Catalyst catalytic oxidation reactions over

Cutlip, M. B., and C. N. Kenney, Limit cycle phenomena during catalytic oxidation reactions over a supported platinum catalyst, ACS Symp. Sen, 65, 475-486 (1978). 

Limit Cycle Phenomena during Catalytic Oxidation Reactions over a Supported Platinum Catalyst... 

Reactor System. A general purpose reactor system shown in Figure 1 was used in this work to study catalytic oxidation reactions over supported platinum catalyst pellets. This equipment allowed up to six precise gas mixtures to be prepared and made available for feed to the reactor. The switching valve directed a desired gas mixture flow to the reactor while another gas mixture flow was precisely measured by the bubble flow meter. 

In the cases of the selective oxidation reactions over metal oxide catalysts the so-called Mars-van Krevelen or redox mechanism [4], involving nucleophilic oxide ions 0 is widely accepted. A possible role of adsorbed electrophilic oxygen (molecularly adsorbed O2 and / or partially reduced oxygen species like C , or 0 ) in complete oxidation has been proposed by Haber (2]. However, Satterfield [1] queried whether surface chemisorbed oxygen plays any role in catalytic oxidation. 

The present chapter will primarily focus on oxidation reactions over supported vanadia catalysts because of the widespread applications of these interesting catalytic materials.5 6,22 24 Although this article is limited to well-defined supported vanadia catalysts, the supported vanadia catalysts are model catalyst systems that are also representative of other supported metal oxide catalysts employed in oxidation reactions (e.g., Mo, Cr, Re, etc.).25 26 The key chemical probe reaction to be employed in this chapter will be methanol oxidation to formaldehyde, but other oxidation reactions will also be discussed (methane oxidation to formaldehyde, propane oxidation to propylene, butane oxidation to maleic anhydride, CO oxidation to C02, S02 oxidation to S03 and the selective catalytic reduction of NOx with NH3 to N2 and H20). This chapter will combine the molecular structural and reactivity information of well-defined supported vanadia catalysts in order to develop the molecular structure-reactivity relationships for these oxidation catalysts. The molecular structure-reactivity relationships represent the molecular ingredients required for the molecular engineering of supported metal oxide catalysts. 

Most of the critical effects in oxidation reactions over Pt metals were observed under isothermal conditions. Hence the complex dynamic behaviour can be directly due to the structure of the detailed catalytic reaction mechanism, specifically to the laws of physico-chemical processes in the "reaction medium-catalyst systems. The types and properties of mathematical models to describe critical effects are naturally dependent on those physico-chemical prerequisites on which these models are often based [4, 9], Let us describe the most important factors used in the literature to interpret critical effects. 

Most oxidation reactions over oxide catalysts are well nnderstood in terms of the redox mechanism, for example, repeated rednction and oxidation of the surface layer or bulk of the oxide catalyst. In the first step, a metal oxide catalyst oxidizes reactant molecules, such as carbon monoxide to carbon dioxide (equation 1 reduction of catalyst). In the second step, the reduced catalyst is oxidized back to its initial state by oxygen molecules supplied by the gas phase (equation 2 reoxidation of catalyst). The catalytic oxidation (equation 3) proceeds by repetition of this redox cycle. 

Experimental facts and theoretical concepts existing in the hterature indicate that the formation of free radicals plays an important role in a number of catalytic oxidation reactions [1-5]. In the present paper we analyze the contribution of fi-ee radicals to several oxidative transformations of lower alkanes over oxide catalysts. Based on the thermochemical data and on the results of kinetic simulations it is shown that the observed reaction kinetics and product compositions in the mentioned above processes are determined by a set of interdependent heterogeneous and homogeneous reactions of fi ee radicals, i.e. they should not be considered as spectators taking part in side reactions, but as principal intermediates causing the main features of lower alkanes oxidation and design of catalysts. 

Industrial catalytic oxidation reactions are carried out at high reactant concentrations over a variety of supported metal catalysts. Because most industrial processes operate with well-characterized inlet streams (usually one reactant plus an oxidant), there has been little need to understand the complex processes that may occur in mixtures. As shown in Table 2, these reactions are typically carried out at temperatures greater than 400 °C, with the exception of ethene and CO oxidation. Such temperatures are generally required to achieve economical reaction rates (high ac-... 

Fig. 8.7 Schematic representation of catalytic cycle for NO oxidation reaction over metal-exchanged zeolite catalysts. Redox sites are associated with oxo-metal (isolated or binuclear) ion-exchanged sites...

Over the past two decades, Raman spectroscopy has been extensively applied during catalytic oxidation reactions by mixed-metal oxides and metals under in situ and operando spectroscopy conditions, which has allowed the direct identification of the catalytic active sites involved in the oxidation reactions. Among the multiple spectroscopic techniques that can provide information about the catalytic active sites under oxidation reaction conditions, Raman spectroscopy is unique because of its ability to directly provide molecular level information that allows discrimination among the different catalytic active sites which may be present in the oxidation catalyst. This chapter provides a snapshot of the types of fundamental information obtainable by Raman spectroscopy, and the different types of catalytic materials and oxidation reactions that have been reported, especially under oxidation reaction conditions. 

Hydroxylamine sulfate is produced by direct hydrogen reduction of nitric oxide over platinum catalyst in the presence of sulfuric acid. Only 0.9 kg ammonium sulfate is produced per kilogram of caprolactam, but at the expense of hydrogen consumption (11). A concentrated nitric oxide stream is obtained by catalytic oxidation of ammonia with oxygen. Steam is used as a diluent in order to avoid operating within the explosive limits for the system. The oxidation is followed by condensation of the steam. The net reaction is... 

The production of acetic acid from n-butene mixture is a vapor-phase catalytic process. The oxidation reaction occurs at approximately 270°C over a titanium vanadate catalyst. A 70% acetic acid yield has been reported. The major by-products are carbon oxides (25%) and maleic anhydride (3%) ... 

Oxidation kinetics over platinum proceeds at a negative first order at high concentrations of CO, and reverts to a first-order dependency at very low concentrations. As the CO concentration falls towards the center of a porous catalyst, the rate of reaction increases in a reciprocal fashion, so that the effectiveness factor may be greater than one. This effectiveness factor has been discussed by Roberts and Satterfield (106), and in a paper to be published by Wei and Becker. A reversal of the conventional wisdom is sometimes warranted. When the reaction kinetics has a negative order, and when the catalyst poisons are deposited in a thin layer near the surface, the optimum distribution of active catalytic material is away from the surface to form an egg yolk catalyst. 

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