Water gas catalytic reaction

From a consideration of the equilibrium of reaction (3) as a function of temperature (Fig. 14), it is noticed that this reaction occurs readily to the right at temperatures of 900° to 1000° C. The (COa - - CH4) reaction is catalyzed by substances similar to those used for the methane-steam reaction, i.e., 90 per cent nickel oxide-10 per cent thoria, etc. A combination of reaction (2) and reactions (3) and (4) may, hence, be considered as a means of producing hydrogen and carbon monoxide mixtures or by use of the water-gas catalytic reaction, (6), of producing hydrogen. A combination of these reactions thus becomes ... 

Where hydrogen is desired, it is necessary to oxidize the carbon monoxide by further reaction with steam through the water-gas catalytic reaction since by this means an extra mol of hydrogen is obtained per mol of carbon monoxide present in the gas. 

It is claimed that the use of pressure makes it possible to increase the rate of the water-gas catalytic reaction.89 Since the reaction occurs without any change in volume, the equilibrium conversion at a given temperature will not be affected by an increase in pressure, excepting in so far as the gaseous reactants may deviate from the gas laws in their behavior but as the reaction is necessarily a catalytic process, the use of pressure may affect changes in the adsorption of the reactants at the catalyst surface in such a manner as to give an increase in the rate. 

Study of the mechanism of this complex reduction-Hquefaction suggests that part of the mechanism involves formate production from carbonate, dehydration of the vicinal hydroxyl groups in the ceUulosic feed to carbonyl compounds via enols, reduction of the carbonyl group to an alcohol by formate and water, and regeneration of formate (46). In view of the complex nature of the reactants and products, it is likely that a complete understanding of all of the chemical reactions that occur will not be developed. However, the Hquefaction mechanism probably involves catalytic hydrogenation because carbon monoxide would be expected to form at least some hydrogen by the water-gas shift reaction. 

The mixture of carbon monoxide and hydrogen is enriched with hydrogen from the water gas catalytic (Bosch) process, ie, water gas shift reaction, and passed over a cobalt—thoria catalyst to form straight-chain, ie, linear, paraffins, olefins, and alcohols in what is known as the Fisher-Tropsch synthesis. 

Prior to methanation, the gas product from the gasifier must be thoroughly purified, especially from sulfur compounds the precursors of which are widespread throughout coal (23) (see Sulfurremoval and recovery). Moreover, the composition of the gas must be adjusted, if required, to contain three parts hydrogen to one part carbon monoxide to fit the stoichiometry of methane production. This is accompHshed by appHcation of a catalytic water gas shift reaction. 

Synthesis Gas Chemicals. Hydrocarbons are used to generate synthesis gas, a mixture of carbon monoxide and hydrogen, for conversion to other chemicals. The primary chemical made from synthesis gas is methanol, though acetic acid and acetic anhydride are also made by this route. Carbon monoxide (qv) is produced by partial oxidation of hydrocarbons or by the catalytic steam reforming of natural gas. About 96% of synthesis gas is made by steam reforming, followed by the water gas shift reaction to give the desired H2 /CO ratio. 

In addition to platinum and related metals, the principal active component ia the multiflmctioaal systems is cerium oxide. Each catalytic coaverter coataias 50—100 g of finely divided ceria dispersed within the washcoat. Elucidatioa of the detailed behavior of cerium is difficult and compHcated by the presence of other additives, eg, lanthanum oxide, that perform related functions. Ceria acts as a stabilizer for the high surface area alumina, as a promoter of the water gas shift reaction, as an oxygen storage component, and as an enhancer of the NO reduction capability of rhodium. 

Dehydrogenation processes in particular have been studied, with conversions in most cases well beyond thermodynamic equihbrium Ethane to ethylene, propane to propylene, water-gas shirt reaction CO -I- H9O CO9 + H9, ethylbenzene to styrene, cyclohexane to benzene, and others. Some hydrogenations and oxidations also show improvement in yields in the presence of catalytic membranes, although it is not obvious why the yields should be better since no separation is involved hydrogenation of nitrobenzene to aniline, of cyclopentadiene to cyclopentene, of furfural to furfuryl alcohol, and so on oxidation of ethylene to acetaldehyde, of methanol to formaldehyde, and so on. 

CO2 can be readily obtained in small amounts by the action of acids on carbonates. On an industrial scale the main source Is as a byproduct of the synthetic ammonia process in which the H2 required is generated either by the catalytic reaction (a) or by the water-gas shift reaction (b) ... 

Alkali promoters are often used for altering the catalytic activity and selectivity in Fischer-Tropsch synthesis and the water-gas shift reaction, where C02 adsorption plays a significant role. Numerous studies have investigated the effect of alkalis on C02 adsorption and dissociation on Cu, Fe, Rh, Pd, A1 and Ag6,52 As expected, C02 always behaves as an electron acceptor. 

In the sixth chapter the activation of O-H bonds of water, alcohols and carboxylic acids, and their addition to multiple bonds is reported. Since the formally oxidative addition of ROH gives rise to hydrido(hydroxo) complexes, [MH(OR)Ln] which are postulated as intermediates in many important reactions (water gas shift reaction, Wacker-chemistry, catalytic transfer hydrogenations etc.) the authors of this chapter,... 

The synthesis of [Ircp Cl(bpy-cd)]Cl, where bpy-cd is a /3-cyclo-dextrin attached at the 6 position to a bpy ligand, is detailed.138 The complexes [Ircp (diimine)X]+, X = C1, H, diimine = bpy, phen, are active catalysts for the light-driven water-gas-shift reaction.139 The hydride complexes luminesce at 77 K and room temperature, whereas the chloride complexes do not.140 The three-legged piano-stool arrangement of the ligands in [Ircp (bpy)Cl]+ and [Ircp (4,4 -COOFl-bpy)Cl]+ is confirmed by X-ray crystallography.141,142 Further mechanistic studies on the catalytic cycle shown in reaction Scheme 11 indicate that Cl- is substituted by CO and the rate-determining step involves loss of C02 and H+ to leave the Ir1 species, which readily binds Fl+ to yield the lrIH hydride species.143... 

Cerium oxides are outstanding oxide materials for catalytic purposes, and they are used in many catalytic applications, for example, for the oxidation of CO, the removal of SOx from fluid catalytic cracking flue gases, the water gas shift reaction, or in the oxidative coupling reaction of methane [155, 156]. Ceria is also widely used as an active component in the three-way catalyst for automotive exhaust pollution control,... 

CH ligands, (2) to initiate homogeneous catalytic reactions such as hydrogenation, hydroformylation, and the water gas shift reaction, and (3) to study the mechanism of thermal reactions by the photochemical preparation of possible intermediates. 

As a result of the kinetics and the equilibria mentioned above, all iodide in the system occurs as methyl iodide. The reaction in Equation (2) makes the rate of the catalytic process independent of the methanol concentration. Within the operation window of the process, the reaction rate is independent of the carbon monoxide pressure. The selectivity in methanol is in the high 90s but the selectivity in carbon monoxide may be as low as 90%. This is due to the water-gas shift reaction ... 

Other catalytic hydrocarbon reactions indude decomposition of olefins over a powdered nickel catalyst [84], hydrogenation of alkenes, hydrocracking of cycloalk-enes, and water-gas shift reactions [64]. 

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