Metal surfaces hydrodesulfurization

Supported Rhodium Catalysts Alkali Promoters on Metal Surfaces Cobalt-Molybdenum Sulfide Hydrodesulfurization Catalysts Chromium Oxide Polymerization Catalysts... 

The total surface areas (Sbet) were determined by means of nitrogen adsorption at 77K and the metallic surface area (Sni) by using reactive adsorption of 3-methylthiophen in the liquid phase according to a protocol already published [3]. It has been shown previously that the hydrodesulfurization of thiophene on chromium... 

Sulfur (S) is the most severe poison as it chemisorbs readily on any metal surface. A desulfurization step is carried out before the fuel is led into the reformer to avoid this poisoning. This is usually accomplished with a zinc oxide sulfur polisher and the possible use of a hydrodesulfurizer, if required. 

Studies of the Kinetics and Mechanisms of Ammonia Synthesis and Hydrodesulfurization on Metal Single-Crystal Surfaces... 

TETRA HDS [High density solids] A process for aiding the removal of heavy metals from wastewaters. It is a physical process which controls the characteristics of heavy metal hydroxide precipitates so that they settle quicker. The precipitates have a hydrophobic surface, so they are easy to de-water. Developed and licensed by Tetra Technologies, Houston, TX. Widely used by the iron and steel industry in the United States. Not to be confused with hydrodesulfurization, often abbreviated to HDS. 

Smectite-type materials containing transition metal divalent cations (Ni2+, Co2, and Zn2+) in octahedral sheets were synthesized. The synthetic smectites were thermally stable and had large surface areas and high pore volumes after evacuation at 873 K. Catalytic activities of synthetic smectites were investigated. The Ni2 -containing smectites were active for the isomerization of 1-butene and the oligomerization of ethylene. The Co2+-containing smectites were active for the hydrodesulfurization of thiophene. 

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... 

Residua and heavy oils contain impurities other than sulfur, nitrogen, and oxygen, and the most troublesome of these impurities are the organometallic compounds of nickel and vanadium. The metal content of a residuum or heavy oil can vary from several parts per million (ppm) to more than 1000 parts per million (Table 6-15), and there does seem to be more than a chance relationship between the metals content of a feedstock and its physical properties (Reynolds, 1997 Speight, 1999). In the hydrodesulfurization of the heavier feedstocks the metals (nickel plus vanadium) are an important factor since large amounts (over 150 ppm) will cause rapid deterioration of the catalyst. The free metals, or the sulfides, deposit on the surface of the catalyst and within the pores of the catalyst, thereby... 

In industrial practice, catalytic surfaces are often very complex, not only structurally but also chemically. An example is shown in Fig. 1 from Chianelli et al. [6] for hydrodesulfurization catalysts. The data indicate that maximum dibenzothiophene hydrodesulfurization activity is achieved at intermediate heats of formation of metal sulfides, i.e., at intermediate metal-sulfur bond strengths. Again, while such surface energetic considerations do not have ab initio predictive ability, they are valuable tools for catalyst synthesis and prescreening. 

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). 

Beckler, R. K. and M. G. White, Polynuclear Metal Complexes as Model Mixed Oxide Catalysts Selective Chemisorption of NH3 and NO , J. Catal, 109, pp. 25-36 (1988) Beckler, R. K. and M. G. White, Polynuclear Metal Complexes as Model Mixed Oxide Catalysts Isomerization Activity , J. Catal, 110, pp. 364-374 (1988). Coulier, L., V. G. Kishan, J. A. R. van Veen, and J W. Niemantsverdriet, Surface science models for CoMo Hydrodesulfurization Catalysts the Influence of the support on hydrodesulfurization acidity , J. Vac Scl Technol A. 19, Issue 4, 1 July/August 2001, pp 1510-5. 

Molybdenum sulfide-based catalysts have been used for hydrodesulfurization (HDS) [6]. The preparation of highly dispersed molybdenum sulfides is one of the ways to increase HDS activity. Zeolite-supported molybdenum sulfide catalysts have received extensive attention because of intrinsically high dispersion of Mo on the high surface area support [4,5]. Furthermore, a combination of highly dispersed metal sulfide and zeolite acidity... 

Paul-Boncour, Hilaire and Percheron-Guegan have extended the earlier chapter 43, on interactions at surfaces of metals and alloys, to reactions such as hydrogenation, methanation, ammonia synthesis, saturated hydrocarbon reactions, dehydrogenation of hydrogenated materials, hydrodesulfurization, and carbon monoxide oxidation. 

Rather than survey all of the possible modifications that can be made to an alumina surface, we will focus on a subset involved in two different types of surface-catalyzed chemical reactions, namely, the partial oxidation of ethylene to ethylene oxide (EO) and hydrodesulfurization (HDS) processes. Both of these catalytic systems have functional points in common, in that alumina serves as a support (a-alumina for the EO process and 7-alumina for the HDS process) and alkali-metal salts serve as promoters for both reactions. To illustrate this commonality, this section will be divided into three parts (1) the adsorption of alkali-metal salts to 7-alumina, as reflected in the Rb and Cs solid-state NMR spectroscopy of these systems (2) the absorption of ethylene to silver supported on aluminas in the presence and absence of cesium salts, as followed by C NMR spectroscopy, and (3) the solid-state Mo NMR of fresh and reduced/ sulfided molybdena-alumina catalysts. 

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