Desulfurization, catalytic hydrogenation

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. 

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... 

Catalytic hydrogenation of thiophene poses a problem since noble metal catalysts are poisoned, and Raney nickel causes desulfurization. Best catalysts proved to be cobalt polysulfide [425], dicobalt octacarbonyl [426], rhenium heptasulfide [5i] and rhenium heptaselenide [54]. The last two require high temperatures (230-260°, 250°) and high pressures (140, 322 atm) and give 70% and 100% of tetrahydrothiophene (thiophane, thiolene), respectively. 

The sulfonyl group in sulfones resists catalytic hydrogenation. Double bonds in a, -unsaturated sulfones are reduced by hydrogenation over palladium on charcoal (yield 94%) [686, 687] or over Raney nickel (yield 62%) without the sulfonyl group being affected [686]. In p-thiopyrone-1,1-dioxide both double bonds were reduced with zinc in acetic acid but the keto group and the sulfonyl group survived [655]. Raney nickel may desulfurize sulfones to hydrocarbons [673]. 

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... 

Catalytic hydrogenation of peptides containing a Phe(4-N02) residue, to be subsequently converted into Phe(4-N3), that also contain cystine and/or methionine residues, requires extended reaction times. This may lead to desulfuration. Therefore, a Phe(4-NH2) residue is used as a precursor for Phe(4-N3) in the synthesis of AVP to give Phe(4-N3) residues at either position 2 or 3.1281 In this solution-phase synthesis, the 4-amino group in the 4-amino-... 

In the actual process (Figure 10-5), the natural gas feedstock must first be desulfurized in order to prevent catalyst poisoning or deactivation. The desulfurization step depends upon the nature of the sulfur-containing contaminants and can vary from the more simple ambient temperature adsorption of the sulfur-containing materials on activated charcoal to a more complex high-temperature reaction with zinc oxide to catalytic hydrogenation followed by zinc oxide treatment. 

Hydrofining a fixed-bed catalytic process to desulfurize and hydrogenate a wide range of charge stocks from gases through waxes. 

Ultralining a fixed-bed catalytic hydrogenation process to desulfurize naphthas and upgrade distillates by essentially removing sulfur, nitrogen, and other materials. 

The H-Coal process is a development of Hydrocarbon Research Inc. (HRI). It converts coal by catalytic hydrogenation to substitutes for petroleum ranging from a low sulfur fuel oil to an all distillate synthetic crude, the latter representing a potential source of raw material for the petrochemical industry. The process is a related application to HRI s H-Oil process which is used commercially for the desulfurization of residual oils from crude oil refining. 

ARDS [Atmospheric Residue DeSulfurization] A process for upgrading petroleum residues by catalytic hydrogenation. 

Feedstock Purification. In feedstock purification, mainly desulfurization, adsorption on active carbon was replaced by catalytic hydrogenation over cobalt-molybdenum or nickel-molybdenum catalyst, followed by absorption of the H2S on ZnO pellets with formation of ZnS. By itself this measure has no direct influence on the energy consumption but is a prerequisite for other energy saving measures, especially in reforming and shift conversion. 

Additional information about the catalytic performance of the catalysts can be obtained from the analysis of the product distribution, which is affected by the metallic and acid functionalities. Tables 4 and 5 compare the product distributions obtained in the DBT and 4,6-DMDBT reactions with the NiMo/Al203, NiMo/HNaY and NiMo catalysts with 20% of HNaY in their formulation. In the case of DBT, zeolite incorporation into the catalyst changes the contributions of the direct desulfurization (DDS) pathway, which yields biphenyl-type compounds, and of the desulfurization through hydrogenation (HYD) pathway, which gives cyclohexylbenzene-type compounds. Also, the proportion of CHB in the reaction products and the liquid yield decrease with the number of accessible zeolite acid sites in the catalyst. This effect is due to the cracking of CHB on the zeolite acid sites. On the other hand, the formation of DCH is enhanced on the catalysts where Mo precursor phase is more polymerized (NiMo/HNaY-Al203(P) and NiMo/HNaY formulations). 

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