Patent GB-760627-A (GB)
Title: Method of refining liquid hydrocarbons
IPC: C10G49/00
Filed: 1954-05-19
Abstract: Liquid hydrocarbons boiling below 400 DEG C. are refined by treatment with a hydrogen-containing gas in the presence of a cooled sulphur-resistant hydrogenation catalyst at a temperature below 350 DEG C., a hydrogen pressure or partial pressure below 25 atmospheres, and a hydrogen and carbon monoxide pressure or partial pressure (when employing a gas containing carbon monoxide) up to 40 atmospheres, so that sulphur and/or nitrogen compounds contained in the liquid hydrocarbons are decomposed. The liquid hydrocarbons may be derived from (a) the dry distillation of solid carbonaceous fuels, for example the low temperature carbonization or coking of coal, brown coal, peat or oil shale, (b) the gasification of solid carbonaceous fuels for example with air or mixtures of oxygen and air or water vapour, (c) the thermal or catalytic cracking of liquid hydrocarbons such as petroleum oils, tars or distillates of these or (d) the hydrogenation of solid carbonaceous fuels or liquid hydrocarbon fuels.  Sulphur-resistant hydrogenation catalysts mentioned are sulphides of tungsten, molybdenum, chromium, nickel or iron, or mixtures of these with or without promoters and/or carriers.  The hydrogen-containing gas may be prepared by (i) the dry distillation of coal or brown coal, (ii) the gasification of coke by the water gas process, (iii) the gasification of coal, brown coal, peat, oil shale, petroleum, tar or the distillation residues of liquid hydrocarbon fuels with air or with mixtures of oxygen and air or water vapour and/or carbondioxide or (iv) the splitting of methane with water vapour and/or oxygen.  The presence of carbon monoxide in the hydrogen-containing gas suppresses the hydrogenation of aromatic hpdrocarbons and phenols, present in the liquid hydrocarbons, to cyclohexane and cyclohexanol derivatives respectively, but aids the conversion of the phenols to aromatic hydrocarbons. Sulphur-containing substances, such as H2S or CS2, may be added to the hydrogen-containing gas in order to adjust the temperature in the hydrogenation zone.  Some cracking may also take place in the hydrogenation zone.  The refined liquid hydrocarbons may be washed with dilute caustic soda and/or dilute sulphuric acid and redistilled.  Apparatus for carrying out the process of the invention is described.  In the examples, (1) benzine from the pressure gasification of coal is treated in the vapour phase with hydrogen and a hydrogen-rich recycle gas in the presence of a catalyst, made up of molybdenum oxide, cobalt oxide and alumina and cooled so that its temperature is maintained at 330 DEG C., with a gas inlet temperature of 310 DEG C. and a pressure of 25 atmospheres, and the refined benzine is cooled, degasified, washed with dilute caustic soda solution and dilute sulphuric acid and redistilled, (2) benzene from a coke oven is refined as in (1) but using coke oven gas instead of hydrogen and (3) benzine from the pressure gasification of coal is refined as in (1) but using gas obtained by the pressure gasification of coal with oxygen and water vapour instead of hydrogen. Specification 345,738 and 424,531 are referred to.