Metal supported chromium catalysts from

For polyethylene produced with transition metal catalysts, molecular weight distribution is dictated largely by the catalyst employed. Polydispersities typically range from 2-3 for polyethylene made with single site catalysts, 4-6 for polymer produced with Ziegler-Natta catalysts and 8-20 for polyethylene made with supported chromium catalysts. These differences are illustrated... 

Transition metal catalysts are crucial to the production of polyethylene. Indeed, it would not be practical to produce linear versions of polyethylene without these catalysts. It is difficult to imagine a world without products made from these versatile polymers in our homes, vehicles and workplaces. Ziegler-Natta and supported chromium catalysts will continue to be the dominant catalysts for LLDPE and HOPE for the foreseeable future. However, as single-site catalyst... 

These siUca-supported catalysts demonstrate the close connections between catalysis in solutions and catalysis on surfaces, but they are not industrial catalysts. However, siUca is used as a support for chromium complexes, formed either from chromocene or chromium salts, that are industrial catalysts for polymerization of a-olefins (64,65). Supported chromium complex catalysts are used on an enormous scale in the manufacture of linear polyethylene in the Unipol and Phillips processes (see Olefin polymers). The exact stmctures of the surface species are still not known, but it is evident that there is a close analogy linking soluble and supported metal complex catalysts for olefin polymerization. 

Table IV presents the results of the determination of polyethylene radioactivity after the decomposition of the active bonds in one-component catalysts by methanol, labeled in different positions. In the case of TiCU (169) and the catalyst Cr -CjHsU/SiCU (8, 140) in the initial state the insertion of tritium of the alcohol hydroxyl group into the polymer corresponds to the expected polarization of the metal-carbon bond determined by the difference in electronegativity of these elements. The decomposition of active bonds in this case seems to follow the scheme (25) (see Section V). But in the case of the chromium oxide catalyst and the catalyst obtained by hydrogen reduction of the supported chromium ir-allyl complexes (ir-allyl ligands being removed from the active center) (140) C14 of the...

Thermal reduction at 623 K by means of CO is a common method of producing reduced and catalytically active chromium centers. In this case the induction period in the successive ethylene polymerization is replaced by a very short delay consistent with initial adsorption of ethylene on reduce chromium centers and formation of active precursors. In the CO-reduced catalyst, CO2 in the gas phase is the only product and chromium is found to have an average oxidation number just above 2 [4,7,44,65,66], comprised of mainly Cr(II) and very small amount of Cr(III) species (presumably as Q -Cr203 [66]). Fubini et al. [47] reported that reduction in CO at 623 K of a diluted Cr(VI)/Si02 sample (1 wt. % Cr) yields 98% of the silica-supported chromium in the +2 oxidation state, as determined from oxygen uptake measurements. The remaining 2 wt. % of the metal was proposed to be clustered in a-chromia-like particles. As the oxidation product (CO2) is not adsorbed on the surface and CO is fully desorbed from Cr(II) at 623 K (reduction temperature), the resulting catalyst acquires a model character in fact, the siliceous part of the surface is the same of pure silica treated at the same temperature and the anchored chromium is all in the divalent state. 

Catalysts based on other metals, such as gallium and vanadium oxides, can be also employed in DH processes [8, 9]. For example, silica-supported gallium oxide catalyst has been found to be moderately active, but quite selective in propane dehydrogenation (up to 80%) and results in much less coking, 1/10 of that using a silica-supported chromium oxide [8], There is an extensive research aimed to find new DH catalysts that will perform well at moderate temperatures, suffer less from coke deposition and maintain catalytic activity for long periods of time without regeneration. 

Chromium compounds are widely used in many industries metal finishing and electroplating, leather tanning, pigments manufacturing, photography and catalysts production [1]. The presence of chromium species in wastewater of all of these industries is a problem because of the affect onto die human physiolo. Chromium removal from wastewaters by adsorption onto activated charcoals is an important process in the environmental protection [2]. On the other hand the chromium species adsorption from aqueous solution is one of the processes for chromium catalysts supported on activated c ons production [3],... 

Improvements in acrylonitrile yield are also reported with other vapor phase promoters. A patent assigned to Monsanto Co. (125) describes the use of sulfur and sulfur-containing compounds in the feed gas mixture for production of acrylonitrile or methacrylonitrile from propane or isobutane over metal oxide catalysts. Examples of effective sulfur-containing compounds include alkyl or dialkyl sulfides, mercaptans, hydrogen sulfide, ammonium sulfide, and sulfiir dioxide. Best results are apparently achieved using a molar ratio of sulfur (or sulfur compound) to hydrocarbon of 0.0005 1 to 0.01 1. Nitric oxide has also been examined as a gas-phase promoter for propane and isobutane ammoxidation (126). However, it does not appear to be as effective as halogen or sulfur. Selectivities to acrylonitrile from propane are only about 30% over an alumina-supported chromium-nickel oxide catalyst. 

Catalysts used for preparing amines from alcohols iaclude cobalt promoted with tirconium, lanthanum, cerium, or uranium (52) the metals and oxides of nickel, cobalt, and/or copper (53,54,56,60,61) metal oxides of antimony, tin, and manganese on alumina support (55) copper, nickel, and a metal belonging to the platinum group 8—10 (57) copper formate (58) nickel promoted with chromium and/or iron on alumina support (53,59) and cobalt, copper, and either iron, 2iac, or zirconium (62). 

All mechanisms proposed in Scheme 7 start from the common hypotheses that the coordinatively unsaturated Cr(II) site initially adsorbs one, two, or three ethylene molecules via a coordinative d-7r bond (left column in Scheme 7). Supporting considerations about the possibility of coordinating up to three ethylene molecules come from Zecchina et al. [118], who recently showed that Cr(II) is able to adsorb and trimerize acetylene, giving benzene. Concerning the oxidation state of the active chromium sites, it is important to notice that, although the Cr(II) form of the catalyst can be considered as active , in all the proposed reactions the metal formally becomes Cr(IV) as it is converted into the active site. These hypotheses are supported by studies of the interaction of molecular transition metal complexes with ethylene [119,120]. Groppo et al. [66] have recently reported that the XANES feature at 5996 eV typical of Cr(II) species is progressively eroded upon in situ ethylene polymerization. 

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],... 

More than three decades ago, skeletal rearrangement processes using alkane or cycloalkane reactants were observed on platinum/charcoal catalysts (105) inasmuch as the charcoal support is inert, this can be taken as probably the first demonstration of the activity of metallic platinum as a catalyst for this type of reaction. At about the same time, similar types of catalytic conversions over chromium oxide catalysts were discovered (106, 107). Distinct from these reactions was the use of various types of acidic catalysts (including the well-known silica-alumina) for effecting skeletal reactions via carbonium ion mechanisms, and these led... 

A wide range of nonacidic metal oxides have been examined as catalysts for aromatization and skeletal isomerization. From a mechanistic point of view, chromium oxide catalysts have been, by far, the most thoroughly studied. Reactions over chromium oxide have been carried out either over the pure oxide, or over a catalyst consisting of chromium oxide supported on a carrier, usually alumina. Depending on its history, the alumina can have an acidic function, so that the catalyst as a whole then has a duel function character. However, in this section, we propose only briefly to outline, for comparison with the metal catalyzed reactions described in previous sections, those reactions where the acidic catalyst function is negligible. 

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