Patent GB-454391-A (GB)
Title: Improvements in the manufacture and production of valuable hydrocarbons by the thermal treatment of carbonaceous materials
IPC: C10G1/08
Filed: 1935-05-07
Abstract: The thermal treatment of carbonaceous materials, e.g. processes such as destructive distillation, cracking and treatment with hydrogenating gases, is carried out in presence of catalysts comprising graphitic acid produced by an oxidative conversion of solid carbonaceous materials, e.g. graphite, coal, shale, &c. or with solid substances produced from the graphitic acid by further heat treatment.  The oxidation may be carried out by means of a solution of potassium chlorate or permanganate in sulphuric and nitric acids. The further decomposition of the graphitic acid is obtained by heating it to 200--350 DEG  C. an increase of volume of several hundred times occurring.  The graphitic catalyst may be applied in colloidal form finely suspended in the materials to be treated or when working in the gas phase may be pressed into pills and arranged rigidly in the reaction chamber.  The graphitic acid may be used in conjunction with other catalysts particularly elements or their compounds of the 6th Group, and may be pretreated with hydrogen sulphide or hydrogen sulphide and ammonia.  50 kgs. graphite are introduced into a mixture of 875 litres of sulphuric acid and 438 litres of nitric acid and 325 kgs. of potassium chlorate are added during 24 hours.  A yellowish green graphitic acid is obtained by washing the reaction mass with water and drying and is finally decomposed by heating to 200--350 DEG  C., the final apparent volume being 600 times the original volume. The catalyst thus obtained is used in the treatment at 520 DEG  C. and at atmospheric pressure of isobutane to a product containing 11 per cent isobutylene and 2,4 per cent propylene.  With recirculation the yield of isobutylene may be increased to 82,5 per cent.ALSO:The thermal treatment of carbonaceous materials, e.g. processes such as destructive distillation, cracking, and treatment with hydrogenating gases, is carried out in presence of catalysts comprising graphitic acid produced by an oxidative conversion of solid carbonaceous materials, e.g. graphite, coal, shale, &c., or with solid substances produced from the graphitic acid by further heat treatment.  The oxidation may be carried out by means of a solution of potassium chlorate or permanganate in sulphuric and nitric acids.  The further decomposition of the graphitic acid is obtained by heating it to 200--350 DEG  C. an increase of volume of several hundred times occurring.  The graphitic catalyst may be applied in colloidal form finely suspended in the materials to be treated or when working in the gas phase may be pressed into pills and arranged rigidly in the reaction chamber.  The graphitic acid may be used in conjunction with other catalysts particularly elements or their compounds of the 6th Group, and may be pretreated with hydrogen sulphide or hydrogen sulphide and ammonia.  50 Kgs. graphite are introduced into a mixture of 875 litres of sulphuric acid and 438 litres of nitric acid and 325 kgs. of potassium chlorate are added during 24 hours.  A yellowish green graphitic acid is obtained by washing the reaction mass with water and drying and is finally decomposed by heating to 200--350 DEG  C., the final apparent volume being 600 times the original volume. The catalyst thus obtained is used (1) in the form of pills suspended in a reaction chamber for the hydrogenation of middle oil at 460 DEG  C. and 200 atmos. pressure--46 per cent of the middle oil is converted into benzines boiling below 180 DEG  C.; (2) after treatment when moist with hydrogen sulphide, and mixing with 20 per cent crystallized ammonium sulphotungstate, the mixture being decomposed by heating to 300--350 DEG  C., in the destructive hydrogenation of middle oil at 423 DEG C. and 200 atmos.  A 65 per cent conversion to benzines is obtained; (3) In the hydrogenation at 510 DEG  C. and 70 atmos. pressure of a benzine boiling below 150 DEG  C. to obtain a benzine 28 per cent of which boils below 100 DEG  C.  A mixture containing equal proportions of the original and final benzine has an octane value of 77 which is an improvement in octane value of 16 points; (4) in the hydrogenation at 520 DEG  C. and at atmospheric pressure of isobutane to a product containing 11 per cent isobutylene and 2,4 per cent propylene.  With recirculation the yield of isobutylene may be increased to 82,5 per cent.