Preparation methanol synthesis

Besides supported (transition) metal catalysts, structure sensitivity can also be observed with bare (oxidic) support materials, too. In 2003, Hinrichsen et al. [39] investigated methanol synthesis at 30 bar and 300 °C over differently prepared zinc oxides, namely by precipitation, coprecipitation with alumina, and thermolysis of zinc siloxide precursor. Particle sizes, as determined by N2 physisorpt-ion and XRD, varied from 261 nm for a commercial material to 7.0 nm for the thermolytically obtained material. Plotting the areal rates against BET surface areas (Figure 3) reveals enhanced activity for the low surface area zinc... 

Another study on the preparation of supported oxides illustrates how SIMS can be used to follow the decomposition of catalyst precursors during calcination. We discuss the formation of zirconium dioxide from zirconium ethoxide on a silica support [15], Zr02 is catalytically active for a number of reactions such as isosynthesis, methanol synthesis, and catalytic cracking, but is also of considerable interest as a barrier against diffusion of catalytically active metals such as rhodium or cobalt into alumina supports at elevated temperatures. 

Unpromoted Cu/Si02 is found to have a low activity for methanol synthesis from H2/CO mixtures, whereas an increased activity from H2/CO2. Alkali metal promotion increases the activity for methanol synthesis from the H2/CO mixtures, probably due to the increase in surface OH groups engaged in the formation of the formate species which are the precursors to the methanol. Cu/Si02 powder catalysts (with 5 wt% Cu) can be prepared by ion exchange of silica with Cu(NOs)2 in aqueous solution, followed by calcination and reduction. Such preparations contain very fine Cu particles ( 0.5 nm) on a powdered silica support as revealed by HRTEM. 

Because of the pure performance of traditional Cu catalysts in the hydrogenation of C02, efforts have been made to find new, more effective catalysts for direct C02 hydrogenation. The problem is to improve selectivity, specifically, to find catalysts that display high selectivity toward methanol formation and, at the same time, show low selectivity in the reverse water-gas shift reaction, that is, in the formation of CO. It appears that copper is the metal of choice for methanol synthesis from C02 provided suitable promoters may be added. Special synthesis methods have also been described for the preparation of traditional three-component Cu catalysts (Cu-ZnO-A1203 and Cu-Zn0-Cr203) to improve catalytic performance for C02 reduction. 

The low-pressure methanol synthesis process utilizes ternary catalysts based on copper, zinc oxide, and another oxide, such as alumina or chromia, prepared by coprecipitation. Cu-Zn0-Al203 and Cu-Zn0-Cr203 are usually the most important industrial catalysts. A significant advance was made when a two-stage precipitation was suggested in which ZnAl2C>4, a crystalline zinc aluminate spinel, was prepared prior to the main precipitation of copper-zinc species.372 This alteration resulted in an increase in catalyst stability for long-term performance with respect to deactivation. Catalyst lifetimes industrially are typically about 2 years. 

Thus a variety of hydrocarbons, ranging from natural gas to coal, are used in methanol production. Regardless of the feedstock used to prepare the synthesis gas, it is necessary to remove sulfur so that the converter catalyst is not poisoned. Before natural gas or naphtha is reformed, the feedstock is desulfurized. In the partial oxidation and coal gasification processes, the feedstock is first oxidized and the resulting synthesis gas is desulfurized before entering the converter. 

Oxidative methanolysis of azetidinone 176 followed by hydrogenolysis of compound 177 afforded /3-lactam 178, which was protected to obtain the protected amine 179. The best conditions for rearrangement of 179 were found using TFA. Conversion of compound 180 to carbacephem 183 was accomplished by ketone reduction, alcohol protection, and elimination of methanol. Synthesis of carbacephem derivative 186 has been performed by rhodium(n)-catalyzed cycliza-tion of iodonium ylide 185 <1997TL6981> (Scheme 33). The iodonium ylide 185 was easily prepared from the corresponding /3-keto ester 184 and [(diacetoxy)iodo]benzene in good yield. 

Several series of methanol synthesis catalysts were prepared by the coprecipitation of the appropriate metal salts in either Na2C03 or (NH4)2C03 using the CaviPro 300 (dual-orifice processor) at both high and low pressures. The experiments were carried out using a 0.152-mm first orifice while varying... 

The preparation of Cu/ZnO catalysts and precursors for the methanol synthesis reaction have been described [87, 88], while others [89] used a mixture of Pt, Ru and a leachable metal such as A1 to prepare catalysts for CO-tolerant catalysts for fuel cells. 

W. Wieldraaijer, et ah, Methanol Synthesis over Cu/ZnO Catalysts prepared by Ball Milling, Catalysis Lett., 1997, 48, 55. 

If catalysts are prepared by coprecipitation, the composition of the solutions determine the composition of the final product. Often the composition of the precipitate will reflect the solution concentrations, as was shown for CuO/ZnO catalysts for methanol synthesis [18], but this is not necessarily the case. For al-minum phosphates it was found that at low P A1 ratios the precipitate composition is identical to the solution composition, but if the P A1 ratio in the solution comes close to and exceeds unity, the precipitate composition asymptotically approaches a P A1 ratio of 1 [19]. Deviations from solution composition in coprecipitation processes will generally occur if solubilities of the different compounds differ strongly and precipitation is not complete or, if in addition to stoichiometric compounds, only one component forms an insoluble precipitate this the case for the aluminum phosphate. 

Elements such as B, Ga, P and Ge can substitute for Si and A1 in zeolitic frameworks. In naturally-occurring borosilicates B is usually present in trigonal coordination, but four-coordinated (tetrahedral) B is found in some minerals and in synthetic boro- and boroaluminosilicates. Boron can be incorporated into zeolitic frameworks during synthesis, provided that the concentration of aluminium species, favoured by the solid, is very low. (B,Si)-zeolites cannot be prepared from synthesis mixtures which are rich in aluminium. Protonic forms of borosilicate zeolites are less acidic than their aluminosilicate counterparts (1-4). but are active in catalyzing a variety of organic reactions, such as cracking, isomerization of xylene, dealkylation of arylbenzenes, alkylation and disproportionation of toluene and the conversion of methanol to hydrocarbons (5-11). It is now clear that the catalytic activity of borosilicates is actually due to traces of aluminium in the framework (6). However, controlled substitution of boron allows fine tuning of channel apertures and is useful for shape-selective sorption and catalysis. 

Figure 5.3.9 (A) Simplified geometric model [46, 89] for the preparation of industrial Cu/ZnO catalysts comprising subsequent meso- and nanostructuring of the material from [56], In a first micro structure directing step (mesostructuring), the Cu,Zn coprecipitate crystallizes in the form of thin needles of the zincian malachite precursor, (Cu,Zn)2(0H)C03. In a second step, the individual needles are decomposed and demix into CuO and ZnO. The effectiveness of this nanostructuring step depends critically on a high Zn content in the precursor, which in zincian malachite is limited to Cu Zn ca. 70 30 due to solid-state chemical constraints [75]. Finally, interdispersed CuO/ZnO is reduced to yield active Cu/ZnO. (B) Chemical memory Dependence of catalytic activity in methanol synthesis on the conditions of the coprecipitation and aging steps, from [85].

Shen GC, Fujita SI, Takezawa N. Preparation of precursors for the Cu/ZnO methanol synthesis catalysts by coprecipitation methods - effects of the preparation conditions upon the structures of the precursors. J Catal. 1992 138(2) 754—8. 

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