Carbon monoxide surface compositions

Because the synthesis reactions are exothermic with a net decrease in molar volume, equiUbrium conversions of the carbon oxides to methanol by reactions 1 and 2 are favored by high pressure and low temperature, as shown for the indicated reformed natural gas composition in Figure 1. The mechanism of methanol synthesis on the copper—zinc—alumina catalyst was elucidated as recentiy as 1990 (7). For a pure H2—CO mixture, carbon monoxide is adsorbed on the copper surface where it is hydrogenated to methanol. When CO2 is added to the reacting mixture, the copper surface becomes partially covered by adsorbed oxygen by the reaction C02 CO + O (ads). This results in a change in mechanism where CO reacts with the adsorbed oxygen to form CO2, which becomes the primary source of carbon for methanol. 

A convenient method for assessing the extent of surface oxidation is the measurement of volatile content. This standard method measures the weight loss of the evolved gases on heating up to 950°C in an inert atmosphere. The composition of these gases consists of three principal components hydrogen, carbon monoxide, and carbon dioxide. The volatile content of normal furnace blacks is under 1.5%, and the volatile content of oxidized special grades is 2.0 to 9.5%. 

Tn the synthesis of methane from carbon monoxide and hydrogen, it is desired to operate the reactor or reactors in such a way as to avoid carbon deposition on catalyst surfaces and to produce high quality product gas. Since gas compositions entering the reactor may vary considerably because of the use of diluents and recycle gas in a technical operation, it is desirable to estimate the effects of initial gas composition on the subsequent operation. Pressure and temperature are additional variables. 

Such a proof of the carbon monoxide oxidation was first given by one of us (28). It is very important to remark that the catalysts containing impurities were prepared by firing together in air at 600°C. for 3 hr. a mechanical mixture of the required components in adequate proportions. As pointed out by Fensham (54), this is much too low a temperature to ensure homogeneous solid solutions. Consequently, when a catalyst is described as NiO + 0.1% Li2O, there is no assurance that this nominal composition is realized at all either in the surface layer or in the bulk of the sample. As will be shown, this reservation is quite essential. 

The oxidation of carbon monoxide on nickel oxide has often been investigated (4, 6, 8, 9, II, 16, 17, 21, 22, 26, 27, 29, 32, 33, 36) with attempts to correlate the changes in the apparent activation energy with the modification of the electronic structure of the catalyst. Published results are not in agreement (6,11,21,22,26,27,32,33). Some discrepancies would be caused by the different temperature ranges used (27). However, the preparation and the pretreatments of nickel oxide were, in many cases, different, and consequently the surface structure of the catalysts—i.e., their composition and the nature and concentration of surface defects— were probably different. Therefore, an explanation of the disagreement may be that the surface structure of the semiconducting catalyst (and not only its surface or bulk electronic properties) influences its activity. 

Over the past 35 years, much has been learned about the electrooxidation of methanol on the surface of noble metals and metal alloys, in particular platinum and ruthenium [2, 4, 6, 7]. Significant overpotential losses occur in the reaction due to poisoning of the alloy catalyst surface by carbon monoxide. Yet, Pt-based metal alloys are still the most popular catalyst materials in the development of new fuel cell electrocatalysts, based on the expectation that a more CO-tolerant methanol catalyst will be developed. The vast ternary composition space beyond Pt-Ru catalysts has not been adequately explored. This section demonstrates how the ternary space can be explored using the high-throughput, electrocatalyst workflow described above. 

The product yields are particularly dependent upon the composition of the polymeric material, the temperature, and the ventilation conditions. Once the temperature of the surface is raised sufficiently (generally to around 300°C), then a process of thermal decomposition by oxidative pyrolysis begins. The products of nonflaming decomposition tend to be rich in partly decomposed organic molecules (many of which are irritants), carbon monoxide, and smoke particulates. This scenario presents a particular hazard to a sleeping subject in a small enclosure such as a closed bedroom, which can reach a lethal dose over a number of hours.6... 

Reactions of organic molecules sometimes follow a complex path through various intermediates. Where a reaction can be broken down into two or more steps, each may prefer to proceed on a different type of atom or on an active centre of a size and composition that uniquely fits it. Migration from one site or atom to another could proceed by surface migration or might require desorption and movement through the fluid phase (Scheme 8.1A). If this can happen, there is no necessity for both elements to occupy the same particle. Where carbon monoxide is a product of the reaction, as with... 

Indeed, lattice parameters of both the copper and the zinc oxide were found to depend on the catalyst composition. The lattice extension of copper was attributed to alpha brass formation upon partial reduction of zine oxide, and an attempt was made to correlate the lattice constant of copper with the decomposition rate of methanol to methyl formate. Furthermore, the decomposition rate of methanol to carbon monoxide was found to correlate with the changes of lattice constant of zinc oxide. Although such correlations did not establish the cause of the promotion in the absence of surface-area measurements and of correlations of specific activities, the changes of lattice parameters determined by Frolich et al. are real and indicate for the first time that the interaction of catalyst components can result in observable changes of bulk properties of the individual phases. Frolich et al. did not offer an interpretation of the observed changes in lattice parameters of zinc oxide. Yet these changes accompany the formation of an active catalyst, and much of this review will be devoted to the origin, physicochemical nature, and catalytic activity of the active phase in the zinc oxide-copper catalysts. 

BET area (Table V) and the copper area from oxygen chemisorption. Table VII summarizes the copper and zinc oxide areas so determined for the whole compositional range. The oxygen chemisorption method suffers from the uncertainty that some oxygen may be adsorbed on the copper solute and on defects in the zinc oxide surface that are formed only in the presence of copper. There is indirect evidence from a comparative study of carbon monoxide and oxygen chemisorption, however, that this is not the case and that oxygen titrates only the copper metal surface. 

Quantitative and qualitative changes in chemisorption of the reactants in methanol synthesis occur as a consequence of the chemical and physical interactions of the components of the copper-zinc oxide binary catalysts. Parris and Klier (43) have found that irreversible chemisorption of carbon monoxide is induced in the copper-zinc oxide catalysts, while pure copper chemisorbs CO only reversibly and pure zinc oxide does not chemisorb this gas at all at ambient temperature. The CO chemisorption isotherms are shown in Fig. 12, and the variations of total CO adsorption at saturation and its irreversible portion with the Cu/ZnO ratio are displayed in Fig. 13. The irreversible portion was defined as one which could not be removed by 10 min pumping at 10"6 Torr at room temperature. The weakly adsorbed CO, given by the difference between the total and irreversible CO adsorption, correlated linearly with the amount of irreversibly chemisorbed oxygen, as demonstrated in Fig. 14. The most straightforward interpretation of this correlation is that both irreversible oxygen and reversible CO adsorb on the copper metal surface. The stoichiometry is approximately C0 0 = 1 2, a ratio obtained for pure copper, over the whole compositional range of the... 

Carbon dioxide and hydrogen also interact with the formation of surface formate. This was documented for ZnO by the IR investigation of Ueno et al. (117) and, less directly, by coadsorption-thermal decomposition study (84). Surface complex was formed from C02 with H2 at temperatures above 180°C, which decomposed at 300°C with the evolution of carbon monoxide and hydrogen at the ratio CO Hs 1 1. When carbon dioxide and hydrogen were adsorbed separately, the C02 and H2 desorption temperatures were different, indicating conclusively that a surface complex was formed from C02 and H2. A complex with the same decomposition temperature was obtained upon adsorption of formaldehyde and methanol. Based upon the observed stoichiometry of decomposition products and upon earlier reported IR spectra of C02 + H2 coadsorbates, this complex was identified as surface formate. Table XVI compares the thermal decomposition peak temperatures and activation energies, product composition, and surface... 

The presence of the catalyst provides a lower-energy chemical path than that offered by a thermal reaction. A catalyst accelerates oxidation of hydrocarbon/carbon monoxide/air mixtures that lie outside the flammability range required for thermal reactions. In the exhaust of the automobile the composition of the pollutants is far below the flammability range yet the oxidation reactions occur by the catalyst providing a lower-energy chemical path to that offered by the thermal reaction. An excellent example is the oxidation of CO with and without a catalyst. Without a catalyst the rate-limiting step is 02 dissociation at 700°C followed by reaction with gas phase CO. In the presence of the Pt catalyst 02 dissociation is rapid and the rate-limiting step becomes the surface reaction between adsorbed O atoms and CO that occurs below 100°C. 

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