Catalytic desulfurization

Hydrogenation Hydroformylation 100-300 edible oils hydrogasification hydrocracking desulfurization catalytic cracking naphtha hydroforming coal liquefaction fatty alcohols 1-6-hexanediol 1-4-butanediol hexamethylenedi amine C4 to Cl5 products... 

For example, in the case of light Arabian crude (Table 8.16), the sulfur content of the heavy gasoline, a potential feedstock for a catalytic reforming unit, is of 0.036 weight per cent while the maximum permissible sulfur content for maintaining catalyst service life is 1 ppm. It is therefore necessary to plan for a desulfurization pretreatment unit. Likewise, the sulfur content of the gas oil cut is 1.39% while the finished diesel motor fuel specification has been set for a maximum limit of 0.2% and 0.05% in 1996 (French specifications). 

In the catalytic steam reforming of natural gas (see Fig. 2), the hydrocarbon stream, principally methane, is desulfurized and, through the use of superheated steam (qv), contacts a nickel catalyst in the primary reformer at ca 3.04 MPa (30 atm) pressure and 800°C to convert methane to H2. 

Nascent atomic hydrogen released by a process reaction such as catalytic desulfurization... 

Catalytic desulfurization Raney Ni/DMF, column, few hours, satisfactory yields." ... 

The o-nitrobenzenesulfenamide has been used for the protection of amino acids. o-Nitrobenzenesulfenamides, B, are also cleaved by acidic hydrolysis (HCl/Et20 or EtOH, 0°, 1 h, 95% yield)" by nucleophiles (13 reagents, 5 min-12 h, 90% cleaved) by PhSH or HSCH2CO2H, 22°, 1 h by 2-mercaptopyri-dine/CH2Cl2, 1 min, 100% yield) by NH4SCN, 2-methyl-1-indolylacetic acid and by catalytic desulfurization (Raney Ni/DMF, column, a few hours, satisfactory yield). 

FCC feed hydrotreating Gasoline end point reduction FCC gasoline hydrotreating Catalyst additives Bio-catalytic desulfurization... 

The catalytic hydrogenation of fatty oils, the desulfurization of liquid petroleum fractions by catalytic hydrogenation, Fischer-Tropsch-type synthesis in slurry reactors, and the manufacture of calcium bisulfite acid are familiar examples of this type of process, for which the term gas-liquid-particle process will be used in the following. 

All these gas-liquid-particle operations are of industrial interest. For example, desulfurization of liquid petroleum fractions by catalytic hydrogenation is carried out, on the industrial scale, in trickle-flow reactors, in bubble-column slurry reactors, and in gas-liquid fluidized reactors. 

Catalytic desulfurization is at present carried out industrially by at least three of the major types of gas-liquid-particle operations referred to in Section I trickle reactors, bubble-column slurry reactors, and gas-liquid fluidized reactors. 

Van Driesen and Stewart (V4) have reported temperature measurements for various locations in commercial gas-liquid fluidized reactors for the large-scale catalytic desulfurization and hydrocracking of heavy petroleum fractions (2500 barrels per day capacity). The hydrogenation was carried out in two stages the maximum and minimum temperatures measured were 774° and 778°F for the first stage and 768° and 770°F for the second. These results indicate that gas-liquid fluidized reactors are characterized by a high effective thermal conductivity. 

The low reactivity of alkyl and/or phenyl substituted organosilanes in reduction processes can be ameliorated in the presence of a catalytic amount of alkanethiols. The reaction mechanism is reported in Scheme 5 and shows that alkyl radicals abstract hydrogen from thiols and the resulting thiyl radical abstracts hydrogen from the silane. This procedure, which was coined polarity-reversal catalysis, has been applied to dehalogenation, deoxygenation, and desulfurization reactions.For example, 1-bromoadamantane is quantitatively reduced with 2 equiv of triethylsilane in the presence of a catalytic amount of ferf-dodecanethiol. 

Metal polysulfido complexes have attracted much interest not only from the viewpoint of fundamental chemistry but also because of their potential for applications. Various types of metal polysulfido complexes have been reported as shown in Fig. 1. The diversity of the structures results from the nature of sulfur atoms which can adopt a variety of coordination environments (mainly two- and three-coordination) and form catenated structures with various chain lengths. On the other hand, transition metal polysulfides have attracted interest as catalysts and intermediates in enzymatic processes and in catalytic reactions of industrial importance such as the desulfurization of oil and coal. In addition, there has been much interest in the use of metal polysulfido complexes as precursors for metal-sulfur clusters. The chemistry of metal polysulfido complexes has been studied extensively, and many reviews have been published [1-10]. 

Sweetening of petroleum products implies the removal of dissolved free sulfur and its compounds like hydrogen sulfide, and mercaptans in order that the product has no bad odour and does not tend to cause corrosion. The removal of these is accomplished by oxidation processes, solvent processes or catalytic desulfurization processes. 

The catalytic desulfurization method removes all types of sulfur, except for heterocyclic sulfur compounds. The sulfur compounds are decomposed at high temperature, yielding H2S and are removed by fractionization. The processes that belong to this category are ... 

The bicyclic ozonides 12 23) and thiaozonides 13 2S) afford on catalytic hydrogenation (Pd-C) the expected 1,4-diones 61 (Eq. 47). Alternatively, deoxygenation of 12 or desulfurization of 13 with triphenylphosphine led to the same products essentially quantitatively. Both reductions served for the chemical characterization of these... 

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