Sulfuric CATALYSTS - SUPPORTED

Several processes are available for the recovery of platinum and palladium from spent automotive or petroleum industry catalysts. These include the following. (/) Selective dissolution of the PGM from the ceramic support in aqua regia. Soluble chloro complexes of Pt, Pd, and Rh are formed, and reduction of these gives cmde PGM for further refining. (2) Dissolution of the catalyst support in sulfuric acid, in which platinum is insoluble. This... 

A selective poison is one that binds to the catalyst surface in such a way that it blocks the catalytic sites for one kind of reaction but not those for another. Selective poisons are used to control the selectivity of a catalyst. For example, nickel catalysts supported on alumina are used for selective removal of acetjiene impurities in olefin streams (58). The catalyst is treated with a continuous feed stream containing sulfur to poison it to an exacdy controlled degree that does not affect the activity for conversion of acetylene to ethylene but does poison the activity for ethylene hydrogenation to ethane. Thus the acetylene is removed and the valuable olefin is not converted. 

Materials, such as activated carbons, that are derived from natural products differ greatly in their effectiveness when used as catalyst supports, but it is difficult to delimit the factors present in the carbon that influence performance, Certain broad statements, such as that carbons with excessive sulfur or ash content tend to make inferior catalysts, only begin to touch on the problem. One of the advantages of buying commercial catalysts, instead of using laboratory preparations, is that commercial suppliers have solved this problem already by empirical testing of many carbons. They provide catalysts that are best by test. 

A platinum catalyst supported on AI2O3 is used for the oxidation of sulfur dioxide ... 

Poisoning of deNOx catalysts by SO2 could also be a problem since diesel fuels contain small amounts of sulfur compounds. Only a few studies deal with this subject [11-13]. It appears from the literature that for Cu catalysts the use of MFI as a support reduces the inhibition by SO2. Support effects also appear in the case of Co since Co/MFI is much less sensitive to SO2 than Co/ferrierite [13]. Since this support effect may be related to acidity, it becomes important, to investigate the influence of SO2 on the properties of Cu catalysts supported on Si02, AI2O3, MFI, BEA and unpromoted or sulfate promot Ti02 and Zr02- These latter have been reported active for deNOx [14]. 

Figure 7. SEM and XRMA microphotographs of palladium catalysts supported on the amphiphilic resin made by DMAA, MTEA, MBAA (cross-linker) [30]. Microphotographs (a) and (b) show an image and the radial palladium distribution after uptake of [Pd(OAc)2] from water/acetone the precursor diffuses only into the outer layer of the relatively little swollen CFP after reduction the nanoclusters remain close to the edge of the catalyst beads. Microphotographs (c) and (d) show the radial distribution of sulfur and palladium, respectively, after uptake of [PdCU] from water after reduction palladium is homogenously distributed throughout the catalyst particles. This indicates that under these conditions the CFP was swollen enough to allow the metal precursor to readily penetrate the whole of polymeric mass. (Reprinted from Ref. [30], 2005, with permission from Elsevier.)...

The transformation of straw and agrofood residues with high sulfur and ash content requires the development of materials for sulfur abatement at high temperature, tar cracking and as monolith for syngas production by exothermic or autothermal processes thanks to catalysts supported on materials with a high thermal conductivity. 

Occurs in nature in abundance the principal forms are bauxites and lat-erites. The mineral corundum is used to produce precious gems, such as ruhy and sapphire. Activated aluminas are used extensively as adsorbents because of their affinity for water and other polar molecules and as catalysts because of their large surface area and appropriate pore sturcture. As adsorbents, they are used for drying gases and liquids and in adsorption chromatography. Catalytic properties may be attributed to the presence of surface active sites (primarily OFT, 02, and AF+ ions). Such catalytic applications include sulfur recovery from H2S (Clauss catalysis) dehydration of alcohols, isomerization of olefins and as a catalyst support in petroleum refining. 

Bimetallic Ni-based catalysts were also studied for SR of higher hydrocarbons in order to avoid the carbon formation and sulfur poisoning problems of conventional Ni catalysts.Murata et prepared a series of bimetallic catalysts by adding alkali and alkaline-earth metals to Ni catalyst supported on zirconia and alumina for SR of i-Cg and methylcyclohexane (MCFI). The performance of various bimetallic catalysts for SR of i-Cg and MCH are summarized in Figures 21a and 21b, respectively. It was reported that the stability of Ni/Zr02 is considerably improved by the addition of alkaline-earth metals (M), particularly strontium, to the catalyst with an M/Ni ratio of 0.5 by... 

Catalytic hydrodesulfurization (HDS) is a very important industrial process that involves removal of sulfur from crude oils by high-temperature ( 400°C) treatment with hydrogen over Co- or Ni-promoted Mo or W catalysts supported on alumina. In an attempt to determine the mechanism of this process, many transition metal complexes of thiophene, a sulfur-containing heterocycle that is particularly difficult to desulfurize, have been prepared and their reactivities studied in order to compare their behavior with those of the free thiophenes that give H2S and C4 hydrocarbons under HDS conditions (88ACR387). Thiophene can conceivably bind to the catalyst surface by either cr-donation via a sulfur electron pair or through a variety of -coordination modes involving the aromatic system... 

In order to achieve the goal of reducing sulfur levels in fuels, there is a clear need for understanding the mechanism of the reaction (Chapter 4) in conjunction with the nature of the catalyst and support. Most of the work has been carried out with the traditional cobalt-molybdenum catalyst supported on alumina. This system is a time-tested and effective. 

Catalytic visbreaking has been proposed in which the severity of thermal decomposition is increased by the addition of a selenium-, tellurium-, or sulfur containing catalyst supported on a porous substrate (Yan, 1991). 

Nitration of o-xylene with N02 has been performed in the gas phase over several zeolites (HBeta, HY, HZSM-5 and HMordenite), as well as on sulfuric acid supported on silica and sulfated zirconia at temperatures between 50 and 130°C.[72] HBeta was found the most active and selective catalyst for the production of 4-o-NX giving ratios of 4-o-NX 3-o-NX as high as 6 1, whereas no dinitro-o-xylene compounds were detected. 

EXAFS studies showed that a nickel atom in a sulfided Ni-Mo catalyst supported on j/-A1203 or on carbon is surrounded by four or five sulfur atoms at a distance of 2.2 A, by one or two molybdenum atoms at a distance of 2.8 A, and by one nickel atom at a distance of 3.2 A (20). These data are consistent with a model in which the nickel atoms are located at the M0S2 edges in the molybdenum plane in a square pyramidal coordination. The nickel atoms are connected to the M0S2 by four sulfur atoms, and depending on the H2S partial pressure a fifth sulfur atom may be present in the apical position in front of the nickel atom (Fig. 4). Recent density functional... 

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