Methanol Synthesis

(from Xin-Mei Liu, G. Q. Lu, Zi-Feng Yan, and Jorge Beltramini, Ind. Eng. Chem. Res. 2003, 42, 6518-6530) With the rapid changes and development in modern industry, the energy and environmental issues have become two major concerns. Methanol has been a common chemical feedstock for several important chemicals such as acetic acid, methyl tert-butyl ether (MTBE), formaldehyde, and chloromethane for over 30 years. Methanol, being a clean liquid fuel, could provide convenient storage of energy for fuel cell applications, particularly in transportation and mobile devices. When used as a fuel, it is a cleaner energy compared with most other sources. For these reasons, methanol synthesis is still attracting interest despite the fact that the current technology process was developed a long time ago. Commercially, methanol has been produced from syngas using natural gas or coal, mainly containing CO and H2 along with a small amount of CO2.2 Methanol synthesis through hydrogenation of carbon dioxide has attracted continuous worldwide research interest in the past 15 years because of its environmental impact. The potential use of CO2, the most important greenhouse gas, as an alternative feedstock replacing CO in the methanol production has received attention as an effective way of CO2 utilization. A recent study showed that a mixture with a proper proportion of CO2 and CO not only can increase the yield of methanol but also decreases the apparent activation energy of the reaction. Of special interest is that the presence of CO2 could maintain the active copper sites in the oxidation state or prevent an over-reduction of the ZnO component when Cu/Zn catalysts are used during methanol synthesis. The active site is yet to be fully understood. It is generally accepted that the coordination, chemisorption, and activation of carbon monoxide and the homogeneous splitting of hydrogen take place on Cu0 or Cu+ and that the heterogeneous splitting of hydrogen, which provides H+ and H- in the catalytic process, takes place on ZnO. However, different points of view on the nature and valence of copper sites still exist. Some researchers pointed out that metallic Cu atoms were uniformly active for methanol synthesis. Pan et al found that the activity of the catalyst is directly proportional to the surface area of metallic Cu and methanol is formed on a metallic Cu surface of a Cu-based catalyst. Similarly, Deng et al. reported that the catalytic activity of a

Cu/ZnO/Al2O3 ternary catalyst for carbon dioxide hydrogenation increases with an increase in the metallic copper surface area, reached a maximum, and then decreased at a Cu/ZnO molar ratio of 8. Rasmussen investigated methanol synthesis by hydrogenation of CO2 on Cu(100) at total pressures of 1-4 bar and reported that metallic copper is actual an active site. They formulated a kinetic model for the elementary steps of methanol synthesis. It indicated that the calculated reaction rate and the activation energy for methanol synthesis were in accord with those measured on Cu(100). They excluded the possibility of Cu+ active sites because only metallic copper was observed on the Cu(100) surface used. Similarly, Askgaard et al supported the metallic Cu model by applying a kinetic model based on experimental data to the methanol synthesis reaction using a Cu single crystal. However, in the presence of CO2 and with a large fraction of the Cu0 surface covered by oxygen-containing species, the catalytic activity toward methanol synthesis is found to be independent of the Cu0 surface area. This finding can be explained by the fact that the Cu+ sites might be acting as active sites in methanol synthesis. Subsequently, Herman et al reported that active Cu+ ion sites are dissolved on the surface of the ZnO matrix. They based their findings on the fact that there was not any new phase other than the normal crystal structure of Cu metal and zinc oxide that coexisted in the mixed Cu/ZnO catalysts. It can be deduced that the promotion effect could only stem from the catalytic activity of a solid solution such as Cu+/ZnO and active centers of the Cu-based catalyst should be Cu+ ions dissolved in ZnO. Traditionally, zinc oxide is a good hydrogenation catalyst that activates hydrogen by heterogeneous splitting, giving rise to ZnH and OH. Furthermore, hydrogen spillover has been observed with ZnO acting as a reservoir of hydrogen for the hydrogenation of CO over Cu surfaces. Dennison et al. observed that hydrogen is adsorbed on ZnO to a much greater extent when Cu is present in the catalyst. On the other hand, Burch found that hydrogen spillover from Cu to ZnO occurs very rapidly from a partially oxidized Cu surface but only to a very small extent from a fully reduced copper surface. Moreover, the hydrogen atoms were trapped at surface defects or at interstitial sites of ZnO, but they were not held too strongly. This means that a possible role of ZnO might serve as a reservoir to provide H atoms for subsequent hydrogenation of adsorbed reaction intermediates.