Hydrodesulfurization catalysis

Rigorous hydrogenating conditions, particularly with Raney Nickel, remove the sulfur atom of thiophenes. With vapor-phase catalysis, hydrodesulfurization is the technique used to remove sulfur materials from cmde oil. Chemically hydrodesulfurization can be a valuable route to alkanes otherwise difficult to access. 

The properties of the molybdenum-sulfur compounds described are of direct importance to hydrodesulfurization catalysis. Hydrodesulfurization and the nature of the catalysts used have been adequately described elsewhere and will not be presented here. References in which this system is described in detail include Refs.161) and 214) through221). 

Research into cluster catalysis has been driven by both intrinsic interest and utilitarian potential. Catalysis involving "very mixed -metal clusters is of particular interest as many established heterogeneously catalyzed processes couple mid and late transition metals (e.g., hydrodesulfurization and petroleum reforming). Attempts to model catalytic transformations arc summarized in Section II.F.I., while the use of "very mixed -metal clusters as homogeneous and heterogeneous catalysis precursors are discussed in Sections I1.F.2. and I1.F.3., respectively. The general area of mixed-metal cluster catalysis has been summarized in excellent reviews by Braunstein and Rose while the tabulated results are intended to be comprehensive in scope, the discussion below focuses on the more recent results. 

In this paper we will discuss the results that we have obtained studying two important processes, the synthesis of ammonia over Fe and Re catalysts and the hydrodesulfurization of thiophene on Mo. These examples illustrate two problems in catalysis to which our methods are particularly sensitive. The first is the effect of the structure of the catalyst on reaction rates. The sensitivity of the... 

The studies of ammonia synthesis over Fe and Re and the hydrodesulfurization of thiophene over Mo, described above, illustrate the importance and success of our approach of studying catalysis over single crystal samples at high pressures. The use of surfaces having a variety of orientations allows the study of reactions that are surface structure sensitive 6Uid provides insight into the nature of the catalytic site. Here we have shown that the ammonia synthesis... 

Mossbauer spectroscopy is one of the techniques that is relatively little used in catalysis. Nevertheless, it has yielded very useful information on a number of important catalysts, such as the iron catalyst for Fischer-Tropsch and ammonia synthesis, and the cobalt-molybdenum catalyst for hydrodesulfurization reactions. The technique is limited to those elements that exhibit the Mossbauer effect. Iron, tin, iridium, ruthenium, antimony, platinum and gold are the ones relevant for catalysis. Through the Mossbauer effect in iron, one can also obtain information on the state of cobalt. Mossbauer spectroscopy provides valuable information on oxidation states, magnetic fields, lattice symmetry and lattice vibrations. Several books on Mossbauer spectroscopy [1-3] and reviews on the application of the technique on catalysts [4—8] are available. 

OrganometaUic catalysts hydrodesulfurization, 42 413, 417-425, 432 OrganometaUic chemistry, role of phase-transfer catalysis, 35 398-400 OrganometaUic clusters heterogeneous catalysts, 38 283-288 precursors, 38 391-392... 

In general, it can be concluded, that although a large scale biphasic solution process for hydrodesulfurization and hydrodenitrogenation is not likely to come soon, there are promising results in homogeneous catalysis which can lead to constmction of such processes in the future. 

It should also be noted that polysulfido complexes are not only interesting because of their structures and reactivity, but also because of their possible applications. They can, for example, be used to prepare sulfur rings of predetermined size and they are also suspected to play a role in catalysis (particularly in hydrodesulfurization). 

The replacement of conventional catalytic processes for purification of mixtures by processes involving extraction with ionic liquids has also been envisioned. For example, the extractive removal of sulfur compounds from fuels has shown promising leads for high selectivity for aromatic sulfur compounds, and removal of such compounds has been a major challenge in conventional heterogeneous hydrodesulfurization catalysis (27,296). 

Whitehurst, Isoda, and Mochida write about catalytic hydrodesulfurization of fossil fuels, one of the important applications of catalysis for environmental protection. They focus on the relatively unreactive substituted di-benzothiophenes, the most difficult to convert organosulfur compounds, which now must be removed if fuels are to meet the stringent emerging standards for sulfur content. On the basis of an in-depth examination of the reaction networks, kinetics, and mechanisms of hydrodesulfurization of these compounds, the authors draw conclusions that are important for catalyst and process design. 

It is well known that the accessibility of the mesoporous materials would play an important role in catalysis, and catalytic activity depends on the free diffusion of the reactants, intermediates and products [5], Thus, a mesoporous molecular sieve with better mass transport pore would be a more suitable candidate for some industrial catalytic reactions of the largesized hydrocarbons in dehydrogenation, hydrocracking or hydrodesulfurization. 

In the light of common parallelisms between catalysis and electrocatalysis, it is interesting to note that Co and Mo are used in catalytic processes of hydrodesulfurization [450], The activity of sulfide electrodes changes with time [439, 442, 446]. Normally, there is an initial period during which the overpotential decreases, then it increases again or levels off at a constant activity. The initial improvement is interpreted in various ways but it is generally attributed to some stabilization of the electrode surface (Fig. 23). It seems that a hydride phase is formed initially [442],... 

Over the past 30 years, our laboratory has examined the synthesis of nanostructured materials for advanced catalysts. The first process for the synthesis of fine grains of cobalt molybdates for hydrodesulfurization catalysis... 

Recently, however, the implementation of several forms of modern, high resolution spectroscopy has made it possible to characterize, in relatively detailed fashion, the evolving chemistry of heterogeneous catalytic-type systems. In some cases, in fact, it has been possible to map the behavior of actual commercial catalysts, even following use. For example, much of our present understanding of the functionality of hydrodesulfurization catalysis has been a direct result of investigations of commercial systems with modern surface spectroscopies, as is also the case in the development of the basis reference for metals-support interactions (1). 

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