GB828679A - Improvements in the pressure hydrogenation of crude oils, tars or their residues - Google Patents

Abstract

A process for the pressure hydrogenation of crude oils, shale oils, tars or their residues at temperatures between 350 DEG and 550 DEG C. whereby the initial materials are preheated before the actual pressure hydrogenation in a preliminary stage in the presence of large-surfaced substances, comprises treating the initial material in a preliminary stage wherein the large-surfaced substances occupy about 40 to 80% of the free space at a temperature above 250 DEG C. but below 400 DEG C., and carrying out in the same stage an increase in the temperature of the reaction material of at least 30 DEG C. Hydrogenation is effected by means of hydrogen, illuminating gas, town gas, water gas, cracking gas, coke-oven gas or low-temperature carbonization gas. The catalyst may be an oxide, sulphide, selenide, telluride, sulphate, borate, nitrate, carbonate, halide, phosphorous compound or a silicate of vanadium, molybdenum, tungsten, chromium, uranium, rhenium, iron, nickel, cobalt, gold, silver, copper, tin, titanium, lead, zinc, magnesium, cadmium, zirconium, antimony, bismuth, manganese, platinum, or palladium. The catalyst may also contain a promoter such as gold, silver, mercury, titanium, copper, zinc, tin, uranium or lead or their compounds. The catalyst may be supported on a carrier such as acid-treated montmorillonite, active silicic acid, silica gel, preferably with the oxides of titanium, thorium, zirconium or magnesium, titania gel or titanium oxide together with 0.1 to 30% by weight of SiO2 as silicates, bleaching earths, fuller's earth or synthetic aluminium or magnesium silicate. The carrier may advantageously be treated with gases, such as ammonia, hydrogen, sulphur dioxide, halogen; or with an acid such as hydrochloric acid, hydrogen fluoride, chlorsulphonic acid, formic acid or oxalic acid. The increase in temperature may be effected by the hydrogenation temperature, but additional heat may be supplied by adding carbon monoxide to the reactant gases. Large surfaces are produced by means of rings, hemispheres, cubes, cones, truncated cones, boxes and pyramids made of metal, porcelain, clay, cement, pumice, bleaching earths, aluminas, synthetic silicates, graphite or plastic material. In a typical Example (No. 1) the residue from a Near East crude oil boiling above 365 DEG C. is heated at 330 DEG C. under a pressure of 100 atmospheres together with hydrogen and led into a preliminary vessel filled with Raschig rings of alumina impregnated with MoO3. The reactants leave at 360 DEG C. and are then heated to 408 DEG C. and are led to a second chamber which they leave at 435 DEG C. The reactants then enter the reaction chamber proper and are treated at 430 DEG C. in the presence of a catalyst consisting of active alumina with 5% of silicic acid containing also cobalt and molybdenum oxide. The product comprises 70% of components boiling up to 480 DEG C. and a sulphur content of 1.6%. The catalyst is regenerated by nitrogen and air.