Oxide-based catalysts

Isobutyl alcohol [78-83-1] forms a substantial fraction of the butanols produced by higher alcohol synthesis over modified copper—zinc oxide-based catalysts. Conceivably, separation of this alcohol and dehydration affords an alternative route to isobutjiene [115-11 -7] for methyl /-butyl ether [1624-04-4] (MTBE) production. MTBE is a rapidly growing constituent of reformulated gasoline, but its growth is likely to be limited by available suppHes of isobutylene. Thus higher alcohol synthesis provides a process capable of supplying all of the raw materials required for manufacture of this key fuel oxygenate (24) (see Ethers). 

Vanadium phosphoms oxide-based catalysts ate unstable in that they tend to lose phosphoms over time at reaction temperatures. Hot spots in fixed-bed reactors tend to accelerate this loss of phosphoms. This loss of phosphoms also produces a decrease in selectivity (70,136). Many steps have been taken, however, to aHeviate these problems and create an environment where the catalyst can operate at lower temperatures. For example, volatile organophosphoms compounds are fed to the reactor to mitigate the problem of phosphoms loss by the catalyst (137). The phosphoms feed also has the effect of controlling catalyst activity and thus improving catalyst selectivity in the reactor. The catalyst pack in the reactor may be stratified with an inert material (138,139). Stratification has the effect of reducing the extent of reaction pet unit volume and thus reducing the observed catalyst temperature (hot... 

N. Singh, "VOC Destmetion at Low Temperatures Using a Novel Thermally Stable Transition-Metal Oxide-Based Catalyst," presented at the First North American Conference on Emerging Clean Air Technologies and Business Opportunities, Toronto, Canada, Sept. 1994. 

The width of molecular weight distribution (MWD) is usually represented by the ratio of the weight—average and the number—average molecular weights, MJM. In iadustry, MWD is often represented by the value of the melt flow ratio (MER), which is calculated as a ratio of two melt indexes measured at two melt pressures that differ by a factor of 10. Most commodity-grade LLDPE resias have a narrow MWD, with the MJM ratios of 2.5—4.5 and MER values in the 20—35 range. However, LLDPE resias produced with chromium oxide-based catalysts have a broad MWD, with M.Jof 10—35 and MER of 80-200. 

LLDPE resias are produced ia iadustry with three classes of catalysts (11—14) titanium-based catalysts (Ziegler), metallocene-based catalysts (Kaminsky and Dow), and chromium oxide-based catalysts (Phillips). 

Chromium Oxide-Based Catalysts. Chromium oxide-based catalysts were originally developed by Phillips Petroleum Company for the manufacture of HDPE resins subsequendy, they have been modified for ethylene—a-olefin copolymerisation reactions (10). These catalysts use a mixed sihca—titania support containing from 2 to 20 wt % of Ti. After the deposition of chromium species onto the support, the catalyst is first oxidised by an oxygen—air mixture and then reduced at increased temperatures with carbon monoxide. The catalyst systems used for ethylene copolymerisation consist of sohd catalysts and co-catalysts, ie, triaLkylboron or trialkyl aluminum compounds. Ethylene—a-olefin copolymers produced with these catalysts have very broad molecular weight distributions, characterised by M.Jin the 12—35 and MER in the 80—200 range. 

Dehydrogenation, Ammoxidation, and Other Heterogeneous Catalysts. Cerium has minor uses in other commercial catalysts (41) where the element s role is probably related to Ce(III)/Ce(IV) chemistry. Styrene is made from ethylbenzene by an alkah-promoted iron oxide-based catalyst. The addition of a few percent of cerium oxide improves this catalyst s activity for styrene formation presumably because of a beneficial interaction between the Fe(II)/Fe(III) and Ce(III)/Ce(IV) redox couples. The ammoxidation of propjiene to produce acrylonitrile is carried out over catalyticaHy active complex molybdates. Cerium, a component of several patented compositions (42), functions as an oxygen and electron transfer through its redox couple. 

Much like the oxidation of propylene, which produces acrolein and acrylic acid, the direct oxidation of isobutylene produces methacrolein and methacrylic acid. The catalyzed oxidation reaction occurs in two steps due to the different oxidation characteristics of isobutylene (an olefin) and methacrolein (an unsaturated aldehyde). In the first step, isobutylene is oxidized to methacrolein over a molybdenum oxide-based catalyst in a temperature range of 350-400°C. Pressures are a little above atmospheric ... 

The results of catalytic activities in the dehydrogenation of ethylbenzene with various iron oxide based catalysts are shown in Fig. l(a-b). The number in the parentheses of the catalyst codes indicates the weight fi-action of metal per gram carbon. On oxidized CNF alone less than 20% conversion of EB is observed after 3 h on stream. The conversion of ethylbenzene... 

V-Sb-oxide based catalysts show interesting catal)dic properties in the direct synthesis of acrylonitrile from propane [1,2], a new alternative option to the commercial process starting from propylene. However, further improvement of the selectivity to acrylonitrile would strengthen interest in the process. Optimization of the behavior of Sb-V-oxide catalysts requires a thorough analysis of the relationship between structural/surface characteristics and catalytic properties. Various studies have been reported on the analysis of this relationship [3-8] and on the reaction kinetics [9,10], but little attention has been given to the study of the surface reactivity of V-Sb-oxide in the transformation of possible intermediates and on the identification of the sxirface mechanism of reaction. 

Jibril, B.Y. Propane oxidative dehydrogenation over chromium oxide-based catalysts. Appl. Catal. A General 2004, 264, 193-202. 

Taylor, H. and O Leary, R. A study of uranium oxide based catalysts for the oxidative destruction of short chain alkanes, Appl. Catal, B Environmental, 2000, Volume 25, Issues 2-3, 137-149. 

OPTIMIZATION OF ALKALINE EARTH METAL OXIDE Base catalyst... 

Analysis of structure-activity relationships shows that various species characterized by different reactivities exist on the surface of vanadium oxide-based catalysts.339 The redox cycle between V5+ and V4+ is generally accepted to play a key role in the reaction mechanism, although opposite relationships between activity and selectivity, and reducibility were established. More recent studies with zirconia-supported vanadium oxide catalysts showed that vanadium is present in the form of isolated vanadyl species or oligomeric vanadates depending on the loading.345,346 The maximum catalytic activity was observed for catalysts with vanadia content of 3-5 mol% for which highly dispersed polyvanadate species are dominant. 

Unlike Ziegler catalysts, chromium oxide based catalysts are extremely sensitive to minor changes in the preparation or calcining history. The active sites no doubt respond to the local electronic environment, which determines the molecular weight distribution of the polymer. Therefore, replacing the... 

Chromium oxide-based catalysts, which were originally developed for the manufacture of HDPE resins, have been modified for cthylcnc-< -olcfin copolymerization reactions. These catalysts use. a mixed silica-titania support containing from 2 to 20 wt % of Ti. 

Metal oxide-based catalysts were also studied57 in the early days of development of olefin epoxidation with alkyl hydroperoxides. M0O3 was an excellent catalyst, WO3 showed moderate activity and other oxides (V2O5, Se02,... 

With this in mind we found it worthwhile to investigate this oxidation reaction in the gas phase over a solid catalyst, thereby avoiding the formation of the by-products mentioned above. In this paper we describe some catalyst screening experiments and the development of a process using an heterogeneous catalyst. As will be shown, copper oxide based catalysts exhibit high... 

Methyl-4-penten-2,3-dione (2) can be obtained in high selectivity (>95%) by oxidative dehydrogenation of 3-hydroxy l-methyl-4-penten-2-one (1) over copper oxide based catalysts. 

S. Zine, A. Sayari and A. Ghorbel, Catalytic Nitroxydation of Paraxylene over chromium oxide Based catalysts the Canadian Journal of chemical Engeneering, vol. 65 February, 1987 pp 127 - 131. 

Solid heteropoly compounds are suitable oxidation catalysts for various reactions such as dehydrogenation of O- and N-containing compounds (aldehydes, carboxylic acids, ketones, nitriles, and alcohols) as well as oxidation of aldehydes. Heteropoly catalysts are inferior to Mo-Bi oxide-based catalysts for the allylic oxidation of olefins, but they are much better than these for oxidation of methacrolein (5). Mo-V mixed-oxide catalysts used commercially for the oxidation of acrolein are not good catalysts for methacrolein oxidation. The presence of an a-methyl group in methacrolein makes the oxidation difficult (12). The oxidation of lower paraffins such as propane, butanes, and pentanes has been attempted (324). Typical oxidation reactions are listed in Table XXXI and described in more detail in the following sections. 

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. 

Initial experimentation aimed at demonstrating the principle feasibility of the appealingly simple adsorptive Claus process concept described in the previous section yielded promising results indicating excellent harmonization between the catalytic and adsorptive processes for a commercial titanium oxide-based catalyst and a 3A zeolite adsorbent, respectively [30], The amounts of water vapor adsorbed... 

In this work we have studied two commercial oxide-based catalysts with a variety of feeds containing hydrocarbons, chlorocarbons, and mixtures of the two. The experiments deal primarially with oxidation at constant total conversion (> 99%) over extended periods of time, and much data are presented as the temperature-required vs time-on-stream to maintain the set conversion level [4]. Hydrocarbon oxidation has, of course, been studied for many years. The total oxidation of halogenated VOC s is, though, a relatively new area [5,6] ... 

---