Patent GB-488651-A (GB)
Title: Improvements in or relating to the production of hydrocarbon products of low boilingpoint by the treatment of carbonaceous materials of elevated temperatures
IPC: C10G1/08
Filed: 1936-12-07
Abstract: Carbonaceous materials containing more than one carbon atom in the molecule, e.g. coal, tars, oils, hydrocarbon gases, &c. are subjected to treatment at elevated temperatures to obtain valuable hydrocarbons in presence of catalysts comprising a component (a) consisting of one or more of the metals manganese, iron, copper, and zinc in the form of preformed sulphur compounds, e.g. sulphide or preformed phosphorus compounds, e.g. phosphates (the phosphate of zinc being always employed as a neutral phosphate and only used when working in the presence of extraneous hydrogen) and a p  component (b) consisting of one or more of the metals molybdenum, tin, tungsten, rhenium, uranium, vanadium, chromium, nickel, or cobalt or compounds thereof, the amount by weight of component (a) in the catalyst being greater than the amount by weight of component (b).  Thermal treatments specified comprise (a) destructive hydrogenation and like hydrogenation reactions, e.g. aromatizing hydrogenation, hydroforming, dealkylation or isomerization, conversion of cresols to phenol, reduction of hydroxyl groups of phenols &c., hydrofining and purifying crude materials containing asphalts, and nitrogen, oxygen, and sulphur impurities, "low temperature" hydrogenation, (b) cracking, (c) dehydrogenation, (d) thermal treatment of hydrocarbon oils with gaseous hydrocarbons, e.g. butane, propane.  Specific components of Group (a) are ferrous, ferric, and ferrous-ferric sulphides, cuprous and cupric sulphides, manganous and manganic sulphides, sulphates, sulphites, thiosulphates, and mercaptides of these metals; ortho, meta, and pyrophosphates, phosphates or phosphides.  Components of Group (b) comprise oxides, hydroxides, sulphides, sulphates, thioacids, mercaptides, halides, selenides, tellurides, phosphates, carbonates, and organic salts of the metals specified. Intimate mixtures of components of Groups (a) and (b) may be obtained by chemical conversion or precipitation of mixtures or solutions containing the specified components or by sulphidizing alloys containing the required constituents.  Salts of a metal base of component (a) with a thio acid of a metal of group (b) may be decomposed to give a mixture of the sulphides or may be employed direct as a chemical compound of component (a) with component (b), e.g. iron thiotungstate, zinc thiomolybdate provided the proportions of the components are as specified above. The mixed catalyst may be applied to carriers suitably activated, e.g. by treatment with steam, hydrogen fluoride, acids, gases volatile sulphur compounds free from oxygen, oxides of carbon hydrogen phosphide, &c.  In examples: (1) middle oil is treated with hydrogen at 495 DEG  C. and 250 atmos. in presence of a mixture of 90 parts ferrous sulphide and 10 parts tungsten disulphide, (2) as in (1) but in presence of 85 parts manganous sulphide and 15 parts molybdenum sulphide, (3) benzene refined in presence of tungsten disulphide at 200 DEG  C. is then passed over catalysts specified in example 1 at 500 C.A. product is obtained containing 5 per cent benzene, 15 per cent toluene, 15 per cent xylene the remaining consisting of high boiling aromatic hydrocarbons suitable as solvents for lacquers or anti-knock agents, (5) middle oil prehydrogenated at 340 DEG  C. and 250 atmos. in presence of tungsten disulphide is then subjected to splitting destructive hydrogenation at 502 DEG  C. in presence of a catalyst comprising 80 parts carbon activated by steam at 800 DEG  C. and supporting a mixture of 12 parts ferrous sulphide and 8 parts tungsten disulphide, (6) crude cresol in converted to neutral oil by treatment with hydrogen at 450 DEG  C. and 250 atmos.  Comparative results are given using as catalyst (a) ferrous sulphide alone, (b) tungsten disulphide alone, (c) mixture of 85 parts tungsten disulphide and 15 parts ferrous sulphide, (8) crude xylenols are converted into neutral oils by treatment with hydrogen in presence of catalyst obtained by treating with hydrogen sulphide at 450 DEG  C. turnings obtained from a specified steel containing 22,7 per cent tungsten, 0,5 per cent molybdenum, 1,1 per cent nickel, and 1,4 per cent vanadium, (13) a cracking residue containing 12 per cent asphalt is treated with hydrogen at 600 atmos. pressure and at 485 DEG  C. in presence of a catalyst comprising 90 per cent ferrous sulphide and 10 per cent tungsten disulphide.  The asphalt content of the product is reduced to 1 per cent and a Diesel oil having a cetene number of 50 is obtained, (17) a benzine containing phenols, naphthenes, and aromatic hydrocarbons is passed with hydrogen at 475 DEG  C. over a catalyst obtained by treating a mixture of nickel carbonate and tungstic acid with hydrogen sulphide and mixing the sulphides obtained with precipitated ferrous sulphide.  A product free from phenols and containing 1 per cent naphthenes and 59 per cent aromatic hydrocarbons is obtained, (21) vapours of a middle oil having a cetene number of 20 are passed with hydrogen at 440 DEG  C. over a catalyst obtained by pouring a solution of 33 grs. of ammonium thiomolybdate in 500 cms. ammonium sulphide solution into a solution of 250 grs. ferrous sulphate and filtering, washing, and drying in hydrogen the black precipitate obtained.  A Diesel oil having a cetene number of 50 is obtained, (25) bituminous coal admixed with 1 per cent of a catalyst comprising 80 parts iron sulphide and 20 parts ammonium phosphomolybdate and with 1 1/2 parts of tetrahydronaphthalene is heated in a revolving bomb at 400 DEG  C. and 100 atmos. pressure for 3 hours, 80 per cent of a pitchy extract free from ash is obtained.  Multi-stage hydrogenation treatments of which one or more stage take place in presence of catalysts of the kind specified are described in examples 10, 11, 12, 14, 16, 23 while a preliminary treatment with liquid sulphur dioxide to segregate components poor in hydrogen is described in examples 19 and 20. Specifications 331,558, [Class 32], 333,511, [Class 1 (i), 348,690, 379,335, and 434,141, are referred to.ALSO:Carbonaceous materials containing more than one carbon atom in the molecule, e.g. coal, tars, oils, hydrocarbon gases, &c. are treated at elevated temperatures to obtain valuable hydrocarbons in presence of catalysts comprising a component (a) consisting of one or more of the metals manganese, iron, copper and zinc in the form of preformed sulphur compounds, e.g. sulphides or preformed phosphorus compounds, e.g. phosphates (the phosphate of zinc being always employed as a neutral phosphate and only used when working in the presence of extraneous hydrogen) and a component (b) consisting of one or more of the metals molybdenum, tin, tungsten, rhenium, uranium, vanadium, chromium, nickel, or cobalt or compounds thereof, the amount by weight of component (a) in the catalyst being greater than the amount by weight of component (b).  Thermal treatments specified comprise (1) destructive hydrogenation and like hydrogenation reactions, e.g. aromatizing hydrogenation, hydroforming, dealkylation or isomerization, conversion of cresols to phenol, reduction of hydroxyl groups of phenols, &c., hydrofining and purifying crude materials containing asphalts, and nitrogen, oxygen, and sulphur impurities, " low temperature " hydrogenation, (2) cracking, (3) dehydrogenation. Specific components of Group (a) are ferrous, ferric, and ferrous-ferric sulphides, cuprous and cupric sulphides, manganous and manganic sulphides; sulphates, sulphites, thiosulphates and mercaptides of these metals; ortho, meta, and pyrophosphates; phosphates and phosphides.  Components of Group (b) comprise oxides, hydroxides, sulphides, sulphates, thioacids, mercaptides, halides, selenides, tellurides, phosphates, carbonates, and organic salts of the metals specified.  Intimate mixtures of components of Groups (a) and (b) may be obtained by chemical conversion or precipitation of mixtures or solutions containing the specified components or by sulphidizing alloys containing the required constituents.  Salts of a metal base of component (a) with a thioacid of a metal of group (b) may be decomposed to give a mixture of the sulphides or may be employed direct as a chemical compound of component (a) with component (b), e.g. iron thiotungstate, zinc thiomolybdate provided the proportions of the components are as specified above.  The mixed catalyst may be applied to carriers suitably activated, e.g. by treatment with steam, hydrogen fluoride, acids, gases, volatile sulphur compounds free from oxygen, oxides of carbon, hydrogen phosphide, &c.  In examples: (1) middle oil is treated with hydrogen at 495 DEG  C. and 250 atmos. in presence of a mixture of 90 parts ferrous sulphide and 10 parts tungsten disulphide; (2) as in (1) but in presence of 85 parts manganous sulphide and 15 parts molybdenum sulphide; (3) benzene refined in presence of tungsten disulphide at 200 DEG  C. is then passed over catalysts specified in example 1 at 500 DEG  C.  A product is obtained containing 5 per cent benzene, 15 per cent toluene, 15 per cent xylene, the remaining consisting of high boiling aromatic hydrocarbons suitable as solvents for lacquers or as anti-knock agents; (5) middle oil prehydrogenated at 340 DEG C. and 250 atmos. in presence of tungsten disulphide is then subjected to splitting destructive hydrogenation at 502 DEG  C. in presence of catalyst comprising 80 parts carbon activated by steam at 800 DEG  C. and supporting a mixture of 12 parts ferrous sulphide and 8 parts tungsten disulphide; (6) crude cresol is converted to neutral oil by treatment with hydrogen at 450 DEG  C. and 250 atmos. Comparative results are given using as catalyst (a) ferrous sulphide alone, (b) tungsten disulphide alone, (c) mixture of 85 parts tungsten disulphide and 15 parts ferrous sulphide; (8) crude xylenols are converted into neutral oils by treatment with hydro