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Methanol Synthesis The transformation of synthesis gas to methanol [Eq (33)] is a process of major industrial importance From the point of view of hydrocarbon chemistry, the significance of the process is the subsequent conversion of methanol to hydrocarbons (thus allowing Fischer-Tropsch chemistry to become more selective) Since other possible transformations, such as, formation of dimethyl ether, higher alcohols, and hydrocarbons, are accompanied with higher negative free-energy change, methanol is thermodynamically a less probable product Therefore, solely on a thermodynamic basis, these compounds as well as methane should be formed in preference to methanol To avoid the formation of the former compounds, the synthesis of methanol requires selective catalysts and suitable reaction conditions Under such conditions, methanol is the predominant product This indicates that the transformations leading to the formation of the other compounds are kinetically controlled In the methanol-to-hydrocarbon conversion, dimethyl ether generally is converted similarly to methanol.

Data obtained via the Show Custom Dialog step overrides any existing validation settings for the input fields including the Strict option. As such, it might not be a good idea to use Show Custom Dialog to input data into fields for which critical validation criteria have been set. Similarly, this step also overrides the Allow Entry into Field field formatting option. That is, even if Allow Entry is disabled, the Show Custom Dialog step will still be allowed to receive and record input for the field.

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An industrial process to produce methanol from carbon monoxide and hydrogen was developed by BASF in 1923 using a zinc oxide-chromia catalyst 361 ,362 Since this catalyst exhibited relatively low specific activity, high temperature was required The low equilibrium methanol concentration at this high temperature was compensated by using high pressures This so-called high-pressure process was operated typically at 200 atm and 350 C The development of the process and early results on methanol synthesis were reviewed by Natta 63 The high-pressure synthesis was superseded in the 1960s by the ICI low-pressure method after introducing Cu-ZnO-based catalysts 61,362,364,365 Conditions applied in this technology are 50-100 atm and 220-250 C A similar process was developed by Lurgi employing a CuO-ZnO catalyst 361 ,366,367 Since copper-based catalysts are sensitive to sulfur and chlorine in the feed, a precondition for their industrial application is the use of high-purity synthesis gas prepared from methane.

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At present the low-pressure technology dominates the worldwide production of methanol The introduction of copper-based catalysts spurred an intense research activity resulting in several review articles on the topiC OO,368-371 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-ZnO-Al203 and Cu-ZnO-Cr203 are usually the most important industrial catalysts A significant advance was made when a two-stage precipitation was suggested in which ZnA1 20 4, a crystalline zinc aluminate spinel, was prepared prior to the main precipitation of copper-zinc species 72 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.

The Cu-ZnO binary catalyst has been known to exhibit high activity in methanol formation at low temperature, but fast deactivation prevented commercialization 73 The addition of a third component, however, results in stable catalyst activity The.

q2(z)a(z) = [q2(z)g1(z) + l]b(z) + r2(z) (6.15)

These unit operations, with the exception of dispersion, involve mass transfer between the solid and liquid phases. Dispersion of solids is a physical process where solid particles or aggregates are suspended and dispersed by the action of an agitator in a uid to achieve a

than the monofunctional metal cyclization. Pt in the form of single crystals has been extensively studied as catalyst for the dehydrocyclization reaction. Results related to the aromatization reaction, however, were complicated because of the existence of other competing transformations such as isomerization and hydrogenolysis. Alloying Pt with a suitable metal can modify reactivity and selectivity. An especially well suited catalyst is CU3Pt(l1l) allowing significant observations to be acquired. Aromatization reactions were studied in detail with several C6 hydrocarbons, including I_hexene,310,314,315 cyclohexene,315 polyunsaturated linear and cyclic compounds,310,315 and 4-phenyl-l-butene 16 In the case of C6 hydrocarbons, cyclization is the rate-determining step and mono- and biunsaturated cyclic compounds are not suggested to be intermediates for the dehydrocyclization of I-hexene to benzene 15

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