GB488856A - Process for the production of valuable high boiling products by the treatment of solid carbonaceous materials with hydrogenating gases - Google Patents

Abstract

In the production of high - boiling liquid hydrocarbon products from solid carbonaceous materials made into a paste with oil by treatment with hydrogenating gases in an amount over 1000 cubic metres per ton of coal paste, catalysts comprising sulphides of the 5th, 6th, or iron group of the periodic system which have been formed into pieces are employed and the temperature is kept below 415 DEG C., preferably between 330 and 400 DEG C. The coal paste may contain 10 to 50 per cent of coal in an oil boiling above 200 DEG C. and free from asphalt. Hydrogenating gases at pressures of 100 to 1000 atmospheres or more and in quantities of 1500 to 7000 or more cubic metres per ton of paste may be employed. Preferably the temperature of the material increases as it passes through the reaction zone, being maintained below 370 DEG C. during the first quarter of the whole reaction time. The catalysts are used in concentrated form or on carriers which do not decrease their action, e.g. bleaching earth treated with hydrofluoric acid. They are shaped into pieces of over 3 mm. diameter by moulding, extrusion, cutting, &c., and are arranged so as not to offer much resistance to the flow of the paste. Volatile catalysts, e.g. organic halogen compounds such as carbon tetrachloride, or volatile sulphur compounds such as hydrogen sulphide or carbon disulphide may be added, and the coal may be impregnated with a solution of a catalyst, or may be treated with acid prior to the hydrogenation. The through-put is preferably between 0,05 and 0,5 kg. of coal per litre of reaction space per hour. The products may be re-cycled or may be subjected to further known treatments. In an example, brown coal after neutralization with sulphuric acid is pasted with browncoal tar in the proportion 40 : 60 and then treated with hydrogen in an amount of 2000 cubic metres per ton of paste, being passed at 250 atmospheres and 355 DEG C. downwards through a reaction space filled with alternate layers of massive cylinders (outer diameter 10 mm.) and hollow cylinders (outer diameter 15 mm.) consisting of an equimolecular mixture of molybdic acid, zinc oxide and magnesia previously treated with hydrogen sulphide at 400 DEG C. and 10 atm. A 78 per cent conversion of the coal is obtained. Specification 365,892 is referred to.