Oxide-based catalysts silica

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. 

It takes place at atmospheric pressure, between 450 and 550 C in the presence of a silver oxide based catalyst deposited on silica or of earth alkali metal oxides, thallium and lead, and with excess propylene. An inert (nitrogen, steam, etc.) is used as diluent, in order to absorb the heat generated daring the conversion, whose molar yield is 7Q per cent in relation to propylene. 

Chromium oxide-based catalysts from Phillips Petroleum Co. these are mixed silica titania support containing 2-20 wt% of titania and a co-catalyst (i.e., trialkylaluminum compounds). These catalysts produce LLDPEs of very broad MWD (M v/Mp in the range of 12-35) and MI in the 80-200 range... 

Generally, there are two possibilities how to use mesoporous molecular sieves as supports for metathesis catalysts. First, to apply them as supports for heterogeneous metal oxide-based catalysts instead of classical silica or alumina. Second, to use them for preparation of heterogenized versions of originally homogeneous metathesis catalysts, especially for anchoring well-defined carbene complexes. 

DeDiox A process for destroying polychlorinated dioxins and furans in flue-gases by catalytic oxidation with hydrogen peroxide. The catalyst is based on silica and the process is operated at 80 to 100°C. Developed by Degussa from 1994. The business was offered for sale in 1998. 

F-T Catalysts The patent literature is replete with recipes for the production of F-T catalysts, with most formulations being based on iron, cobalt, or ruthenium, typically with the addition of some pro-moter(s). Nickel is sometimes listed as a F-T catalyst, but nickel has too much hydrogenation activity and produces mainly methane. In practice, because of the cost of ruthenium, commercial plants use either cobalt-based or iron-based catalysts. Cobalt is usually deposited on a refractory oxide support, such as alumina, silica, titania, or zirconia. Iron is typically not supported and may be prepared by precipitation. 

The Sohio technology is based on a catalyst of bismuth an4 molybdenum oxides. Subsequent catalyst improvements came from the use of bismuth phosphomolybdate on a silica gel, and more recently, antimony-uranium oxides. Each change in catalyst was motivated Jby a higher conversion rate per pass to acrylonitrile. 

Since this initial work there has been a plethora of literature on mesoporous molecular sieves. In addition to the silica and aluminosilicate frameworks similar mesoporous structures of metal oxides now include the oxides of Fe, Ti, V, Sb, Zr, Mn, W and others. Templates have been expanded to include nonionic, neutral surfactants and block copolymers. Pore sizes have broadened to the macroscopic size, in excess of 40 nm in diameter. A recent detailed review of the mesoporous molecular sieves is given in ref [73]. Vartuli and Degnan have reported a Mobil M41S mesoporous-based catalyst in commercial use, but to date the application has not been publicly identified.[74]. 

The catalytic performance of both Co- and Ce-POM supported on NH2-fimctionalized mesoporous silica was assessed in the aerobic oxidation of formaldehyde in H2O under mild conditions (20-40 °C, 1 atm of air) [97,118]. While the Co-POM-based catalyst underwent rapid deactivation, the Ce-POM catalyst could be used repeatedly without significant loss of the catalytic activity as one ean judge from Figure 4 [118]. 

Small amounts of other compounds can be added to Ni-based catalysts to improve the functional characteristics of the final catalyst. Typically, they are calcium aluminate to enhance the mechanical resistance of the catalyst pellets, potassium oxide to improve the resistance to coke formation and silica to form a stable silicate with potassium oxide [34]. Promotion with rare earth oxides such as La2C>3 also results in enhanced resistance to coking. 

The concept presented in Fig. 6 could use also other type of ordered mesoporous membranes, based on silica for example. As discussed before, oxides such as Ti02 provide better multi-functionalities for the design of such a type of nanofactory catalysts. Worth to note is that in the cover picture of the recent US DoE report Catalysis for Energy a very similar concept was reported. This cover picture illustrates the concept, in part speculative, that to selectively convert biomass-derived molecules to fuels and chemicals, it is necessary to insert a tailored sequence of enzyme, metal complexes on metal nanoparticles in a channel of a mesoporous oxide. 

Ermakova and co-workers manipulated the Ni particle size to achieve large CF yields from methane decomposition. The Ni-based catalysts employed for the process were synthesized by impregnation of nickel oxide with a solution of the precursor of a textural promoter (silica, alumina, titanium dioxide, zirconium oxide and magnesia). The optimum particle size (10 0 nm) was obtained by varying the calcination temperature of NiO. The 90% Ni-10% silica catalyst was found to be the most effective catalyst with a total CF yield of 375 gcp/gcat- XRD studies by the same group on high loaded Ni-silica... 

Oxidation in the original Sohio process941,942 was carried out over a bismuth molybdate catalyst, which was later superseded by bismuth phosphomolybdate with various amounts of additional metal ions (Ce, Co, Ni), and multicomponent metal oxides based on Mo, Fe, and Bi supported on silica. 

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