Alumina-based catalyst support oxidation reactions

In this paper, we describe methods for the preparation of single or binary inorganic oxide aerogels that could be used as carriers for high performance supported Pd automotive catalysts. Indeed we have shown that alumina - based aerogel supported palladium catalysts were very active in propane oxidation [2]. Here we present the catalytic performances, in the reaction CO + NO -1- O2, of palladium catalysts supported on some of the prepared aerogels and compare their performances with those of Pd or Pt-Rh catalysts supported on a commercial alumina. 

Early reports on this reaction were focused on iron oxide-based catalysts, supported on different supports alumina, zeolite, and active carbon, among others. Later, hydrotalcite-like compounds, and the topical V-Mg-0 catalysts were explored. Park and his group, one of the most active in this field, first reported the use of zirconia as a catalyst, " and later on that of ceria-zirconia-based catalysts and vanadium-antimony oxide-based catalysts. Publications up to 2007 have been subject of several reviews. Therefore, the most relevant feamres will be revised hereinafter, as well as more recent publications, and the reader is invited to get further details in the aforementioned reviews. 

Nitrogen-doped CNTs have also been reported recently by Pham-Huu and coworkers as an efficient metal-free catalyst in the partial oxidation of H2S into elemental sulfur [139]. Such reaction is mostly catalyzed by iron-based catalysts supported on different carriers such as silica, alumina, or silicon carbide [140,141]. The optimization process was further conducted... 

Other metal oxide catalysts studied for the SCR-NH3 reaction include iron, copper, chromium and manganese oxides supported on various oxides, introduced into zeolite cavities or added to pillared-type clays. Copper catalysts and copper-nickel catalysts, in particular, show some advantages when NO—N02 mixtures are present in the feed and S02 is absent [31b], such as in the case of nitric acid plant tail emissions. The mechanism of NO reduction over copper- and manganese-based catalysts is different from that over vanadia—titania based catalysts. Scheme 1.1 reports the proposed mechanism of SCR-NH3 over Cu-alumina catalysts [31b],... 

The same authors (77) also investigated the Michael addition of nitromethane to a,/l-unsaturated carbonyl compounds such as methyl crotonate, 3-buten-2-one, 2-cyclohexen-l-one, and crotonaldehyde in the presence of various solid base catalysts (alumina-supported potassium fluoride and hydroxide, alkaline earth metal oxides, and lanthanum oxide). The reactions were carried out at 273 or 323 K the results show that SrO, BaO, and La203 exhibited practically no activity for any Michael additions, whereas MgO and CaO exhibited no activity for the reaction of methyl crotonate and 3-buten-2-one, but low activities for 2-cyclohexen-l-one and crotonaldehyde. The most active catalysts were KF/alumina and KOH/alumina for all of the Michael additions tested. 

The sulfur oxidation is carried out at pressure higher than 8 atm and below 180 °C, with a proprietary supported-Mo oxide-based catalyst, for example, an alpha alumina-supported MgMo04 catalyst, operating at 110 °C and 17 atm [59c]. All the products produced by oxidation side reactions and by hydroperoxide reduction are separated from the gas oil stream together with the sulfones. This operation may result in diesel yield loss therefore, the valorization or upgrade of this oxidized stream affects the process economics. This stream can be blended into the heating oil pool or treated in a hydrocracking unit to recover valuable products. 

Soon after the invention of the Wacker process the formation of vinyl acetate by the oxidative acetoxylation of ethylene using Pd(OAc)2 was discovered by Moiseev [16], and the industrial production of vinyl acetate based on this reation was developed. At present, vinyl acetate is produced commercially by a gas-phase reaction of ethylene, acetic acid and O using Pd catalyst supported on alumina or silica (eq. 1.11). 

Aluminas are used in various catalytic applications, a-, y-, and -aluminas are all used as support materials, the first one in applications where low surface areas are desired, as in partial oxidation reactions. The latter two, and especially y-alumina, in applications where high surface areas and high thermal and mechanical stability are required. One of the most prominent applications of y-alumina as support is the catalytic converter for pollution control, where an alumina washcoat covers a monolithic support. The washcoat is impregnated with the catalytically active noble metals. Another major application area of high-surface aluminas as support is in the petrochemical industry in hydrotreating plants. Alumina-supported catalysts with Co, Ni, and/or Mo are used for this purpose. Also, all noble metals are available as supported catalysts based on aluminas. Such catalysts are used for hydrogenation reactions or sometimes oxidation reactions. If high... 

A simple oxide catalyst can be used in either the bulk state or supported on an inert oxide support material. The bulk oxides are usually prepared using a precipitation-calcination sequence similar to those described in Chapter 9 for the preparation of support oxides. " In general, the simple semiconductor oxides are not very good catalysts for synthetic reactions. The insulator oxides, however, can be used as solid acids and bases for a number of reactions. Alumina has been used as an acid catalyst for the vapor phase rearrangement of cyclohexanone oxime to caprolactam (Eqn. 10.9). Modification of the y-alumina surface by the addition of 10-20% of B2O3 increased its activity for this reaction, giving caprolactam in 80% selectivity even after several hours of continuous operation. "... 

A series of 7-aiumina- and silica-supported oxides as MnzOs, C03O4 and Sm-Mn, Sm-Co bimetallic combinations was prepared by incipient wetness impregnation of the supports with aqueous solutions containing the nitrates of the metals and citric acid. The results obtained with these catalysts in the acetone complete oxidation reaction have shown a predominant effect of the support and the transition metal nature. The silica-supported oxides exhibited a bulk-like behaviour with relatively little difference between the Mn and Co catalysts. In contrast, when supported on alumina the performance of the Mn catalysts was remarkably better than that of the Co-based ones. In this case, whereas the Sm-Mn catalysts maintained a rather good performance relative to that of Mn/Al203, the temperatures required for acetone combustion over the Sm-Co catalysts were significantly lower than the ones over C0/AI2O3. 

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