Sulfide catalysts catalytic materials

CatalyticaHy Active Species. The most common catalyticaHy active materials are metals, metal oxides, and metal sulfides. OccasionaHy, these are used in pure form examples are Raney nickel, used for fat hydrogenation, and y-Al O, used for ethanol dehydration. More often the catalyticaHy active component is highly dispersed on the surface of a support and may constitute no more than about 1% of the total catalyst. The main reason for dispersing the catalytic species is the expense. The expensive material must be accessible to reactants, and this requires that most of the catalytic material be present at a surface. This is possible only if the material is dispersed as minute particles, as smaH as 1 nm in diameter and even less. It is not practical to use minute... 

The performance of a supported metal or metal sulfide catalyst depends on the details of its preparation and pretreatraent. For petroleum refining applications, these catalysts are activated by reduction and/or sulfidation of an oxide precursor. The amount of the catalytic component converted to the active ase cind the dispersion of the active component are important factors in determining the catalytic performance of these materials. This investigation examines the process of reduction and sulfidation on unsupported 00 04 and silica-supported CO3O4 catalysts with different C03O4 dispersions. The C03O4 particle sizes were determined with electron microscopy. X-ray diffraction (XRD), emd... 

The chapter Fundamental Studies of Transition-Metal Sulfide Catalytic Materials by Chianelli, Daage, and Ledoux reviews current understanding of the relationship between structural and other properties of these catalysts and their catalytic activity and selectivity in hydrodesulfurization. In view of increasing environmental demands, this field has been heavily researched. The authors show how systematic studies and applications of novel methods can provide considerable understanding of these important catalysts. 

Since the first synthesis of mesoporous materials MCM-41 at Mobile Coporation,1 most work carried out in this area has focused on the preparation, characterization and applications of silica-based compounds. Recently, the synthesis of metal oxide-based mesostructured materials has attracted research attention due to their catalytic, electric, magnetic and optical properties.2 5 Although metal sulfides have found widespread applications as semiconductors, electro-optical materials and catalysts, to just name a few, only a few attempts have been reported on the synthesis of metal sulfide-based mesostructured materials. Thus far, mesostructured tin sulfides have proven to be most synthetically accessible in aqueous solution at ambient temperatures.6-7 Physical property studies showed that such materials may have potential to be used as semiconducting liquid crystals in electro-optical displays and chemical sensing applications. In addition, mesostructured thiogermanates8-10 and zinc sulfide with textured mesoporosity after surfactant removal11 have been prepared under hydrothermal conditions. 

The presence of V3S4 crystals can only be attributed either to an autocatalytic mechanism of this type or the migration of the deposited metals. It is known that deposited Ni and V sulfides possess some catalytic activity (see Section IV). Slurry processes have been proposed which utilize Ni and V deposited from the oil onto a slurry material (Bearden and Aldridge, 1981). Studies have appeared in the literature demonstrating that nearly all of the transition metals are catalytically active for HDS reactions and presumably for HDM (Harris and Chianelli, 1984). Rankel and Rollmann (1983) impregnated an alumina catalyst base with Ni and V and concluded that these sulfides display an order of magnitude lower activity than the standard Co-Mo sulfide catalyst for HDS reactions, but exhibited similar activity for HDM reactions. 

Many minerals or their synthetic equivalents are of industrial importance, and the possibilities of greater understanding of their behavior and properties through application of the methods described in this book is a major stimulus to research. Two examples are chosen for discussion here The first is the zeolites, a group of framework alumino-silicates (with interstitial Na+, Ca +, and HjO), characterized by very open frameworks with large interconnecting spaces or channels the second is the transition-metal sulfide catalysts, materials already generally discussed in Chapter 6, but considered here specifically in relation to their catalytic properties. 

Catalytic hydrodesulfurization (HDS), the removal of sulfide in the form of H2S from petroleum, is a critical step in the industrial refinement process and one of increasing importance as the cleaner world supplies of petroleum feedstocks dwindle and the poorer quality feedstocks have to be used. The removal of sulfur (and certain other impurities such as nitrogen in hydrodenitrogenation) is undertaken using transition-metal sulfide catalysts (Weisser and Landa, 1973). The most widely used materials... 

Transition Metal Salts and Oxides on Alumina. Transition metal salts, particularly chlorides and nitrates, are frequently used as starting materials for the preparation of supported transition metal oxides or supported precursors for supported metal catalysts. Also, many catalytic materials, particularly supported molybdenum and tungsten oxide and sulfide catalysts, contain transition metal ions, namely Co, Ni , and Fe " as promoters. Thus, it is interesting to study the spreading and wetting behavior of salts of these transition metals and of their oxides. This is of particular importance for promoted catalyst materials, since in practice the incorporation of the active phase and the promoter should be possible in one step for economic reasons. 

The future of Raman spectroscopy in the research and the development of catalysts appears to be extremely promising. The recent revolution in Raman instrumentation has dramatically increased the ability to detect weak Raman signals and to collect the data in very short times. Thus, it is now possible to perform real-time Raman analysis and to study many catal) c systems that give rise to unusually weak Raman signals. The enormous strides in Raman instrumentation now allow for the characterization of a wide range of catalytic materials bulk mixed oxides, supported metal oxides, zeolites, supported metal systems, metal foils, as well as single crystal surfaces. Few Raman studies have been reported for sulfides, nitrides, or carbides, but these catalytic materials also give rise... 

With the sulfided catalyst at 200°C the distribution of aromatics including the adsorption of PNA was found to be the same as for the unimpregnated carrier, and also the same amount of coke was found on the surface of the used catalyst, see Table 2. Since the active catalytic material is assumed to cover a significant part of the carrier surface, this could indicate that coke is deposited both on the free surface of the carrier and on the active phase. 

The first step in regenerating the coated, inactive nickel sulfide catalysts is to remove the reactants and products of the catalytic reaction aloi with the extraneous material coating the catalyst. In most cases, extraction of the catalytic mass with solvents, or purging with steam is adequate for this clean-up. The more resistant film of coke or tar is then removed by oxidation with air under carefully controlled conditions to avoid over-heating the catalyst. During this oxidation, the nickel sulfide is usually oxidized to NiO. This NiO is then reduced and sulfided in the same manner as in the initial preparation of the catalyst. 

Catalyst carriers are often manufactured in a two-step process. In the first step, the solid material, e.g., silica or alumina, is precipitated from a solution and filtered. Then the wet powder is brought into the desired shape, as grains or pellets of a certain size, e.g., by spray drying, pressing or extrusion. The resulting particles are then dried and sintered at elevated temperatures. The more active catalytic material may be formed by co-precipitation. At elevated temperatures oxides are usually formed, that may be reduced to obtain a pure metal. Sometimes oxides or sulfides are the active species. 

Except the lanthanum oxides and lanthanum-containing composite oxides with various struetures and morphology, the lanthanum oxysulfide, sulfide and oxynitrides, as some novel catalytic materials, can be also used as catalysts with excellent catalytic behaviors for heterogeneous catalysis. 

In Chapter 1 we emphasized that the properties of a heterogeneous catalyst surface are determined by its composition and structure on the atomic scale. Hence, from a fundamental point of view, the ultimate goal of catalyst characterization should be to examine the surface atom by atom under the reaction conditions under which the catalyst operates, i.e. in situ. However, a catalyst often consists of small particles of metal, oxide, or sulfide on a support material. Chemical promoters may have been added to the catalyst to optimize its activity and/or selectivity, and structural promoters may have been incorporated to improve the mechanical properties and stabilize the particles against sintering. As a result, a heterogeneous catalyst can be quite complex. Moreover, the state of the catalytic surface generally depends on the conditions under which it is used. 

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