, by analogy with meth- However, Chang and Heinemann [ 171 have re-
ane steam reforming, the production of synthesis examined Co/MgO for methane partial oxidation
gas from CH,/O* mixtures is thermodynamically and found that catalysts with high cobalt content
feasible at the elevated pressures preferred for were able to initiate the reaction of methane with
commercial operation. oxygen at temperatures of around 773 K. High
However, carbon deposition which is thermo- conversions of methane (about 70%) and very
dynamically favourable should also be considered high selectivities for hydrogen and carbon mon-
in the above calculations, namely the formation oxide (about 90%) were also obtained at high
of carbon by the Boudouard reaction, Eq. (lo), reactant gas space velocities. They found, using
or by catalytic methane decomposition, Equation.
an infrared radiation thermometer, that the cata-
(11). lyst temperatures during methane partial oxida-
2co=c+co, (10) tion to synthesis gas were actually extremely high
( 1473-1573 K) even though the furnace was at
CH,=C-t2H, (11) 773 K.
The equilibrium constants for both these reactions We have investigated the Ni/MgO catalyst
[ 31 lie substantially above the values calculated described by Choudhary. The effect of flow-rate
for the exit gas compositions for the lower tem- on the catalyst-bed temperature was investigated
perature range. Thus, under the stated conditions and the data are shown in Table 1 and Fig. 2. The
6 XC. Tsang et al. /Catalysis Today 23 (1995) 3-15
later showed that Ni, Ru, Rh, Pd, Pt and Ir, either GHSVof5OOOh-andCl&/02ratioof8:1 [28].
supported on alumina, or present in a mixed oxide The supports included oxides of metals of groups
precursor also catalysed partial oxidation and dry IIIa and IVa, rare-earth oxides, /-A&O3and SiOZ.
reforming: however, with the nickel and palla- Methane conversions varied from 33.4% to 66.9%
dium catalysts substantial carbon deposition was but surprisingly they all gave more than 99%
observed. No macroscopic carbon deposition or selectivity to CO. No data for hydrogen selectivity
catalyst deactivation was observed for the iridium were given. However, the methane conversions in
and rhodium catalysts [ 8,9]. all cases exceeded the theoretical maximum
Jones et al. have examined europium iridate (25%) for synthesis gas production under their
( EuZIr207) catalysts using in-situ X-ray diffrac- fixed methane and oxygen ratio. In addition, their
tion and mass spectrometry [ 251. This showed space velocity of 5000 h - GHSV is very small
the pyrochlore structure of the iridate was compared with those of other researchers. It is thus
destroyed during the initiation of catalysis, giving probable that carbon deposition over the palla-
an active catalyst that was shown to comprise par- dium catalysts is responsible for the difference in
ticles of iridium metal of about 30 A in diameter methane conversions.
supported on europium oxide. The sudden A detailed comparison of supported ruthenium
increase in synthesis gas production, monitored and nickel catalysts at 1073 K with CH,/O,/He
by mass spectrometry, corresponded to the onset ratios of 8/4/3 and at extremely fast flow-rates
of reduction of pyrochlore. Ashcroft et al. [ 261 (0.893 mol CH, kg- s-l) has been reported
reached similar conclusions in a study of the rare- [ 291. In all cases the product gas compositions
earth iridium pyrochlore catalysts using in-situ deviated from equilibrium values, indicating
energy dispersive X-ray diffraction by synchro- kinetic control of the products. Interestingly, they
tron radiation. found that a ruthenium catalyst with as little as
Kunimori and his co-workers [ 271 found that 0.015 wt.-% Ru loading on A1203 gave higher
RhV04/Si02 and unpromoted Rh/SiOz are excel- activity and selectivity than 5 wt.-% Ni on SiOZ.
lent partial oxidation catalysts giving greater than We note that the relative metal activity for steam
90% methane conversion to synthesis gas at reforming is Ru = Rh > Ni > Ir > Pd = Pt 3
around 973 K. They have also compared the activ- Co =Fe [ 301. The activity order for methane
ity of the two catalysts at temperatures between reforming with carbon dioxide was also found to
573 K and 993 K at atmospheric pressure, and a be Ru > Rh, Ni, Ir > Pt > Pd [ 3 11. The similarity
CH4/02 ratio of 2 with nitrogen dilution. It was between the orders of activity of the metals for
found that, for RhV04/SiOz, the onset of activity partial oxidation of methane, steam reforming and
occurred around 773 K, whilst the unpromoted dry reforming of methane is apparent.
Rh/SiO* catalyst showed the onset of activity at Recently, Hochmuth [ 321 has investigated par-
the higher temperatures (above 873 K) . Investi- tial oxidation of methane over Pt-Pd impregnated
gation of the used catalysts showed that the aver- monolith catalyst under fast reactant flow in pilot
age rhodium particle size for RhV04/Si02 was plant experiments. He analysed the axial gas com-
smaller than the rhodium particles in the unprom- positions and temperature profiles along the cat-
oted Rh/SiOz. The difference in activity at low alyst bed and concluded that there was initial
temperature was ascribed to the importance of exothermic combustion on the front catalyst bed
metal particle size, morphology and its interaction which generated steam, carbon monoxide and car-
with the oxide support. bon dioxide but little production of hydrogen.
The activity towards partial oxidation of meth- Then this was followed by steam and dry reform-
ane of catalysts composed of 1 wt.-% palladium ing together with the water-gas shift reaction. The
supported on a range of oxides has been studied. precious metal based catalyst is extremely active
The reaction was carried out at 1023 K, using a driving both reforming reactions to equilibrium
S. C. Tsang et al. /Catalysis Today 23 (I 995) 3-1.5 9
very quickly, although, equilibrium was not times, but the calculated gas compositions neglect
reached with regard to the water-gas shift reac- consideration of the thermodynamically feasible
tion. carbon deposition reactions, (reactions 10 and
Hickman et al. [ 33-371 investigated rhodium 11). Claridge et al. [39] have systematically
and platinum impregnated foam monoliths as cat- investigated carbon deposition on some metal cat-
alysts for the partial oxidation of methane. The alysts during the partial oxidation of methane to
reactions were carried out using extremely short synthesis gas. It was found that the relative rate of
residence times of between lop4 and lo- sec- carbon deposition follows the order of
onds, under adiabatic conditions. Very high selec- Ni > Pd > Rh, Ru, Pt, Ir. Very little carbon dep-
tivities to synthesis gas ( > 90%) were observed osition was found over the noble metal catalysts
and almost complete conversion of methane could especially those of platinum and iridium for
be achieved. They pointed out that the partial oxi- which, even after 200 hours, negligible carbon
dation of methane has a residence time advantage deposition and no deactivation was observed. This
over conventional steam reforming, which has observation agrees with earlier work on catalysts
residence times of the order of a few seconds (this for ethane steam reforming, which showed less
being due to heat transfer limitations). This means carbon formation over noble metal catalysts. It
the size of plant could be greatly reduced. also demonstrates that the causes of macroscopic
carbon deposition are independent of the mecha-
3.3. Miscellaneous catalysts nism for synthesis gas production and that carbon
deposition can be kinetically avoided by using
Otsuka et al. [38] have shown that cerium suitable catalysts.
oxide is able to convert methane to synthesis gas Electron micrograph studies of used nickel cat-
with a 2/l ratio of HZ/CO at 873-1073 K. They alysts with a high loading show clearly both
demonstrated that the redox properties of cerium whisker and encapsulate carbon (Fig. 4).
oxide allows the direct formation of synthesis gas These two forms of carbon have also been
from methane (reaction 12) and the partially observed on steam reforming catalysts, in partic-
reduced cerium oxide can be reoxidised by COZ ular for nickel, iron, and cobalt catalysts [ 3,401.
giving CO as the sole product (reaction 13). They Whisker carbon deposition does not alter the rate
also showed that addition of platinum black into of synthesis gas production, which may explain
cerium oxide will accelerate synthesis gas for- why no deactivation was reported using similar
mation. However, the HJCO ratios became catalysts for the partial oxidation of methane
greater than 2 if their catalyst reduction time was [ 10,14,28]. Recently, Rostrup-Nielsen and Bak
longer than 60 min. This implies that carbon dep- Hansen [ 311 also found no whisker carbon on
osition occurs during the later stages of reduction. their noble metal catalysts used for dry reforming.
Fig. 4. Micrograr ,h showing the different forms of carbon deposited on the surface of the nickel catalyst. (A) Whisker carbon; (B) encaplsulate
carbon. The scale: bar is 50 nm.
5.1. Combu. stion and reforming reactions was followed by a temperature drop in the inner
mechanism, CRR part of catalyst bed (Fig. 5). This 1lhenomt :non
has also been observed by other researc:hers
The CRR mechanism was first proposed by [ lo,21 1. This temperature profile reflects the
Prettre et al., [ 61, after it was observed that the occurrence of initial exothermic corn13ustion I
temperature at the front of the catalyst bed was tions (reactions 4-6) to give carbor1 oxides and
much higher than the furnace temperature, and this
XC. Tsang et al. /Catalysis Today 23 (1995) 3-15
Temp
Furnace Temp
I
Front of catalyst bed End of catalyst bed
Fig. 5. Schematic representation of the temperature found in partial oxidation catalyst beds (e.g. refs. [ 6,101, etc.)
water which is followed by endothermic reform- case of Rh was found to be lower than with Pt,
ing (reactions 7,8) and water-gas shift reactions suggesting that the Rh surface is more selective
(reaction 9) to give the synthesis gas. CO and H, for direct synthesis gas formation than Pt (com-
are the secondary products in this mechanistic plete oxidation to COZ and HZ0 generates more
scheme. The consequences of changes of space heat). Interestingly, they also found no significant
velocity [ 9, lo] and oxygen/methane ratio [ 9,171 improvement in conversion and selectivity as they
show that selectivities to CO2 and HZ0 increase doubled the residence times. Replacing the mon-
at the expense of CO and Hz at larger space veloc- olith catalyst with layers of Pt-10% Rh gauze
ities or higher oxygen/methane ratios. The group (further decreasing the residence time) showed
VIII metals have been independently shown to that the methane conversion and synthesis gas
achieve complete combustion [ 411, and drive car- selectivity over these materials increased with
bon dioxide reforming reactions [42,43], steam increasing flow-rates, which contradicts previous
reforming reactions and water-gas shift reactions
to equilibrium [ 31. All these observations support
CRR mechanisms.
5.2. iThe
direct partial oxidation mechanism,
DPO
observations [9,21 J. At a fixed flow-rate, no dation and slow reforming would be unlikely to
change in selectivity and conversion was observed be achieved, thus selective desorption of CO and
as the number of layers of gauze increased, pro- H2 from the surface could lead to production of
vided that there were at least three layers present. CO and Hz. This DPO route to synthesis gas for-
In addition, the product distributions were far mation has the advantage of giving a higher pro-
from water-gas shift or reforming equilibrium and ductivity of H2 and CO. Unfortunately, it gives
Hz/CO ratios are lower than predicted at equilib- poorer CO and H2 selectivities compared with
rium. All of these observations cannot be those achieved under the CRR mechanism, even
explained by the CRR mechanism. They postu- at the higher operating temperatures. In addition,
lated a sequence of surface reactions for direct the influence of non-catalytic, gas phase synthesis
formation of synthesis gas, described here as DPO gas production over the monolith at high reaction
mechanism. temperatures has not been studied.
CH,,=C+4H (14) 5.3. Reaction routes for carbon formation
02=20 (15)
The Boudouard (reaction 10) and methane
2H=H2 (16) decomposition (reaction 11) reactions are both
c+o=co (17) thermodynamically favourable. Claridge et al.
[ 391 have investigated the rates of carbon depos-
O+H=OH (18)
ited from pure CH4 and pure CO over a supported
OH+H=HzO (19) nickel catalyst at various temperatures. The results
are shown in Fig. 6. They show that both reactions
co+o=co~ (20)
are catalysed but to varying extents depending on
The difference in Hz selectivity between Pt and the operating temperature. At the typical methane
Rh was explained by the relatively high activation partial oxidation temperature of 1050 K, the
energy for reaction ( 18) on a Rh surface [ 34,371. amount of carbon from pure CO via the Bou-
The selectivity to CO and Hz should be optimised douard reaction is very low compared with the
at short residence times against subsequent further amount from the methane decomposition reaction
oxidation. They then developed a model with a (20 times less) and methane/oxygen reaction (5
19-step surface mechanism, including those cru- times less). This indicates that catalytic methane
cial reactions above and found that the product decomposition is the principal route for carbon
selectivities observed under different reaction formation. Supporting evidence arises from the
conditions could be predicted. observation that the carbon build up occurs at the
It should be noted that both CRR and DPO front of the catalyst bed where the methane partial
mechanisms could be correctly describing the pre- pressure is highest.
dominant reaction path, depending on the reaction Carbon formation from reactions of hydrocar-
regimes. Hickman and Schmidt conducted their bons and CO over metal particles has been inves-
experiments under very different conditions to tigated [ 441. Commonly for nickel and palladium
other researchers. Their residence times are about based catalysts, the carbon grows as a fibre with a
10 to 100 times shorter than in other work. Also, metal crystal at the end (whisker). It has been
the adiabatic conditions cause the catalyst-bed suggested chemisorbed carbon has a high solubil-
temperature to vary, usually > 1300 K compared ity in the metal lattice. Adsorbed carbon atoms
with isothermal temperatures of ca. 1000 K and at that do not react with gaseous molecules diffuse
slightly elevated pressure ( 1.4 atm) . Under these into the metal crystal and nucleate at an unexposed
conditions, especially at such short residence crystal face. Kinetic approaches to preventing car-
times, equilibria for the relatively slow total oxi- bon formation, including passivating the metal
S. C. Tsang et al. / Catalysis Today 23 (I 995) 3-15 13
surface with other chemical species to alter its over the metal surfaces, and this can also be
adsorptivity or solubility have been reported for achieved by sulphur passivated nickel [ 3 1] .
steam and dry reforming [ 45,461. Rostrup-Nielsen and Bak Hansen have shown
the order of reactivity for dry reforming to be
Ru > Rh > Ni = Ir > Pt > Pd. This is similar to the
proposed order for steam reforming, but the supe-
6. Methane reforming reaction with carbon riority of rhodium and ruthenium is less pro-
dioxide (dry reforming) nounced. It was found that the replacement of
steam by carbon dioxide over noble metal cata-
This reaction (reaction 3) was first studied by lysts gave similar activation energies, indicating
Fischer and Tropsch over a number of base metal a very similar mechanism of the two cases [ 3 11.
catalysts [ 471. Calculations indicate that the reac- An interesting new catalyst for dry reforming
tion is thermodynamically favoured above 913 K. reaction has been described by Krylov and his co-
It is more endothermic than steam reforming workers [ 591. They showed that a mixed oxide
(reaction 1) . Carbon deposition is predicted [ 481, catalyst, 5 wt.-% Ca-12 wt.-% MnO on Al,O,
and carbon formation over metal catalysts during gave high yield of synthesis gas from methane and
the carbon dioxide reforming reaction has been carbon dioxide. No deactivation and no carbon
observed [ 43,461. An industrial process, the Cal- deposition were claimed at 1200 K. They postu-
car process, has been developed, which uses meth- lated a reaction scheme involving gas-solid and
ane and a large excess of COz to make CO rich solid-solid reactions to produce synthesis gas
synthesis gas, a nickel based catalyst is indicated however, their catalyst appears to have lower
[ 49,501. activity and equilibrium was not achieved even at
Ferrous metals Fe [ 5 11, Co [ 521, Ni [ 53-551, the higher temperatures.
and noble metals [56-58,421 have all been
reported to be active for dry reforming. Iridium
supported on Al,O, is also active and no carbon 7. The future
deposition was observed [ 431. This Ir catalyst is
active for the exothermic partial oxidation of Catalytic methane partial oxidation and carbon
methane and endothermic carbon dioxide reform- dioxide reforming reactions without carbon dep-
ing and thus both reactions can be carried out osition have been demonstrated on laboratory and
simultaneously. This introduces the possibility of pilot plant scales [ 32,601. Patents based on these
fine tuning the thermodynamics using a CH4, CO2 two processes have been issued regularly [61-
and O2 feedstock. 66].
Perera et al. [ 581 have also shown that Eu203 Recently Korchnak and Dunster [67] have
doped with either Ir or Ru, are effective in pro- reported significant economic incentives for
ducing synthesis gas and there is no significant methanol plants based on catalytic partial oxida-
coke formation. X-ray absorption spectroscopy tion of natural gas. The replacement of the steam
studies indicated the presence of reduced metal on reforming reaction by catalytic methane partial
the spent Ru/Eu,O, catalysts. Richardson and oxidation to generate synthesis gas for further con-
Paripatyadar [ 561 have also shown that Rh sup- version in low pressure downstream processes,
ported on alumina catalysed dry reforming at low e.g. hydroformylation and the Fischer-Tropsch
ratios of C02/CH4 in the temperature range of process have been proposed [ 68,691. At the pres-
873-1073 K with no coke formation. The kinetic ent stage, these two alternative processes appear
avoidance of carbon formation over noble metals to be promising. However, there remains much
has been attributed to high intrinsic reforming work to be done, including studies on carbon dep-
rates combined with low carbon formation rates osition at elevated pressures, detailed process
14 S.C. Tsang et al. /Catalysis Today 23 (1995) 3-15
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