Applied Catalysis A: General 171 (1998) 301±308

In situ IR studies on the mechanism of methanol synthesis over an ultra®ne Cu/ZnO/Al2O3 catalyst
Qi Suna, Chong-Wei Liub, Wei Panb, Qi-Ming Zhub, Jing-Fa Denga,*

Department of Chemistry, Fudan University, Shanghai 200433, China State Key Laboratory of C1 Chemistry and Technology, Tsinghua University, Beijing 100084, China Received 22 October 1997; received in revised form 4 February 1998; accepted 26 February 1998


Abstract Methanol synthesis from CO2 and CO/CO2 hydrogenation was carried out under real reaction conditions over an ultra®ne Cu/ZnO/Al2O3 (Cu/Zn/Alˆ60/30/10, molar ratio) catalyst. The formation and variation of surface species were recorded by in situ FT-IR spectroscopy. The mechanisms of methanol synthesis and RWGS reaction were discussed. The result revealed that methanol was formed directly from CO2 hydrogenation for CO2/H2 or CO/CO2/H2 reaction systems. b-HCOOÀ was the s necessary intermediate for methanol synthesis. A scheme of methanol and RWGS reaction was proposed. # 1998 Elsevier Science B.V. All rights reserved. Keywords: Methanol synthesis; Mechanism; In situ; FT-IR

1. Introduction In industrial processes, methanol is synthesized from hydrogenation of mixtures of CO and CO2 over Cu-based catalyst. Addition of a small amount of CO2 to the mixture of CO and H2 can promote methanol yield remarkably. Because of this attractive promoting effect, methanol synthesis from CO2 and H2 has caused considerable attention in recent years [1±7]. However, there is still controversy over some important questions, such as: 1. the role of carbon dioxide in the process of methanol synthesis;

*Corresponding author. Fax: +86 2165 641740; e-mail: 0926-860X/98/$19.00 # 1998 Elsevier Science B.V. All rights reserved. PII S0926-860X(98)00096-9

2. whether CO or CO2 serves as the primary carbon source for methanol synthesis; 3. whether the inter-conversion between CO and CO2 via the water-gas shift (WGS)/or reverse water-gas shift (RWGS) is an indispensable process or not; and 4. what are the reaction intermediates involved in methanol synthesis. By the use of the temperature-programmed-desorption (TPD) [8±10], IR spectroscopy [11±13], chemical trapping methods [14] and 14 C or 13 C isotopic tracer [15,16], various surface species were found on Cubased catalyst in the course of methanol synthesis and some reasonable mechanisms were suggested, but most of these experiments were carried out at highvacuum or atmospheric pressure conditions using clean Cu single crystal, supported Cu/SiO2 catalyst

/ Applied Catalysis A: General 171 (1998) 301±308 or Cu-based catalyst with low copper content. 1).0 MPa. A scheme of methanol synthesis formation was suggested. It is found that a few adsorbed CO can be formed easily at room temperatures. molar ratio) used in this study was prepared by ``the oxalate gel co-precipitation method'' similar to that described previously [17±19]. Infrared spectra were recorded with a PerkinElmer system 2000 FT-IR spectrometer. 2 shows part of the IR spectra obtained in ¯owing CO2/H2 reaction gas at 2. high temperature and feed gas continuously flowing over the catalyst). 1. The results obtained under these conditions diverge from the results obtained under real reaction processes. (3) window frame.999%) gases of H2. exceeding the level of 313 K. (2) cell core. Cu surface area measured by N2O titration is 36.9%) were used.302 Q. 2. a high activity ultrafine Cu/ZnO/Al2O3 catalyst (Cu/Zn/Alˆ60/30/10. The band at 2079 cmÀ1 is resolved only at a low temperature range and is attributed to CO adsorbed on a low Miller-index plane of reduced Cu [20]. Infrared experiments were conducted on a 30 mg wafer of the mixture of the catalyst and g-Al2O3 (catalyst/g-Al2O3ˆ1/6. The gases Ê in the in¯ow were puri®ed by passing through a 5 A molecular sieve-trap. weight ratio) crushed to a powder smaller than 500 mesh placed inside an in situ reaction cell (shown as in Fig. Experimental Cu/ZnO/Al2O3 catalyst (Cu/Zn/Alˆ60/30/10. The BET surface area of the Cu/ZnO/Al2O3 catalyst is 49. In this work. . The ultrahigh purity (>99. A resolution of 4. After switching N2 with reaction gas (CO2/H2ˆ1/3 or CO/CO2/H2ˆ20/5/75) and pressurizing slowly to 2. The peaks at 2171 and 2118 cmÀ1 are characteristic of gaseous CO. After reduction by H2 at 513 K for 4 h. Results and discussion Fig. (7) sample wafer. it is found that the intensity of bands of surface adsorbed CO (2079 cmÀ1) and gaseous CO (2118 and 2171 cmÀ1) decrease gradually. (4) NaCl crystal window.0 MPa.3 m2/g and the metallic copper particle size evaluated by XRD and TEM is 10. 3. molar ratio) prepared by ``oxalate gel co-precipitation method'' [17±19] was used as working catalyst to study the mechanism of methanol synthesis from CO2 and CO/CO2 hydrogenation by means of FT-IR spectroscopy under real reaction conditions (high pressure. the reaction cell packed with the catalyst was rapidly cooled to room temperature and ¯ushed with a high-purity N2 for 2 h.7 nm. (6) sample fixing ring.0 cmÀ1 was used throughout the investigation and 50 scans taken over a 20 s interval were averaged to achieve a satisfactory signal-to-noise ratio. N2 and chemical purity CO2 (>99. Sun et al. indicating the decrease of CO concentration over catalyst surface Fig. With increase in the temperature. Schematic diagram of in situ IR reaction cell: (1) cell body. (5) O-ring. temperatureprogrammed-reaction (TPR) experiments (the ¯ow rate of reaction gas was 30 ml/min and the rate of temperature increase was 2 K/min) were performed and IR spectra were recorded synchronously. CO.7 m2/g.

respectively. e. While s the temperature is higher than 393 K. / Applied Catalysis A: General 171 (1998) 301±308 303 Fig. 3. Sun et al. occur and are ampli®ed gradually until the temperature is raised above 433 K. and gas phase. CO species (COs and gaseous CO) and that of m-HCOOÀ decrease.Q. However. It is found that several peaks at 2857 and 2940 cmÀ1. Such a result reveals that. are present at s lower temperatures. the intensity of another peak at 1593 cmÀ1 due to bidentate carbonate species …b-CO2À † also increases more rapidly. it is found that these two peaks weaken again. and b-HCOOÀ species also could be ignored. monodentate formate species (mHCOOÀ) are observed at 1585 cmÀ1.g. although some adsorbed and gaseous CO are present at low temperature. which are characteristic of b-HCOOÀ . it is concluded that methanol is formed directly from hydrogenation of CO2. Formation and variation of methoxy group and methanol during temperature programmed reaction (TPR) process at 2. Up to about 3 493 K. Meanwhile. no CH3Os (adsorbed methoxy species) or CH3OH were formed. and CH3Os as well as product s CH3OH increase due to the increase of b-HCOOÀ . 313 K. the peaks at 2918 and 2965 cmÀ1. the intensity of the peaks at 2857 and 2940 cmÀ1 is also increased and reaches a steady-state concentration above 413 K. As the temperature is raised further. the amount of Fig. and that methanol formation from hydrogenation of carbon monoxide formed via RWGS is negligible.0 MPa. during the increase of the intensity of peak at 1585 cmÀ1. and the rato-vibrational spectrum of H2O (1600±1800 cmÀ1) begins to arise and increase. The key . s From these results. IR spectra for methanol synthesis from CO2/H2 recorded during temperature-programmed-reaction (TPR) process at 2. With the temperature increasing further (higher than 323 K). 2. The results indicate that CO species are formed from dissociative adsorption of CO2 over catalyst surface. Fig.0 MPa for methanol synthesis from CO2‡H2. assigned to CH3Os and CH3OH species. 3 shows the process of formation and change for CH3O and CH3OH species at various temperatures.

CO2. Fig. Furthermore. increase gradually and reach the maximum at 493 K. However.0 MPa. Sun et al. but CH3Os and CH3OH could still be clearly detected due to the existence of surface formate b-HCOOÀ at 2940 cmÀ1. It is found that a sharp peak at 2006 cmÀ1 ascribed to absorbed CO (carbonyl band) varied from weak to intense in the temperature range 293±343 K and then to weak again with the increase of temperature. 4. / Applied Catalysis A: General 171 (1998) 301±308 intermediate species for methanol synthesis from CO2 hydrogenation is bidentate formate …b-HCOOÀ † s instead of monodentate formate …m-HCOOÀ †. It is coincident with the variation of the peak at 1634 cmÀ1 due to the bending mode of H2O physisorbed on Cu. m-CO2À . no formate or carbonate species appear under these conditions. no methanol species could be observed by IR. As the temperature increases to above 353 K. TPR-IR experiments were also conducted with H2/ CO/CO2 feed gas. . m3 HCOOÀ become weaker slowly. This indicates that the necessary intermediate is still Fig. when we switch feed gas CO2/H2 with pure H2. it is also found that. the peak at 2006 cmÀ1 disappears and a broader peak at 1972 cmÀ1 grows rapidly and then decreases gradually. all the band intensities of CO. respectively). 4 shows the spectra obtained when the temperature was increased from 293 K with the rate of 2 K/min at a pressure of 2. This variation is similar to the change of CO2‡H2 in the TPR-IR experiment. When b-HCOOÀ (2940 cmÀ1) fades away. which are characteristic of m-HCOOÀ and b-CO2À 3 species. However. IR spectra for methanol synthesis from CO/CO2/H2 recorded during temperature-programmed-reaction (TPR) process at 2.304 Q. Moreover. This result is in agreement with previous reports [11. besides the bands of 2855 and 2940 cmÀ1 (ascribed to bidentate formate b-HCOOÀ and CH3Os.21]. respectively. when the temperature is increased again. the bands at 1591 and 1601 cmÀ1.0 MPa and gas ¯ow rate of 30 ml/min. The above experimental observation and analysis strongly indicate that the process of the hydrogenation of bidentate formate …b-HCOOÀ † is the rate-limiting step s for methanol synthesis from CO2 hydrogenation. two bands of 1591 and 1601 cmÀ1 diminish. s Further. product CH3OH s is also detected upon the temperature of 443 K.

Pˆ2.73 kcal/mol. The procedures of dissociative adsorption and hydrogenation of CO2 are two parallel competitive reactions. the formation of Fig. CO2/H2 and CO/CO2/ H2 feeds over the ultrafine Cu/ZnO/Al2O3 catalyst.*) and CO/CO2‡H2 (~). Sun et al. It is clear that the addition of CO into CO2/H2 feed gas promotes the formation rate of methanol signi®cantly. Arrhenius plot ln(TOF) for methanol formation and RWGS reaction versus the inverse reaction temperature (1/T) over Cu/ ZnO/Al2O3 catalyst for CO2‡H2 (&. Namely. Methanol synthesis rate for CO/H2. an apparent activation energy could be determined from the slope. It is clear that the addition of CO into CO2/H2 feed gas could lead to the decrease of the activation energy for methanol synthesis. the rate of methanol formation is increased and the methanol selectivity is promoted to a large extent.Q. space velocityˆ4500 hÀ1. After addition of CO into CO2/H2. It is noteworthy that the intensity of bands of the rato-vibrational spectrum of H2O at 1600± 1800 cmÀ1 is obviously weaker for CO/CO2‡H2 system than that for CO2/H2. . It is found that both the methanol formation rates for the individual CO and CO2 hydrogenation are much lower than that for CO/CO2 mixture hydrogenation. 6. So the addition of CO could inhibit the reaction of RWGS. although there is no signi®cant change in the activation energy for RWGS reaction. and the methanol formation rate for CO hydrogenation is lower than for CO2 at 499 K. At low temperatures. After the addition of CO into CO2/H2 feed gas. As a result.52 kcal/mol. Fig. Fig. only a trace of water was detected and the amount is three orders of magnitude lower than that of CO2/H2 reaction system. 6). / Applied Catalysis A: General 171 (1998) 301±308 305 b-HCOOÀ species instead of m-HCOOÀ or other s s species. This is in agreement with the results from this in situ IR experiment. the formation of water species could be suppressed and the formation rate of methanol could be enhanced by the addition of CO into CO2/H2 feed gas. According to the above analysis.0 MPa.7 kcal/mol and that for RWGS reaction is 22. however. This result was also found in this in situ IR±TPRS experiment and in previous kinetic and catalytic activity testing [19]. Especially. we found that the variation of the amount of water is very signi®cant for CO2/H2 and CO/CO2/H2 reaction systems. By plotting the formation rate from kinetic and activity testing versus 1/T (Fig. The activation energy for methanol synthesis is 20. containing only CO and H2 as well as containing CO/CO2 mixture and H2. where the rates of both methanol synthesis and RWGS start to increase rapidly before the conversion signi®cantly alters the gas-phase composition. 5 shows the methanol formation rates for feed gases containing only CO2 and H2. 5. The slope is measured at the temperature ranging from 433 to 453 K. the activation energy for methanol synthesis is decreased to 6. some suggestions for methanol synthesis from CO/CO2/H2 could be proposed: 1. According to the Arrhenius equation. ln(TOF) of methanol formation is proportional to the inverse temperature.

it seems to be ambiguous to explain the fact of the lowering of apparent activation energy after introducing CO gas into CO2/H2 mixture. but could not dissociate to s form COs and OH easily. 3 and then diminish after reaching the maximum. and methanol formation rate and selectivity are promoted significantly. Based on this result. On the other hand. Therefore. 7: In the absence of CO. which is the feed gas for methanol synthesis. This indicates that the formation of CH3Os and CH3OH species are accompanied by the formation of bidentate formate …b-HCOOÀ †. Thus. the limitation of thermodynamic equilibrium for CO2 hydrogenation to CH3OH is removed and leads to a higher methanol yield (methanol synthesis formation rate) and selectivity. when CO is introduced into CO2/H2 feed gas. The reaction tends to take place via pathway (II) to form O=C±OHs. Water produced via methanol synthesis from CO2 hydrogenation is consumed by the fast water-gas shift reaction that simultaneously provides CO2. a direct result is that methanol formation rate and selectivity is increased. However. it is easy to illustrate the pathway of methanol synthesis and RWGS reaction by the scheme shown in Fig. the process of dissociative adsorption for CO2 is inhibited due to the high coverage of CO. respectively) increase gradually. s 3. apparent activation energy for methanol synthesis is decreased. 2. Moreover. The direct result is that IR band absorption intensity at 1600±1800 cmÀ1 ascribed to the rato-vibrational spectrum of H2O in CO/CO2/H2 system is much weaker than that in CO2‡H2 system. when CO is introduced. The effects of addition of CO to the CO2/H2 feed gas are ascribed to the inhibition of the RWGS reaction (or enhancement of the WGS reaction). Although we did not make further study on the adsorption/ desorption species and hydrogenation activity of those adsorbed species on this ultra®ne Cu/ZnO/Al2O3 catalyst. H2O is formed earlier via RWGS reaction and it prohibits the reaction of methanol synthesis. found that two types of adsorbed formate species. we can easily explain the mechanism of methanol synthesis and the . This result has been discussed in kinetic terms previously [19]. the rate of CO2 adsorption/ hydrogenation increases and the process of dissociative adsorption of CO2 is suppressed. this surface (O=C±OH)s could dissociate to form COs and OHs easily due to the absence of CO in gas phase. if the conclusions that b-HCOOÀ s species are a key intermediate and hydrogenation of b-HCOOÀ is the rate-limiting step for methanol synths esis are true. relative high coverage of CO leads to the reduction of dissociative adsorption of CO2 on the catalyst surface and the inhibition of RWGS reaction. From such an analysis. so the peak at 1634 cmÀ1 is observed. it is also found that with the addition of CO into CO2/H2 feed gas. which undergoes stepwise hydrogenation to form CH3Os then to CH3OH. As a result. [23]. The rate-limiting step for methanol synthesis over the ultrafine Cu/ ZnO/Al2O3 catalyst is the hydrogenation of b-HCOOÀ . the process of dissociative adsorption for CO2 could take place easily over the catalyst surface [22] and there is a strong tendency for pathway (I) to happen. the reaction of methanol synthesis can take place quickly. It led to the promotion of methanol formation rate and selectivity. As temperature increases. and b-HCOOÀ species is a key inters s mediate. can be formed and hydrogenate to form CH3O±Zn and then methanol. the Os species formed via b-HCOOÀ hydrogenation to H2COs is consumed by s the adsorbed COs to form [CO2]s rapidly. which then isomerizes to form other intermediate species b-HCOOÀ . some previous research works have given some powerful hints which could be helpful to explain the above divergency. 6. Sun et al.306 Q. but the rate constant of the hydrogenation of HCOO±Cu is about 10 times greater than that of the hydrogenation of HCOO±Zn and the activation energy of the former is lower than that of the latter. These adsorbed oxygen species (Os) combine with nascent hydrogen (Hs) to form hydroxy species (OHs) and then to H2O. so the bands of 1634 and 2007 cmÀ1 diminish gradually and then disappear. even if the reaction occurs via pathway (II). the bands at 1591 and 1601 cmÀ1 (ascribed to m-HCOOÀ and s m-CO2À species. 2918 and s 2940 cmÀ1 (CH3Os) increase gradually along with the variation of the intensity of the band at 2965 cmÀ1 (CH3OH). With the increase of temperature. From Fig. while the bands at 2857 …b-HCOOÀ †. Fujita et al. / Applied Catalysis A: General 171 (1998) 301±308 CO (corresponding to the bands of 2007 cmÀ1) along with the adsorbed Os by dissociative adsorption is a prior process. One explanation is the following: in the absence of CO. HCOO±Cu and HCOO±Zn.

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