Patent GB-400262-A (GB)
Title: Improvements in the catalytic purification of oxygen-containing hydrogenation products of oxides of carbon
IPC: C07C31/04
Filed: 1932-04-22
Abstract: Oxygen-containing products obtained by the catalytic hydrogenation of oxides of carbon, particularly the fractions boiling above 110 DEG C. and consisting largely of higher alcohols, are purified by catalytic hydrogenation at 100-300 DEG  C. and pressures above 50 atmospheres in presence of sulphides or non-reducible oxides of the metals of groups 1, 2, 4, 5, 6 or 8 of the periodic system, compounds of the metals of group 6 being especially suitable.  The catalysts may be oxides, hydroxides, carbonates, and other salts from which the acid radical can be expelled by heat, and salts of the complex acids of silicic or phosphoric acid with molybdic or tungstic acid such as ammonium phosphomolybdate, but simple salts from which the acid cannot be expelled by heat, such as phosphates, silicates, and sulphates are not suitable.  Metals whose compounds are suitable are silver (preferably as molybdate, tungstate or vanadate), copper, zinc, cadmium, tin, lead, vanadium, bismuth, chromium, molybdenum, tungsten, uranium, nickel and cobalt, and compounds obtained from salts of acidic metal oxides of the 5th and 6th groups by complete or partial reduction with hydrogen sulphide are especially suitable. The catalysts may be employed alone or on carriers such as pumice, coke, animal charcoal, active charcoal, or clay.  The purification may be effected with the product in the liquid or vapour phase, for instance in stirring autoclaves with powdered catalysts or in trickling towers with rigid catalysts, or the vapour may be passed over the catalysts at about 200 atmospheres pressure.  A certain amount of reduction to hydrocarbons occurs, but the hydrocarbons are readily separated by distillation as they have lower boiling points than the unchanged alcohols. Preferably the initial substance is a fraction of restricted boilingpoint such as 120-180 DEG  C.  The purified alcohols are solvents for resins, and assist the solution of lower alcohols and benzine, and are suitable additions to fuels containing alcohols. A fuel may consist of 15 volumes methanol, 80 volumes of benzine, and 5 volumes of the purified alcohol product, the mixture only separating into its components at -20 DEG  C.  In the examples an initial fraction boiling at 120-180 DEG  C. is (1) trickled over a catalyst filling consisting of pieces of nickel and tungsten sulphides made by treating nickel tungstate with hydrogen sulphide, the process being effected at 200 DEG  C. and 200 atmospheres of hydrogen; (2) and (4) vaporized in a stream of hydrogen and led over a catalyst consisting of equimolecular quantities of zinc oxide, magnesium oxide, and molybdic acid or of manganese molybdate; (3) vaporized in a stream of hydrogen and passed over pieces of nickel sulpho-vanadate at 200 atmospheres and 265 DEG C.; (5) vaporized in hydrogen and passed over copper chromite at 180 DEG  C. and 200 atmospheres; (6) a fraction boiling at 160-210 DEG C. is passed in liquid form together with hydrogen through a tube containing nickel tungstate at 200 DEG  C. and 200 atmospheres.ALSO:Oxygen-containing products obtained by the catalytic hydrogenation of oxides of carbon, particularly the fraction boiling above 110 DEG  C., and consisting largely of higher alcohols, are purified by catalytic hydrogenation at 100-300 DEG  C. and pressures above 50 atmospheres in presence of sulphides or non-reducible oxides of the metals of groups 1, 2, 4, 5, 6, or 8 of the periodic system, compounds of the metals of group 6 being especially suitable.  The catalysts may be oxides, hydroxides, carbonates, and other salts from which the acid radical can be expelled by heat, and salts of the complex acids of silicic or phosphoric acid with molybdic or tungstic acid, such as ammonium phosphomolybdate, but simple salts from which the acid cannot be expelled by heat, such as phosphates, silicates, and sulphates are not suitable.  Metals whose compounds are suitable are silver (preferably as molybdate, tungstate or vanadate), copper, zinc, cadmium, tin, lead, vanadium, bismuth, chromium, molybdenum, tungsten, uranium, nickel, and cobalt, and compounds obtained from salts of acidic metal oxides of the 5th and 6th groups by complete or partial reduction with hydrogen sulphide are especially suitable. The catalysts may be employed alone or on carriers such as pumice, coke, animal charcoal, active charcoal, or clay.  The purification may be effected with the product in the liquid or vapour phase, for instance in stirring autoclaves with powdered catalysts or in trickling towers with rigid catalysts, or the vapour may be passed over the catalysts at about 200 atmospheres pressure.  A certain amount of reduction to hydrocarbons occurs, but the hydrocarbons are readily separated by distillation as they have lower boiling points than the unchanged alcohols.  Preferably the initial substance is a fraction of restricted boiling-point such as 120-180 DEG  C.  The purified alcohols are solvents for resins, and assist the solution of lower alcohols and benzine, and are suitable additions to fuels containing alcohols.  A fuel may consist of 15 volumes methanol, 80 volumes of benzine, and 5 volumes of the purified alcohol product, the mixture only separating into its components at --20 DEG  C.  In the examples an initial fraction boiling at 120-180 DEG  C. is (1) trickled over a catalyst filling consisting of pieces of nickel and tungsten sulphides made by treating nickel tungstate with hydrogen sulphide, the process being effected at 200 DEG  C. and 200 atmospheres of hydrogen; (2) and (4) vaporized in a stream of hydrogen and led over a catalyst consisting of equimolecular quantities of zinc oxide, magnesium oxide, and molybdic acid or of manganese molybdate; (3) vaporized in a stream of hydrogen and passed over pieces of nickel sulpho-vanadate at 200 atmospheres and 265 DEG C.; (5) vaporized in hydrogen and passed over copper chromite at 180 DEG  C. and 200 atmospheres; (6) a fraction boiling at 160-210 DEG C. is passed in liquid form together with hydrogen through a tube containing nickel tungstate at 200 DEG  C. and 200 atmospheres.