Topics in Catalysis Vol. 22, Nos.

34, April 2003 (# 2003)

137

Fundamentals of methanol synthesis and decomposition

Alexander Ya. Rozovskii and Galina I. Lin
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky Prospect, 117912, Moscow, Russia

Fundamental studies of methanol synthesis and decomposition (mainly over Cu-based catalysts) have been carried out. Various kinetic approaches, i.e. TPD study after various chemical treatments of catalyst, non-steady-state transformation of strongly adsorbed species, tracer technique, and steady-state kinetics, have been used. The macroscopic mechanism and detailed reaction scheme of methanol synthesis, as well as the kinetic description of the process have been established and proven. Methanol synthesis over Cu-based catalysts was found to occur by CO2 hydrogenation only, which was coupled with the water-gas shift reaction. Methanol decomposition and steam reforming over Cu-based catalysts have been studied. It was shown that methanol decomposed into a mixture of CO and H2 via methyl formate as an intermediate. Methanol transformation into the mixture of CO2 and H2 occurred by interaction of methanol and water. The reaction proceeded as the reverse methanol synthesis reaction, accompanied by the reverse water-gas shift reaction. KEY WORDS: reaction mechanism; kinetics; methanol synthesis; methanol decomposition; methanol dehydrogenation; methyl formate synthesis; methyl formate decomposition; surface species; adsorption substitution

1. Introduction Methanol is used as a feedstock in numerous chemical syntheses. It can be used also as an energy carrier for hydrogen storage and transportation. For these reasons, both methanol synthesis and methanol decomposition are of great importance for industry, now and in the near future. Methanol synthesis from syngas CO 2H2 CH3 OH 1

has been commercially operated for many years (from 1923, by BASF). Cu-based catalysts, since being pioneered by ICI in the 60s, are used for the highly selective process. In addition, methanol synthesis can be considered as a key reaction in the combined processes of one-step dimethyl ether (DME) and gasoline syntheses from syngas. Methanol transformation into gaseous mixtures enriched with hydrogen can be performed in two ways, by methanol decomposition CH3 OH CO 2H2 or by methanol steam reforming CH3 OH H2 O CO2 3H2 3 2

the active sites [1,2]. This adsorption is irreversible from a kinetics viewpoint, which means the characteristic time of desorption of these substances from active sites is much greater than that of catalysis. Thus, almost all active sites are covered by strongly adsorbed species in the course of reaction. For this reason, the exchange between the surface and the gas phase occurs in such processes mainly through the reactions of adsorption substitution involving formation of a two-particle intermediate on an active site [3]. This unusual mechanism shows itself in non-trivial kinetic patterns of the reactions above. An analogous evaluation (almost all the active sites are occupied by adsorption species) was made by Matsumura and Tode in kinetic studies of methanol decomposition over silica-supported Ni [4]. Reactions (1) and (2), when proceeding over Cubased catalysts, have another distinction: their mechanisms are quite unlike the ones that can be assumed from reaction stoichiometry. Such is the case of methanol synthesis from CO and H2 ; which proceeds through the intermediate step of CO2 formation by the water-gas shift reaction (WGSR) CO H2 O ! CO2 H2 followed by CO2 hydrogenation to methanol CO2 3H2 ! CH3 OH H2 O 5 4

Cu-based catalysts can be used in all these reactions. Though very different, reactions (1)(3) have one common feature: their mechanisms are similar in that the products of these reactions are adsorbed strongly on
To whom correspondence should be addressed. E-mail: rozovsk@ips.ac.ru

Direct CO hydrogenation to methanol does not take place at all over Cu-based catalysts [1,2]. The reaction of methanol decomposition (2) proceeds, strange as it may seem, through the intermediate
1022-5528/03/04000137/0 # 2003 Plenum Publishing Corporation

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formation of methyl formate, which decomposes then into CO and H2 : 2CH3 OH ! CH3 OCHO 2H2 CH3 OCHO ! 2CO 2H2 : 6 7

These peculiarities will be considered below in detail. Methanol synthesis is paid slightly more attention to here, because the mechanism of this reaction is of fundamental importance also for methanol steam reforming. Although the fact that methanol synthesis over Cu-based catalysts proceeds only through CO2 hydrogenation by reaction (5) was proved a quarter of century ago [57], and some of those results have been reproduced later by Chinchen et al. [8,9], publications still appear where methanol synthesis is proposed through CO or CO=CO2 hydrogenation (e.g., [1014]). Therefore, this paper will deal with the most important experimental results concerning various peculiarities of methanol synthesis mechanisms that seem to escape the attention of many researchers. Decomposition and steam reforming of methanol are less studied processes. The latter, though, can be described as reverse methanol synthesis. It will be shown that data on methanol synthesis mechanism allow one to establish the detailed scheme of the methanol reforming mechanism. As to methanol decomposition, it was noted above that in the case of the absence of water this reaction proceeds over Cu-based catalysts through the formation and the decomposition of methyl formate. The existence of a free site adjacent to an active one is found to be necessary for methyl formate decomposition to proceed.

2. Methanol synthesis Methanol synthesis over Cu-containing catalysts is a well-researched process. Various surface species were determined in studies of methanol synthesis [15]. However, their respective roles in the reaction mechanism are still disputed. For example, Kilo et al. suggested that over Cu=ZrO2 -based catalysts methanol is formed mainly from bidentate surface carbonate via adsorbed CO; -bound formaldehyde and methoxy group [16]. In a paper by Chen et al. [17] another mechanism is proposed: carbonate ! formate ! methoxy group ! methanol. Synergy between Cu and ZnO in the catalysis of methanol synthesis has been the subject of active discussion during recent years. Even in this relatively simple case there is no common opinion on both the nature of the effect and its quantitative expression. Fujitani and Nakamura reported on the anomalous ZnO content dependence of Cu/ZnO catalyst activity (the dependence of activity on metallic copper surface area was linear, while the relationship between the

copper specic activity in methanol synthesis and ZnO content was volcano-like [18]). Waugh [19] assumed that such a difference may occur due to the difference in specic activity of various samples relating to their different morphologies. According to Spencer, the varied results obtained by different groups concerning synergy between ZnO and Cu in methanol synthesis catalysts are a result of different experimental test conditions [20]. K. Futagami and others reported recently [14,21] that reduction of the physical mixture of Cu=SiO2 and ZnO=SiO2 in hydrogen atmosphere at 573723 K increased the yield of methanol produced by CO2 hydrogenation. At the same time, no such promotion was observed for the reverse WGSR [21] and for CO hydrogenation [14], indicating that the active sites for CO2 and CO hydrogenation are different. This conclusion contradicts to the data of Ma et al. who have found that ZnO and Cr2 O3 improved the activities of skeletal copper catalysts in all reactions: methanol synthesis, decomposition, and WGSR [22]. As to the nature of this synergy, it is also interpreted in different manners. Spencer suggested that synergy, if it occurs, arises from H spillover from ZnO to metallic Cu [20,23], while Schilke et al. proposed for the case of Cu=SiO2 Zr catalyst that after CO2 adsorption over ZrO2 as bidentate HCO3 Zr; the latter species is hydrogenated by atomic hydrogen which is generated over metallic Cu, i.e. hydrogen diffusion occurred in the opposite direction [24]. Overall, formate adsorbed over copper seems to be the most probable participant in methanol synthesis from all surface compounds found by different authors. Of course, contradictions in various data do not end here. For example, Fujitani et al. reported on the basis of in situ FTIR measurements that the active sites of methanol synthesis created on the Cu=SiO2 catalyst by interaction with ZnO were found not to promote CO2 and H2 transformation into formate over Cu [25]. Nomura et al., however, demonstrated by the same method that catalyst activity grew along with concentration of surface formate in methanol synthesis from CO2 and H2 over Cu=TiO2 with various promoters including ZnO [26]. The key to understanding these patterns can be found probably in the work of Bando et al. [27], where it is shown by in situ FTIR that, although formate species on copper easily form at CO2 adsorption over various Cu-based catalysts (Cu=TiO2 ; Cu=SiO2 ; Cu=Al2 O3 ), they differ in stability: over Cu=TiO2 they can be hydrogenated at as low a temperature as 150  C; while over other catalysts these particles are stable at 200  C: Thus, the concentration of formate species is dened by the difference in rates of their formation and decomposition, which may be affected by variations in composition of different catalysts and other factors, leading to ambiguity in conclusions. Even in situ

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measurements can be interpreted in various ways due to these reasons. Some conclusions may seem weak when the results of different authors are thoroughly compared; usually this results from the fact that the investigations of the nature of the surface species by methods of surface science are separated from studies of reaction kinetics in most works. Nevertheless, the latter is the only method that, being combined with the results of surface studies, allows one to establish the sequence of the surface intermediates in the reaction mechanism.

2.1. Reaction mechanism The methanol synthesis mechanism had been considered partly [1] and recently in detail [2]. It is summarized in this section. The rst (and still the most important) question under discussion is whether carbon monoxide or carbon dioxide is the source for methanol. From the chemists point of view, sequential reduction of carbon oxides is the most evident way for this reaction: CO2 ! CO ! CH3 OH: 8

However, experimental results from both reaction kinetics studies at small contact time [5] and tracer technique [6,7] have shown that the reaction proceeds via an alternative pathway over Cu-based and ZnCr oxide catalysts as well: CO ! CO2 ! CH3 OH: 9

Moreover, it is the only sequence of reactions that can be observed in the reasonable range of temperatures (180260 8C) and pressures (0.120 MPa). It was shown in a special experiment [7] that a CO=H2 mixture carefully cleaned from CO2 and water (which in turn produces CO2 by WGSR) does not produce methanol. SNM-1, a CuZnOAl2 O3 catalyst originating from methanol industry of the former USSR, was used in this experiment. Methanol synthesis from a CO2 =H2 mixture over a wide range of Cu-based catalysts has been studied in detail in our laboratory ([1]). In all experiments with a CO2 =H2 mixture as the feedstock the initial rate of methanol synthesis was at its maximum value [1],[5]. This agrees with the conclusion that methanol synthesis over Cu-based catalysts proceeds by reaction (9), not by reaction (8). 2.1.1. 14 C label experiments The conclusion above has been supported by results of experiments using 14 C label [6,7]. The results of steady-state methanol synthesis from the mixture containing predominantly 12 CO (30 vol%) and small additions of 14 CO2 (4 vol%) illustrate this point most

evidently. Let us consider some of these results [6,7]. Methanol synthesis was performed under $ 5 MPa pressure over Cu-based catalyst SNM-1. The reaction proceeded in a circulating ow system where methanol and water were removed from the ow by freezing and the total pressure slightly decreased during the run due to methanol synthesis. The label in CO2 continuously decreased during the run, the label in CO increased - due to direct and reverse WGSR. Methanol label was measured at the end of the run. It was, therefore, an integral average value for the run duration. For CO and CO2 ; initial and nal 14 C fractions were measured, as well as those in an integral average gas mixture sample obtained by continuous sampling of gas mixture during the run. The average gas sample can be considered as an equivalent to the methanol sample obtained by freezing, and their labels can be compared directly. Table 1 demonstrates the results of two runs performed at 218 and 250  C with syngas containing either CO or CO2 in excess [6,7]. It is seen from table 1 that when CO was in excess, the 14 C fraction increased in CO while decreasing in CO2 during the run due to isotopic exchange by WGSR. The methanol label was much higher than that of CO, being close to the CO2 label. When CO2 was in excess and 14 CO was added, the methanol label corresponded to the CO2 label just the same. It is clear from these data that CO2 hydrogenation is the only pathway for methanol synthesis. Analogous results were obtained by our research group using tracer technique 14 C in steady-state methanol synthesis over a zincchromium catalyst ([2]), as well as by Chinchen et al. [8,9] in methanol synthesis over a Cu-based catalyst under steady-state conditions. The resulting conclusion can be made that methanol synthesis over Cu-based catalysts occurs through CO2 hydrogenation CO2 3H2 CH3 OH H2 O: This process is accompanied by WGSR CO H2 O CO2 H2 : It can be seen that the combination of these two reactions is a molecular chain reaction where excess oxygen atoms migrate
Table 1 Specic radioactivity (in arbitrary units) of carbon-containing species in methanol synthesis over industrial Cu ZnO Al2 O3 catalyst SNM-1 under a pressure of $ 5 MPa Species Feed: CO2 (4 vol%) and Initial label Final label Integral average label
14 12

CO

CO2

CH3OH

CO (30 vol%), balance H2, 250 8C 0 5900 490 790 430 1480 1500 CO (1.1 vol%), balance H2, 218 8C 406 0 194 11 7

Feed: 12CO2 (19 vol%) and Initial label Final label Integral average label

14

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between CO2 and H2 O; supporting the reaction chain for methanol synthesis from a CO=H2 mixture even at a small content of excess oxygen in CO2 or H2 O: 2.1.2. 18 O label Klier et al. [28] studied label transfer of oxygen and deuterium in steady-state methanol synthesis in a ow reactor using a mixture of syngas and D18 2 O as a feedstock. The ows of participating compounds were measured at the reactor outlet. Most of the 18 O from D18 2 O was found in the methanol ow. Combining these results with the data on D transfer (which will be considered later in this work), Klier et al. concluded that CO and H2 O are the precursors of methanol, which directly conicts with the conclusion above. However, calculations [1] using the data [28] show that in these experiments due to large contact times the isotopic fraction of 18 O at the reactor exit became the same in water (3.3%), CO2 (3.6%) and methanol (3.4%). Thus, both water and CO2 can be the source of oxygen in methanol (not CO, for its content of 18 O is 0.6%, i.e. more than 5 times lower than in water, carbon dioxide or methanol). Less denitive results can be obtained from methanol synthesis studies under non-steady-state conditions. The work of Liu et al. [29] seems to be the most interesting one. A CuZnO catalyst was treated here under steadystate conditions with an initial mixture containing none of the labeled components. C18 O2 was then introduced in the feed and initial formation rates were measured for all components. The conclusion made by the authors was that both CO2 and CO were the source of methanol and that water retarded the CO2 route. However, as was subsequently shown [1], the original data of Liu et al. resulted from the existence of an oxygen buffer on the catalyst surface. Figure 1, reproduced from [1], demonstrates the dynamics of the 18 O fraction in CO2 (the only source of 18 O in the system) and in the produced methanol, as calculated by data [29]. It is seen that the

fraction of 18 O continuously decreased in CO2 while increasing at the same time in methanol. By the end of a 15-minute run, these values became close. Therefore, the relaxation times of the chemisorbed layer exceeded the duration of the experiment markedly. It follows that an oxygen buffer does exist on the surface. Oxygen from C18 O2 is diluted there by oxygen from the surface species. Only then does the oxygen atom with an averaged label participate in the formation of a methanol molecule. Due to oxygen equilibration, the labels in CO2 ; surface buffer and methanol gradually become closer. If CO is present in the feed, it also participates in oxygen exchange with the buffer, supplying 16 O: Thus, the difference in the oxygen isotopic content exists between CO2 and surface buffer until the moment when the 18 O fractions in CO and CO2 are equal. Taking into account that the methanol and the CO2 labels converge (gure 1), it is clear that CO2 is, at least, the most important methanol precursor. The reason for the existence of the oxygen buffer on the surface will become clear from the later discussion of the detailed mechanism of methanol synthesis.

Figure 1. Dynamics of 18 O fraction in CO2 (1) and in forming methanol (2), as calculated from data [29].

2.1.3. TPD experiments and dynamics study In TPD experiments, as a rule, the following standard procedure was used. A catalyst sample after reduction and vacuum pumping was treated with some of the reaction mixture components under various conditions, and then the TPD spectrum was measured. In some experiments sequential treatment with different components was performed before TPD. The temperature increase rate in the TPD procedure was 25 degrees per minute. A mass spectrometer, MX-7301 (made in Russia), was used in these experiments [1]. As follows from TPD experiments with various samples [1,3032], the surface of reduced catalyst is covered with large amounts of strongly adsorbed water Tm $ 350  C and CO2 Tm $ 300  C: The H2 O peak may relate to water or to surface hydroxyl. Pretreatment with water and then with carbon dioxide results in the appearance of another CO2 peak Tm $ 180  C and its corresponding shoulder in the water TPD spectrum (gure 2). Two similar CO2 peaks appear in the TPD spectrum after treatment of the sample with methanol [2], and also after steady-state methanol synthesis over Cu/ZnO catalyst [33]. Upon the contact of the reduced catalyst with CO2 or water, their peaks were observed in the TPD spectrum together with a diffused peak of hydrogen, which was related in the cited works to reactive hydrogen, appearing as the result of the interaction of chemisorbed water with reduced sites on the surface. This conclusion is favored by the following fact: after pre-treatment of the reduced catalyst with hydrogen at 250 8C, the hydrogen peak in the TPD spectrum becomes smaller instead of growing.

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The dynamics of surface species transformations over Cu-based industrial catalysts in methanol synthesis (SNM-1 and 51-2, the latter by ICI) have been considered in detail [1,2]. The catalyst sample [1] was treated with some of the reaction mixture components, then put into a helium ow, which was abruptly switched to gaseous reactant ow. Due to contact with gas components, various reactions took place with the participation of strongly adsorbed species. The progress of such reactions was judged by product concentrations at the reactor outlet and usually took several dozens of seconds. These studies have shown that CO, CO2 and H2 O; strongly chemisorbed on the active sites, can undergo redox transformations and also participate in adsorption substitution reactions with molecules from the gas phase, for example: ZH2 O CO2g , ZH2 O:CO2 , ZCO2 H2 Og ; 10

where Z is a Cu-containing active site. It should be noted that the studies of the dynamics of surface species transformations do not allow assignment of observed species to denitive chemical structures. Thus, ZH2 O can be chemisorbed water or two hydroxyls that produce water under TPD conditions. The only thing known for sure is that an intermediate denoted here as ZH2 O:CO2 includes both H2 O and CO2 : It will be referred to now on as a two-particle intermediate. At low temperatures the intermediate ZH2 O:CO2 is stable, and its decomposition can be observed by TPD (gure 2(a)). At the temperature of methanol synthesis it decomposes quickly, leaving strongly adsorbed water or CO2 . Although in these experiments water and hydroxyl cannot be distinguished, considering that 100 8C is a relatively low temperature for substitution, it can be assumed that adsorbed water participates in the substitution reaction. Studies of substitution dynamics have shown that this reaction proceeds with high rate [1]. Its characteristic time is less than that of methanol synthesis, so this reaction is suitable for the purpose of getting CO2 molecule onto the active center during the synthesis. At the excess of CO in the reaction system two other reactions are possible [34]: ZH2 O COg ! ZH2 O:CO ! ZCO2 H2g 11

Figure 2. TPD spectra of industrial Cu/Zn/Al oxide catalyst SNM-1 reduced by CO: (a) after exposure to H2 O (0.67 kPa, 10 min, 100 8C) followed by exposure to CO2 (0.67 kPa, 10 min, 100 8C); (b) after exposure to H2 O (0.67 kPa, 10 min, 100 8C) followed by exposure to methanol (0.67 kPa, 10 min, 30 8C). 1; H2 O; 2; CO2 ; 3; CO2 directly after reduction, 4; CO2 ; 5; H2 ; 6; H2 O:

ZH2 O COg ! ZH2 O:CO ! Z CO2g H2g : 11a This reaction also proceeds through a two-particle intermediate. Its exact route ((11) or (11a)) remains unclear, though. Nevertheless, it should be noted that it is the reversible reaction (11) which can make possible quick oxygen exchange between CO and CO2 observed in the experiments of Liu et al. [29]. Therefore, this reaction can be considered for inclusion into the mechanism scheme as the more probable.

Studies of the dynamics of surface species transformations allow one to obtain information on chemical properties of the active sites on the surface of Cu-based catalysts of methanol synthesis. These sites are able to participate in redox reactions involving H2 O; H2 and CO: Moreover, they are the only sites on the catalyst surface where adsorbed CO; CO2 and H2 O molecules are able to react with molecules from the gas phase. It is these sites that are active in methanol synthesis and catalytic activity is proportional to their number [1]. For a set of fresh and partly deactivated samples of industrial catalysts (SNM and ICI 51-2), differing in activity by about 5 times, specic activity per active site (turnover frequency) was the same: 0:47 0:05 s1 [1].

2.1.4. Mechanistic scheme The absence of adsorbed species other than CO2 and water on the active sites is one of the most important

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features in methanol synthesis. Another feature of this process is that all active sites are covered with strongly adsorbed species under methanol synthesis conditions, so there are almost no free active sites. This is why substitution reaction (10) is of the most importance, providing the way for methanol formation. Water molecules form as the result of each cycle of the synthesis, and the time of their desorption is dozens of hours, i.e. markedly exceeding the characteristic time of methanol synthesis. It is clear that without such a channel of exchange with the gas phase as reaction (10) methanol synthesis could not proceed at all. An additional channel for the release of strongly adsorbed water from an active site or for water replacement with CO2 is provided by either reaction (11) or (11a). If reaction (11a) does proceed, then ZCO2 forms directly by CO2 adsorption on vacated sites. If reaction (11) occurs, then ZCO2 species cannot be direct methanol precursors. Otherwise 14 C label would transfer from CO into methanol, which is not supported by experiment. Therefore, reaction (11) can be included in the reaction mechanism scheme only if the step of quick exchange of ZCO2 with gas-phase CO2 is added. Ultimately, both pathways can be described by similar theoretical kinetic models, and the differences are almost negligible. The role of reaction (11) or (11a) increases with increase of CO concentration. The question remains open as to further transformations of CO2 -containing species on active sites. Two such species, ZH2 O:CO2 and ZCO2 ; participate in reaction (10), which can be considered as an experimentally established reaction. In principle, methanol can form by hydrogenation of any of these species. It is possible to expect that, in hydrogenation of the former species, at least one hydrogen atom from H2 O will transfer to the CH3 group of methanol, and that in hydrogenation of the ZCO2 species, only hydrogen from the gas phase will be included in the methyl group. Thus, it is possible to discriminate between these two species by using D2 O in methanol synthesis. Such an experiment in steady-state methanol synthesis was performed by Klier et al. [28]. As the CH2 D group was observed in methanol, it was evident that ZH2 O:CO2 is the methanol precursor. Nevertheless, considering that the contact time was too high in the experiments [28] GHSV $ 104 h1 ; an additional study of the effect of D2 O addition on the methyl group composition was performed in our work [35]. Methanol synthesis [35] was conducted in a circulating ow and the products were frozen out. At long contact times, as mentioned before, the results of Klier et al. [28] were reproduced. However, at small contact times (GHSV $ 106 h1 ; at which the reactor became close to the differential one in relation to deuterium transfer) no label transfer from D2 O to the methanol CH3 group was found. It can be seen from the data [35] presented in gure 3 that deuterium fraction in the methanol CH3

Figure 3. Dynamics of deuterium accumulation in hydrogen (open points) and in the CH3 group of methanol (lled points) in methanol synthesis at 240 8C over industrial Cu-based catalyst 512. Partial pressures of the components (in MPa): 1; CO; 0:85; CO2 ; 0:034; H2 ; 3:6; D2 O; 0:024;  5:103 s; 2; CO; 0:037; CO2 ; 0:99; H2 ; 4:1; D2 O, 0:029;  3:103 s:

group varies in the range 14%, being equal to its fraction in hydrogen and much less than its fraction in water (7085% [35]). These data show that ZCO2 is the only methanol precursor from all species on active sites. Its hydrogenation is a multi-step process due to the participation of three hydrogen molecules. The order of the stationary reaction on hydrogen would be a useful value; nH2 1 from the data [1]. Because hydrogen does not participate in any of the previous steps, it follows that the rst hydrogenation step is the rate-limiting one and hydrogen from the gas phase is involved. It should be mentioned that gas-phase hydrogen appears to be the reactant also in hydrogenation of methyl formate into methanol over Cu-based catalysts [36]. The results detailed above are sufcient for establishing the mechanism scheme and theoretical kinetic model on the basis of this mechanism. The only remaining question is which surface species will be produced in this reaction in the end. Species formed after the limiting step are in equilibrium with reaction products and therefore unreachable for kinetic analysis in the investigation of direct reaction. Nevertheless, it is known that a methanol molecule and water molecule will be produced in the end. Considering that both molecules can be strongly bound to active sites, it can be assumed that at least one of them remains on the surface. If it is a methanol molecule that remains on an active site, then the latter undergoes excessive reduction in the reaction involving this molecule, followed by its deactivation. Because the characteristic time of deactivation is much higher than that of methanol synthesis, it can be assumed that the percentage of such occurrences

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is negligible. Therefore, it can be concluded that a methanol molecule in the gas phase and a water molecule strongly bound to the active site are formed as the nal result of ZCO2 hydrogenation. Interaction of ZCO2 species with a hydrogen molecule from the gas phase is the controlling step in the sequence of hydrogenation steps. On this basis two mechanism schemes can be built. Scheme 1 is based on the reaction sequence occurring at relatively low CO content in a feed. Scheme 2 of a more general kind, takes into account the reaction pathway (11). The upper line in scheme 1 is the reaction of adsorption substitution (10) which was observed in an independent experiment. Its intermediate (two-particle complex) is present in the TPD spectrum at lower temperature (100 8C). Participation of hydrogen from the gas phase occurs in the rst hydrogenation step. It is also the rate-limiting step, as follows from the rst order of the reaction of hydrogen. Thus, all steps in scheme 1 except the nal macro step are proved by experiments. Scheme 2, which includes reaction (11), is less adequate, because it includes the hypothetical step of quick CO2 exchange between active surface and gas phase. Quick transfer of oxygen label from CO into CO2 observed in [29] becomes understandable in view of this reaction. All other steps including the formation of

ZH2 O:CO intermediate do proceed, as shown quite denitively by the data on chemisorbed H2 O transformation dynamics [1]. 2.1.5. Surface intermediates The correct assignment of intermediates in the schemes above to the real structures is relatively complicated, although surface species on Cu-based catalysts are studied in detail by various spectroscopic methods (e.g., [16,17,21,2428,33,3744]). Additional complications arise, though, as active centers of the catalysis appear to be clusters of Cu atoms or ions. As was found by ESR spectroscopy [45], treatment of the CuZnAloxide methanol synthesis catalysts with pyridine did not produce isolated pyridinate complexes. Moreover, three types of copper clusters were observed. In the case of CuZnO system clusters up to 1 nm were found by electron microscopy [46]. The complicated and unpredictable structure of Cu-based catalyst surfaces, which change in the process of reduction and catalysis, is also described [37,38]. Nevertheless, the specic activity of Cu-based catalysts (turnover frequency) was found to be the same for two different industrial catalysts (see the ending of section 2.1.3). Therefore, we can conclude that despite the initial difference between the surfaces of various catalysts, quite similar structures may form in the course of catalysis. Species on the surface of Cu-containing catalysts have been actively studied in recent years by various methods, including in situ methods. Nevertheless, information obtained on the role of various surface species in methanol synthesis is confusing. Most authors refer the key role in methanol synthesis to surface formate on copper (e.g., [26,33,3941]). However, some authors [42,43] consider surface formaldehyde to be of the most importance. At present, surface carbonate seems to become more prominent in the mind of many scientists as the rst surface species to undergo hydrogenation [16,17,43,44]. In one paper [44] this step is deemed as the rate-controlling step. Considering these data for the use in assignment of intermediates in schemes 1 and 2, let us take into account that 14 C label does not transfer from CO into methanol. For this reason, the probability is low that intermediate ZCO2 in scheme 1 has a formate structure, which easily forms with participation of CO from the gas phase, especially in the presence of water on the surface. More likely, it has a carbonate structure. Thus, ZH2 O:CO2 may be related to a combination (on adjacent sites) either of carbonate and water or of bicarbonate and hydroxyl. Correspondingly, it can be assumed that the product of the rst hydrogenation step has the structure of formate on copper, which quickly transforms into resulting products. The ZH2 O:CO intermediate in scheme 2, most likely, is also formate on copper, but of some other structure than the product of the rst step of hydrogenation,

Scheme 1. Simplied scheme of methanol synthesis mechanism over Cu-based catalysts at low CO content in syngas.

Scheme 2. Scheme of methanol synthesis mechanism over Cu-containing catalysts considering reaction (11).

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because 14 C label does not transfer into methanol. Its existence is proved by experiments on non-steady-state kinetics of transformations of adsorbed water reacting with CO from the gas phase [1]. Surface carbonates of different structure are referred to in scheme 2 as Z CO2 and ZCO2 ; only the latter species can be hydrogenated into methanol.

2.2. Reaction kinetics Two specic features of the process should be taken into account to establish the theoretical kinetic model: (i) Under conditions of methanol synthesis active centers are covered with various species, mainly water and CO2 : The reaction proceeds in the absence of free centers. (ii) All active centers are equal in their reactivity. The latter conclusion directly follows from the data on dynamics of surface species transformations. It is illustrated by gure 4, where kinetic curves are given for adsorption substitution reaction where adsorbed CO is substituted with water from the gas phase over a freshly reduced and partly deactivated industrial catalyst 51-2 (ICI), according to data [1]. For these measurements the catalyst sample was reduced by CO followed by a gas ow switch to helium at the temperature of the experiment, then to He H2 O: The composition of the gas ow at the reactor outlet was monitored by GC using a procedure similar to the stop-ow method. The increase of rate corresponding to the left branches of the curves in gure 4 is due to the increase of H2 O concentration in the gas ow. As to the right branches, the reaction proceeds at constant H2 O concentration. Conversion curves (dependence of reaction rate on conversion of surface species) are given in the same plot by using average values of reaction rate. The linear form of their right branches allows one to make the denitive conclusion on equal reactivity of active centers (and surface species) participating in the process. Similar curves with linear right branches were obtained for all studied reactions of surface species over Cu-based catalysts. A simplied kinetic model of methanol synthesis according to scheme 1 is given below. A number of nonlinear terms in the denominator which become prominent near the equilibrium is not shown here. k 3 pH 2 1 K
pm pH2 O 3 pm pH pCO2 2

Figure 4. Kinetic (a) and characteristic (b) curves of CO substitution by water from the gas phase at 250 8C over industrial catalyst 512: 1, fresh catalyst; 2, catalyst deactivated in methanol synthesis.

1 K2 pH2 O K2 pH2 O =K1 pCO2

where r is the reaction rate, ki and Ki the corresponding rate constant and equilibrium constant of step i; Kpm the methanol synthesis equilibrium constant and p the partial pressures of components. WGSR can be described in a similar manner.

Although this model is built for the set of active centers that are equal in their reactivity, the denominator of the equation contains non-linear terms, which is surely non-trivial for the kinetics of reactions over a uniform surface. Nevertheless, such a form of kinetic equation is typical for the reactions with participation of strongly adsorbed species [3]. In scheme 2, the reactions of methanol synthesis and WGSR are combined, resulting in unusual kinetic patterns, for example, anomalous increase of effective reaction rate along with contact time in the ow reactor. This is illustrated by gure 5 [2,47], where the contact time dependence of methanol synthesis rate over an industrial catalyst 51-2 is given for the mixture CO2 =H2 and for the mixture where CO is in excess. The anomaly caused by conjugation can be seen clearly in the latter case. A more detailed discussion of scheme 2 and the whole kinetic model for this scheme is presented elsewhere [47,48]. The results of computer modeling made in order to check the applicability of the proposed models to the observed kinetics of methanol synthesis are illustrated in table 2 obtained from data [2].

A.Y. Rozovskii, G.I. Lin/Methanol synthesis and decomposition Table 2 Computer simulation of methanol synthesis accompanied by WGSR using theoretical kinetic models based on schemes 1 and 2 (industrial catalyst 512, 240 8C, 5.2 MPa) PCH3OH, atm Contact time, s Calculated by Experiment Scheme 1 Scheme 2 Experiment Scheme 1 Scheme 2 Calculated by PH2O, atm

145

Feed mixture in vol%: CO2, 23.5; CO, 0.1; H2 76.4 0.015 0.034 0.069 0.127 0.237 0.25 0.38 0.52 0.64 0.86 0.25 0.38 0.54 0.72 0.99 0.22 0.36 0.51 0.67 0.88 0.40 0.59 0.90 1.22 1.53 0.38 0.57 0.81 1.09 1.47 0.40 0.65 0.90 1.18 1.51

Feed mixture in vol%: CO2, 3.3; CO, 18.2; H2 77.9; N2, 0.6 0.020 0.029 0.057 0.126 0.240 0.428 0.457 0.59 0.78 1.56 3.06 4.39 5.44 5.95 0.45 0.60 1.08 2.20 3.89 6.21 6.52 0.63 0.88 1.56 2.84 4.24 5.73 5.91 0.16 0.17 0.19 0.20 0.21 0.24 0.24 0.19 0.19 0.20 0.21 0.23 0.26 0.26 0.15 0.16 0.17 0.19 0.22 0.25 0.25

Figure 5. Kinetics of methanol synthesis (1, 2) and WGSR (3, 4) at 240 8C under a pressure of 5 MPa over industrial catalyst 512 (the curves were calculated from kinetic model, the points correspond to experiment). Feed composition (vol%): 1; 4; CO, 3:6; CO2 ; 21:8; H2 , 74:3; N2 ; 0:3; 2; 3, CO; 18:3; CO2 ; 3:2; H2 ; 77; N2 ; 1:5.

mixtures scheme 1 cannot provide an effective kinetic description. Scheme 2 again appears as the more reasonable one. It can be concluded that a description considering the full scheme 2 would be important not only for unusual cases of anomalous kinetics, but also for the cases of practical importance. The applicability of this model is considered in detail elsewhere [48]. Summarizing the description above, it can be concluded that methanol synthesis studies allow one to build the scheme of the reaction mechanism and, on this basis, the theoretical kinetic model, which matches experimental results well. It is shown that the mechanism scheme of methanol synthesis over Cu-based catalysts is rather specic. The strongly (irreversibly) chemisorbed species play an important role in this mechanism, giving additional non-linearities in the reaction kinetic model. Specic properties of this type of heterogeneous catalytic reaction are considered elsewhere [3].

3. Methanol decomposition Simultaneous progress of the WGSR and methanol synthesis was taken into consideration in these calculations. Gas mixtures of quite different compositions, i.e. one with CO2 in excess and one with CO in excess, were used. In this manner the applicability of the theoretical kinetic model can be tested to the full. As seen from table 2, for the mixtures with high CO2 content both kinetic descriptions match the experiment well; at high contact times scheme 2 matches better. When the synthesis is performed from mixtures enriched with CO, conjugation of WGSR and methanol synthesis reveals itself more evidently. It is seen that in the case of CO-enriched 3.1. Comments on reactions occurring Methanol decomposition is of importance due to the problem of hydrogen production, including the use in low-temperature fuel cells. Due to the extreme sensitivity of fuel cells to CO poisoning it is very important to research the reaction network and to use it in order to control process selectivity. The main products of methanol decomposition over Cu-containing catalysts in the temperature range 150 250 8C are methyl formate (MF), CO, CO2 and H2 [49]. Methanol decomposition dynamics were studied [50] by

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sequential injections of measured amounts of methanol onto a Cu=ZnO=Al2 O3 catalyst reduced by hydrogen. Decomposition products in the gas phase were determined by GC. Strongly adsorbed water, left on the surface after reduction, was consumed in the reaction with methanol affecting the composition of products. Figure 6 illustrates the dynamics of product accumulation in the gas phase at 200 8C (in two sequential methanol injections) and at 300 8C [50]. As seen from the gure, the dynamics of MF and CO accumulation reveal the classic illustration for the case of the intermediate and the end product of consecutive reaction correspondingly. Considering that the initial rate of CO formation is close to zero (gure 6), the conclusion can be made that CO forms over the Cu-based catalyst as the result of the following reactions: 2CH3 OH ! CH3 OCHO 2H2 CH3 OCHO ! 2CO 2H2 : 12 13

The second important result of the described experiment (gure 6) is that these reactions occur intensively only after removal of bulk surface water by the reaction with methanol: ZH2 O CH3 OH ! ZCO2 3H2 : 14

Combination of reactions (14) and 10 gives the reverse reaction of methanol synthesis. Taking into account that water adsorbs strongly on the active sites of a Cu-based catalyst, it can be concluded that in the presence of water in the gas phase the occurrence of reactions (12) and (13) is, at least, of small probability. Because the appearance of CO in the products of methanol decomposition over Cu-based catalysts is caused by reaction (13), the features of this reaction are important for controlling the CO content in methanol decomposition at moderate temperatures.

3.2. The patterns of methyl formate (MF) formation and decomposition The thermodynamics of methanol dehydrogenation into MF (reaction (13)) is interpreted in gure 7. Although MF equilibrium yield increases along with the temperature, the rate of MF decomposition into CO and H2 increases faster than that of MF formation, resulting in low selectivity of methanol dehydrogenation into MF at temperatures higher than 200 8C. Kinetics of MF hydrogenation into methanol (a reverse reaction of (12)) and MF decomposition into CO and H2 were studied in order to obtain information on the mechanism of methanol decomposition [36,52]. Figure 8 illustrates the contact time dependence of MF conversion into CO and H2 by reaction (13) in a ow reactor at 167 8C, under atmospheric pressure and low MF concentrations (up to 1%) in helium ow. Under these conditions MF transforms with high selectivity

Figure 6. Dynamics of product accumulation in the gas phase in methanol decomposition over CuZnOAl2 O3 catalyst: (a) at 200 8C in the rst (open points) and the second (lled points) methanol injections; (b) at 300 8C (methanol initial pressure 50 torr): 1, CO; 2, MF [50].

Figure 7. Equilibrium constants for MF synthesis (1) and decomposition (2), as calculated from data [51].

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practically applied for selective synthesis of MF by methanol dehydrogenation. Some of the results obtained in [52] are given in table 3. These data show that even at relatively high temperature, 240 8C, which is favorable to MF decomposition, under moderately high initial partial pressures of methanol it is possible to achieve selectivity to MF as high as 95%, the conversion being almost at equilibrium (x=x1 0:99).

Figure 8. Contact time dependence of MF conversion into CO and H2 in a ow reactor at 167 8C (feed MF/He).

3.3. Reactions proceeding in the course of methanol decomposition into CO and H2 over Cu-containing catalysts Some additional information can be deduced from the data above. In particular, the results of MF hydrogenation into methanol allow one to conclude that the reverse reaction, methanol dehydrogenation, has at least two consecutive steps of hydrogen release into the gas phase, the second step being rate-limiting.
macro step

into CO and H2 as the only products. As seen from the gure, points corresponding to differing (three-fold) values of the MF initial concentration belong to the same kinetic curve. Thus, at low MF concentrations its conversion in reaction (13) does not depend on concentration, and it can be concluded that the reaction order on MF is 1. As shown in [36], the use of hydrogen instead of helium as carrier gas under the same conditions results in simultaneous MF decomposition and MF hydrogenation into methanolup to a certain point, depending on MF initial concentration. However, at higher MF concentration (5.4 vol%), MF conversion was 46% and no MF decomposition into CO=H2 mixture was detected. The only product of MF conversion was methanol. The MF hydrogenation order on MF was about 1. This value did not change at high MF concentrations, in contrast with MF decomposition. The MF hydrogenation order on hydrogen was also close to 1. The conclusion can be made from these data that in the rst step of MF hydrogenation a hydrogen molecule from the gas phase joins adsorbed MF, and this step is the rate-limiting one. These phenomenathe change in MF decomposition kinetics, i.e. suppression of MF decomposition caused by an increase of MF concentration, while MF hydrogenation kinetics remains the samecan be interpreted in only one way: MF decomposition requires an additional free center. This suppression effect of MF decomposition can be

2CH3 OH 2Z$ IH2 ! Z2 CH3 OCHOH2 ; 15

where I is a relatively stable intermediate, which has been proposed [53] as a surface compound with semiacetal structure. Because MF strongly adsorbs on the active site, its spontaneous desorption during the time of reaction does not occur. MF exchange with a reacting methanol occurs by an adsorption substitution reaction: Z2 CH3 OCHO ! CH3 OH ZCH3 OH
CH3 OHZ

I H2 :

16

Combination of reaction (16) and the second step of reaction (15) corresponds to the kinetic scheme of MF stationary synthesis. MF decomposition can be written roughly as Z2 CH3 OCHO Z ! 3Z 2CO 2H2 : 17

This reaction is surely more complicated. So far, the authors have no solid information on its detailed mechanism. Combining these proven scheme elements of MF formation and decomposition, scheme 3 can be drawn.

Table 3 Highly selective MF synthesis by methanol dehydrogenation over a Cu-based catalyst Feed rate, l/g/h 21.7 20.3 Pressure, P, atm 8.5 8.5 Po methanol , atm 1.4 1.3 Conversion x, % 21.5 44.1 x into MF,% 20.7 42.0 Selectivity, S, % 96 95

T, 8C 190 240

x/x1 73 99

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Scheme 3. MF formation and decomposition over Cu-containing catalysts.

As noted above, the right half of this scheme (MF decomposition) can be realized only in the presence of a free adjacent center, i.e. under low partial pressure of methanol and MF. The whole scheme is effective only in the absence of water in the reaction system. When water is present, methanol transforms over Cu-based catalysts only in terms of reaction (15), the reverse synthesis reaction. The last conclusion does not lend credence to the methanol steam reforming scheme over Cu/Zn/Zr/Al and Cu/Zn/Zr oxide catalysts proposed by Takahashi et al. [54] and then by Breen and Ross [55]. This scheme consists of the following reactions: 2CH3 OH ! CH3 OCHO 2H2 CH3 OCHO H2 O ! HCOOH CH3 OH HCOOH ! CO2 H2 : 12 18 19

As follows from the discussion above, over Cu-based catalysts in the presence of water only two reactions occur: the reverse methanol synthesis CH3 OH H2 O ! CO2 3H2 and reverse WGSR CO2 H2 ! CO H2 O: 4 3

Accordingly, we have never found MF or formic acid among the products of methanol steam reforming over Cu-based catalysts.

3.4. Kinetics of methanol steam reforming Methanol steam reforming kinetics has been reviewed recently [56,57]. In contrast to the approach of those works, our approach is based on the reaction mechanism scheme proved by various independent methods. Other authors [56,57] also defend the proposition that methanol steam reforming involves the participation of two types of active centers. We believe that all the active centers are equal in their activity, as directly proved by

experiments on the dynamics of transformations of surface species (see above). As noted before, at moderate temperatures over Cubased catalysts methanol transforms in the presence of water only by reaction (3), the reverse of its synthesis. The products, CO2 and H2 ; enter reverse WGSR in turn. Because the controlling step for direct and reverse reactions is the same, the kinetic model of methanol steam reforming can be made on the basis of scheme 2. Considering this scheme, one should take into account that intermediate ZCO2 :H2 is in equilibrium with reactants (methanol and water), and that the last hydrogen molecule release is the slowest step. Thus, under the conditions of methanol steam reforming, the formate species ZCO2 :H2 should accumulate over active centers. This is conrmed by various spectroscopic observations (e.g., [57]). The kinetic model of methanol steam reforming was established based on the approach described above using scheme 2. Calculations for our own kinetic data for high pressures (0.5 and 2.0 MPa) have shown a good agreement between experimental and calculated data on the rate of methanol steam reforming. An additional testing of the model was made using experimental data obtained under atmospheric pressure by Kuznetsov et al. [58]. We have chosen their data to check our kinetic model for two reasons. Firstly, the conditions are extremely different from that used in our studies. For example, the values of partial pressures of the reactants were of the order 0.1 atm. Secondly, these data were obtained in a circulating ow installation, where the reaction rate can be determined with the most precision. That is why the calculation of the methanol steam reforming kinetics using previous data [58] appears to be the most radical way to check the theoretical kinetic model. The parameters of the kinetic model of methanol steam reforming were found from the kinetics of the reverse reaction, methanol synthesis. If scheme 2 is correct, the proposed model should describe the kinetics of both methanol synthesis and methanol steam reforming adequately when the same parameter values are used. Figure 9 demonstrates the dependence of methanol synthesis rate on hydrogen partial pressure calculated from previous data [58]. It is seen that the methanol synthesis order on hydrogen under atmospheric pressure is also close to 1. Calculations of methanol steam reforming kinetics under atmospheric pressure are compared with previous results [58] in gures 10 and 11. The water concentration dependence of reaction rate (gure 10) and hydrogen pressure dependence of reaction rate at varying methanol concentrations (gure 11) are depicted correspondingly. It is seen that the calculated and experimental values of reaction rate are close. Thus, the model reects well the inuence of hydrogen, methanol and water

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149

concentrations on the methanol steam reforming rate under atmospheric pressure. It seems that this method, the description of methanol steam reforming on the basis of data and the model of methanol synthesis, can be considered valid at least for Cu-based catalysts.

4. Conclusions Various kinetic approaches were used to study the fundamentals of methanol synthesis and decomposition. Combinations of tracer technique, TPD after various chemical pre-treatment procedures, data on dynamics of surface species reactions with gas-phase reactants, together with steady-state kinetics were employed. On this basis it became possible to build the kinetic mechanistic schemes of methanol synthesis, of methanol dehydrogenation into methyl formate, of methanol decomposition into carbon monoxide and hydrogen, and to determine the rate-limiting steps of these reactions. The approach, where some information on the reaction mechanism and kinetics can be obtained from studies of the reverse reaction mechanism, proved highly useful. In this way important information was obtained on the mechanism of methanol dehydrogenation into methyl formate and on methanol steam reforming. Kinetic models of methanol synthesis and steam reforming were built and proved by comparison with experiments. Highly selective synthesis of methyl formate was performed. It is shown that over Cu-based catalysts at moderate temperatures (up to 300 8C) methanol decomposition into a CO=H2 mixture proceeds through methyl formate as an intermediate product. This pathway is realized when there is no water in the reaction system. In the presence of water this reaction is suppressed and the reaction, which is the reverse to methanol synthesis from CO2 and water, proceeds instead, accompanied by reverse WGSR. All the reactions studied are characterized by the formation of strongly (irreversibly) adsorbed products with characteristic time of desorption markedly exceeding that of catalysis. That is why the exchange between the adsorbed species and molecules from the gas phase proceeds in such systems by reactions of a new type, namely by adsorption substitution. Such a mechanism of the catalytic process results in a new generation of reaction kinetic models. It was shown that these models adequately describe methanol synthesis and methanol steam reforming kinetics.

Figure 9. Hydrogen partial pressure dependence of methanol synthesis rate at 200 8C over industrial catalyst SNM-1 in experiments [58]. Feed composition (vol%): CO, 30; CO2 , 5; remainder H2 and N2 : The calculations were performed using a kinetic model based on scheme 2.

Figure 10. Water partial pressure dependence of methanol steam reforming rate at 200 8C over industrial catalyst SNM-1 in experiments [58]. Methanol partial pressure varied from 0.44 to 0.66 kPa. The calculations were performed using a kinetic model based on scheme 2.

Acknowledgments
Figure 11. Hydrogen partial pressure dependence of methanol steam reforming rate at 200 8C over industrial catalyst SNM-1 in experiments [58]. Partial pressure were: water, $ 2 kPa; methanol, from 0.067 to 0.59 kPa. The calculations were performed using a kinetic model based on scheme 2.

This work was supported by the Russian Foundation for Basic Research (Project No. 98-03-32186), the Russian Foundation for Support of Scientic Schools (Project No. 00-15-97389), and NEDO (Project No.

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98EA4). We would like to thank also I.N. Zavalishin for useful discussions.

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