Alumina support types

A great many materials have been used as catalyst supports in hydrogena-tion, but most of these catalyst have been in a quest for an improved system. The majority of catalyst supports are some form of carbon, alumina, or silica-alumina. Supports such as calcium carbonate or barium sulfate may give better yields of B in reactions of the type A- B- C, exemplified by acetylenes- cjs-olefins, apparently owing to a weaker adsorption of the intermediate B. Large-pore supports that allow ready escape of B may give better selectivities than smaller-pore supports, but other factors may influence selectivity as well. 

Figure 5.21. Schematic presentation of a Type IV BET isotherm, commonly observed for silica and alumina supports.

More recently, Chang reported a ruthenium-based Heck-type reaction in DME/H20 (1 1) by using alumina-supported ruthenium catalysts.154... 

The FTIR data reported in Figure 6.2b showed that only nitrate species were formed upon N02 adsorption, mainly of the ionic type (bands at 1320, 1420-1440 cm-1, vaSymN03 split for the partial removal of the degeneracy 1035-1020 cm-1, vsymN03) and in minor amounts of bidentate type (1560 cm-1, vasymN02 mode expected around 1300 cur1 obscured by the modes of ionic nitrates). Notably, the adsorbed nitrates were related to the Ba component as the surface of the alumina support was almost completely covered by Ba, as pointed out by FTIR data [25], which showed the disappearance of OH groups of the alumina support. 

Conversions obtained in the hydrogenation of RCN in CH on alumina supported Group VIII metals indicated the lower activity of these catalysts compared to the Raney type catalysts (see Table 3). Almost complete conversion (except Co/A1203) was achieved on M/A1203 catalyst at 140 °C for 9 h instead of... 

The total surface areas determined by the N2 BET method for the calcined, supported catalysts are listed in Table II. The X-ray diffraction (XRD) results showed diffraction peaks from a cubic lattice with a unit cell distance of 6.1 A were present on all of the calcined catalysts. Both C03O4 and C0AI2O4 have structures consistent with that lattice spacing, making assignment of the type of crystalline cobalt species present on the alumina supports difficult. 

Two different approaches have been used to graft molybdenum on alumina, namely, either a two-step process involving gas-phase impregnation and further decomposition at high temperature (GPID) or the direct contact of [Mo(CO),5] vapor with the alumina support placed in a hot zone so as to achieve its decomposition. All of the relevant studies point to the existence of a close relationship between the OH group density on the support and the amount of deposited molybdenum as well as the chemical nature of such deposits. Hence, we successively deal with three types of alumina highly, partially and fully dehydroxylated surfaces. 

In the nickel- and cobalt-catalysed reactions [166,207] it was observed that the butene distribution depended upon the temperature of reduction of the catalyst. For both powders and alumina-supported catalysts prepared by reduction of the oxides, reduction at temperatures below ca. 330° C gave catalysts which exhibited so-called Type A behaviour where but-2-ene was the major product and the frans-but-2-ene/cis-but-2-ene ratio was around unity. Reduction above 360° C (Ni) or 440° C (Co) yielded catalysts which gave frans-but-2-ene as the major product (Type B behaviour). It is of interest to note that the yield of cis-but-2-ene was not significantly dependent upon the catalyst reduction temperature with either metal. 

In this work the preparation of orthophenylenediamine (OPDA) from 4-chloro-2-nitroani1ine was studied on alumina supported palladium catalysts. High OPDA yields were obtained on catalysts containing stabilized ionic palladium. In the preparation of the given palladium containing catalysts anchoring type surface reactions were used. The existence of palladium in ionic form was evidenced by XPS and El R measurements. 

An important dopant for rutile-type mixed oxides is Nb oxide [46a]. Banares et al. [49] found that when used as the support for V/Sb/O, Nb205 formed new phases by reaction with V and Sb under catalytic reaction conditions these phases, of unclear nature, affected the catalytic performance in propane ammoxidation. When instead Nb was added as a promoter for the alumina-supported V/Sb/O system, the interaction between the active components led to an improvement of catalytic performance with respect to the undoped V/Sb/O. Nb also forms rutile-type mixed... 

Various Keggin-type polyoxometalates (POMs) were tested as catalysts for the ODS of gas oil with t-butyl hydroperoxide. Alumina-supported phosphomolybdic acid (H3PMoi2O40) proved to be quite active, yielding sulfur conversion higher than... 

Molybdenum oxide - alumina systems have been studied in detail (4-8). Several authors have pointed out that a molybdate surface layer is formed, due to an interaction between molybdenum oxide and the alumina support (9-11). Richardson (12) studied the structural form of cobalt in several oxidic cobalt-molybdenum-alumina catalysts. The presence of an active cobalt-molybdate complex was concluded from magnetic susceptibility measurements. Moreover cobalt aluminate and cobalt oxide were found. Only the active cobalt molybdate complex would contribute to the activity and be characterized by octahedrally coordinated cobalt. Lipsch and Schuit (10) studied a commercial oxidic hydrodesulfurization catalyst, containing 12 wt% M0O3 and 4 wt% CoO. They concluded that a cobalt aluminate phase was present and could not find indications for an active cobalt molybdate complex. Recent magnetic susceptibility studies of the same type of catalyst (13) confirmed the conclusion of Lipsch and Schuit. 

If benzene is the main product desired, a narrow light naphtha fraction boiling over the range 70 to 104°C is fed to the reformer, which contains a noble metal catalyst consisting of, for example, platinum-rhenium on a high-surface-area alumina support. The reformer operating conditions and type of feedstock determine the amount of benzene that can be produced. The benzene product is most often recovered from the reformate by solvent extraction techniques. 

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