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Hydrodesulfurization process

  • US 3,964,995 A
  • Filed: 06/21/1974
  • Issued: 06/22/1976
  • Est. Priority Date: 07/24/1972
  • Status: Expired due to Term
First Claim
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1. In a hydrodesulfurization process wherein a metal- and sulfur-containing petroleum liquid residuum feedstock is treated in a hydrodesulfurizing step byfeeding the residuum together with hydrogen upwardly into a desulfurization reaction zone maintained under ebullated bed hydrodesulfurization conditions with a temperature between about 700°

  • and about 825°

    F and a pressure between about 1000 and about 3000 psig, while maintaining in said desulfurization zone a high density, substantially non-porous particulate solid catalyst selected from the group consisting of cobalt molybdate on alumina and nickel molybdate on alumina in random motion in the liquid, said catalyst having a porosity not greater than 0.1 cc/g of cumulative pore volume for pores having diameters larger than 250A to recover a reiduum containing less than one percent sulfur;

    the improvement which comprises;

    pretreating the metal-containing residuum before substantial desulfurization to remove vanadium or nickel byfeeding said residuum with a hydrogen-containing gas to a pretreatment zone maintained at a temperature between about 700° and

    825°

    F and a pressure between 1000 and 3000 psig;

    maintaining in said pretreatment zone a bed of particulate contact solids containing at least 75 weight percent porous alumina and containing about 71/2 to 22 weight percent metal oxide promoter consisting essentially of a mixture of Fe2 O3, TiO2 and SiO2, and mixtures thereof;

    feeding said contact solids to the reaction zone at a rate sufficient to achieve at least 40 percent removal of vanadium, said contact solids being maintained in random motion in the liquid by the residuum feed and hydrogen-containing gas,whereby the desulfurization catalyst has increased life and sulfur removal is enhanced.

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