Partial oxidation production from

We have summarized below recent results concerning spectroscopic / flow reactor investigations of hydrocarbons partial and total oxidation on different transition metal oxide catalysts. The aim of this study is to have more information on the mechanisms of the catalytic activity of transition metal oxides, to better establish selective and total oxidation ways at the catalyst surface, and to search for partial oxidation products from light alkane conversion. 

Run-on occurs when the engine continues running even after the spark has been switched off. It is caused by autoignition induced by piston compression only. This occurs when active partial oxidation products from... 

Similar data have been obtained for the adsorption of but-l-ene and isobutene on copper(i) and copper(ii) oxides. Although the results are less clear cut than with the propene system, in general a similar pattern emerges. The reversibly adsorbed species has infrared bands characteristic of a 7r-bonded allyl species. Addition of oxygen to reversibly adsorbed but-l-ene at room temperature results in bonds characteristic of acrolein and acetaldehyde. Methyl vinyl ketone is only formed at higher temperatures. The adsorption of the major partial oxidation products on copper(i) oxide was also investigated. Metha-crolein behaves like acrolein and is reversibly adsorbed. Methyl vinyl ketone, however, mainly forms carboxylate and carbonate types of structures. This reflects the ease of oxidation of the partial oxidation product. The reason for the higher selectivities observed with the branched alkenes can thus be ascribed to the relative ease of oxidation of the partial oxidation product from the linear allene. 

Emissions from methanol vehicles are expected to produce lower HC and CO emissions than equivalent gasoline engines. However, methanol combustion produces significant amounts of formaldehyde (qv), a partial oxidation product of methanol. Eormaldehyde is classified as an air toxic and its emissions should be minimized. Eormaldehyde is also very reactive in the atmosphere and contributes to the formation of ozone. Emissions of NO may also pose a problem, especiaHy if the engine mns lean, a regime in which the standard three-way catalyst is not effective for NO reduction. 

Residuals Produced Typical residuals resulting from oxidation are partial oxidation products (e.g., chlorinated organics) and inorganic salts (e.g., NaCl, Mn02). Additional treatment may be required to permit disposal. 

Partial oxidations over complex mixed metal oxides are far from ideal for singlecrystal like studies of catalyst structure and reaction mechanisms, although several detailed (and by no means unreasonable) catalytic cycles have been postulated. Successful catalysts are believed to have surfaces that react selectively vith adsorbed organic reactants at positions where oxygen of only limited reactivity is present. This results in the desired partially oxidized products and a reduced catalytic site, exposing oxygen deficiencies. Such sites are reoxidized by oxygen from the bulk that is supplied by gas-phase O2 activated at remote sites. 

The quantitative analyses of reaction products due to partial or complete oxidation can be performed by different methods. This type of determination is essential to improve electrode composition. Apart from a decrease in the Coulombic efficiency (see Section 11.2), the formation of partially oxidized products can be deleterious for the DMFC application because some of these products (e.g., formic acid) may be in liquid form and are corrosive. 

It is well established that the main products of ethanol electro-oxidation on Pt in acidic media are acetaldehyde and acetic acid, partial oxidation products that do not require C—C bond breaking, with their relative yields depending on the experimental conditions [Iwasita and Pastor, 1994]. Apart from the loss of efficiency associated with the partial oxidation, acetic acid is also unwanted, as it constitutes a catalyst poison. 

A simplified scheme of the dual pathway electrochemical methanol oxidation on Pt resulting from recent advances in the understanding of the reaction mechanism [Cao et al., 2005 Housmans et al, 2006] is shown in Fig. 15.10. The term dual pathway encompasses two reaction routes one ( indirect ) occurring via the intermediate formation of COads. and the other ( direct ) proceeding through partial oxidation products such as formaldehyde. 

All effluents must be characterized in detail when treating agents contaminated with metals from disassembled chemical weapons (i.e., potential trace species and reaction by-products, such as nitrated hydrocarbons, partially oxidized products, and metals, must be identified) and their environmental impacts evaluated. 

One example of membrane reactors is oxidation, in which oxygen from one phase diffuses from one side of an oxygen-permeable membrane to react with a fuel on the other side of the membrane. This avoids a high concentration of O2 on the fuel side, which would be flammable. A catalyst on the fuel side of the membrane oxidizes the fuel to partial oxidation products. One important process using a membrane reactor is the reaction to oxidize methane to form syngas,... 

The reactivity of the supported vanadium oxide catalysts for other oxidation reactions also show similar trends as the oxide support is varied from titania to silica [13]. The activity and selectivity for partial oxidation products of vanadium oxide supported on titania being higher than vanadium oxide supported on silica. The oxidation activity of the supported vanadium oxide catalysts is related to the ability to donate oxygen to form the required oxidation products. The... 

Much recent research (7-5) has been devoted to converting methane to products that are more easily transported and more valuable. Such more valuable products include higher hydrocarbons and the partial oxidation products of methane which are formed by either direct routes such as oxidative coupling reactions or indirect methods via synthesis gas as an intermediate. The topic of syngas formation by oxidation of CH4 has been considered primarily from an engineering perspective (7-5). Most fundamental studies of the direct oxidation of CH4 have dealt with the CH4 + O2 reaction system in excess O2 and at lower temperatures (6-10). 

The present study investigates a different approach. The membrane is used to allow the desired intermediate product to escape from the reaction zone before it is consumed by further reaction. This use of a membrane reactor was first suggested by Michaels [15]. The partial oxidation of methane, which is a challenging reaction of the type propos for this application of membrane reactors, has been analyzed herein. There is no thermodynamic limitation for the production of carbon dioxide and water, actually these products are favored. It is desired to remove any partial oxidation product, for example formaldehyde, before it has a chance to be further oxidized. 

The performance of a number of single oxides of transition metals was studied by Skorbilina et al. [295] using a differential reactor. As usual, o-tolualdehyde, phthalic anhydride and carbon oxides are the main reaction products. The initial selectivity with respect to partial oxidation products decreases in the order Co > Ti > V > Mo > Ni > Mn > Fe > Cu from 71% to 33%. The relatively high initial selectivities demonstrated by the deep oxidation catalysts (e.g. Co, Ni, Mn) indicates that the primary activation is probably the same for all these catalysts, while the differences that actually determine the character of the catalyst are connected with the stability of intermediates and products. 

The catalytic properties of TS-1 appeared to be unique. In oxidation reactions, with H202 as the oxidant, many organic compounds could be oxidized selectively and efficiently. Partial oxidation products could be obtained in high yields, and almost all the oxygen available from H202 was used to produce the desired compounds, with only slight decomposition to give H20 and 02 (Neri et al., 1985, 1986 Romano et al., 1990). 

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