Supports, hydrocracking

It has been shown that steam ammonia treatment of an AlaOs-SiOa hydrocracking support promotes the formation of pentacoordinated aluminum species. The mechanism is associated to a dealumination and aluminum migration from tetrahedral coordination into more distorted Al-Si environment. This generates a larger proportion of strong Lewis acid centers and a broad distribution of acid strength. 

Hydrocracking is catalyzed by substances that promote cracking and hydrogenation together. In commercial use are Ni, Co, Cr, W, and V or their oxides, presulfided before use, on acid supports. Zeolites loaded with palladium also have been used. 

This work is a contribution to the understanding of the effect of spillover hydrogen in a type of catalyst of considerable industrial importance, namely that composed of transition metal sulfides and amorphous acidic solids. This is typically the case of sulfided CoMo supported on silica-alumina used for mild hydrocracking. 

Superficially the Oryx GTL refinery design has much in common with the SMDS process, but there are important differences. There is no separate hydrotreater, which limits production of chemicals, such as waxes. The hydrocracker employs the Chevron Isocracking technology, which is based on a sulfided supported base-metal catalyst that was designed for crude oil conversion. The operating conditions of the hydrocracker are also more severe (>350°C, 7 MPa) than those required by the SMDS process (300-350°C, 3-5 MPa). Only intermediate products are produced (Table 18.13),5 with the naphtha slated as cracker feed and the distillate as blending component for diesel fuel. 

The acid component of a hydrocracking catalyst can be an amorphous oxide, e.g., a silica-alumina ora zeolite, eg., USY. This component usually serves as a support for the metal compound responsible for the hydrogenation function. The metal compound can be a noble metal, e.g., Pt or Pd, or a mixture of sulfides, e.g., of Ni/Mo, NiAV, or Co/Mo. The relative amounts of the respective compounds have to be thoroughly balanced to achieve an optimum performance. 

Hydrocracking, 30 48-52 behavior, thermal, 29 269 catalytic, 26 383 deethylation, 30 50 demethylation, 30 50 metallocarbene formation, 30 51-52 of f -decane, 35 332-333 primary coal liquids, 40 57 procedure, 40 66-67 product distribution, 30 49 reactions, over perovskites, 36 311 suppression by sulfur, 31 229 zeolite-supported catalysts, 39 181-188... 

Figure 16.7 Influence of support type on product distribution in hydrocracking hydrotreated light Arabian gasoil feed hydrocracked over amorphous and high zeolite catalysts differential yields measured in 50°F (10°C) increments.

Recently, we reported that an Fe supported zeolite (FeHY-1) shows high activity for acidic reactions such as toluene disproportionation and resid hydrocracking in the presence of H2S [1,2]. Investigations using electron spin resonance (ESR), Fourier transform infrared spectroscopy (FT-IR), MiJssbauer and transmission electron microscopy (TEM) revealed that superfine ferric oxide cluster interacts with the zeolite framework in the super-cage of Y-type zeolites [3,4]. Furthermore, we reported change in physicochemical properties and catalytic activities for toluene disproportionation during the sample preparation period[5]. It was revealed that the activation of the catalyst was closely related with interaction between the iron cluster and the zeolite framework. In this work, we will report the effect of preparation conditions on the physicochemical properties and activity for toluene disproportionation in the presence of 82. ... 

Throughout these studies, no product other than propane was observed. However, subsequent studies by Sinfelt et al. [249—251] using silica-supported Group VIII metals (Co, Ni, Cu, Ru, Os, Rh, Ir, Pd and Pt) have shown that, in addition to hydrogenation, hydrocracking to ethane and methane occurs with cobalt, nickel, ruthenium and osmium, but not with the other metals studied. From the metal surface areas determined by hydrogen and carbon monoxide chemisorption, the specific activities of... 

In a detailed kinetic study, Sridhar and Ruthven [256], using nickel supported on Kieselghur (58% Ni), alumina (14% and 40% Ni) and silica-alumina (5% Ni), showed that over all four catalysts the rates of both hydrogenation and hydrocracking could be correlated according to the power rate law equation... 

During the last decade, there has been a definite trend towards heavier hydrocracker feedstocks (2). Recognition of the interactions between feed molecular weight and catalyst chemical and physical properties has been necessary to support this trend. 

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. 

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