Patent GB-405282-A (GB)
Title: Improvements in or relating to catalytic production of acetic acid
IPC: C07C51/12
Filed: 1932-06-20
Abstract: Catalysts for the production of acetic acid from methanol and carbon monoxide comprise a hydrated tungsten oxide, preferably containing at least as much oxygen as W2O5, the catalyst being preferably maintained in its hydrated condition by means of water vapour present in the reaction mixture.  The hydrated tungsten oxide may contain an admixture of one or more of the oxides of beryllium, bismuth, zinc, and copper.  The catalyst, may be prepared by reacting a solution of hexahydrated ammonium tungstate with nitric acid, washing the precipitate and (1) incorporating with nitrates of zinc, beryllium and bismuth, drying at 165 DEG  C. and tabletting, the oxides being in the ratio 90 WO3, 10 ZnO, 0.6 BeO, 2.5 Bi2O3; (2) impregnating with a solution of copper and beryllium nitrates, and further treating as above, the oxide ratios being 90 WO3, 10 CuO, 0.6 BeO; (3) adding zinc, copper and beryllium nitrates and treating as above, the oxide ratios being 90 WO3, 72nO, 3 CuO, 0.6 BeO; (4) adding titanium, bismuth and beryllium nitrates and treating as above, the oxide ratios being 90 WO3, 10 Ti O2, 2.5 Bi2O3, 0.6 BeO, but in this mixture the titanium oxide may be replaced by silica or thoria; (5) adding aluminium, zinc and bismuth nitrates and, treating as above, the oxide ratios being 90 WO3, 0.5 Al2O3, 10 ZnO, 2.5 Bi2O3 but in this mixture the alumina may be replaced by cerium oxide.  The reaction is effected in high pressure vessels lined with silver. Reference has been directed by the Comptroller to Specifications 254,819 and 337,014, [both in Class 2 (iii), Dyes &c.].ALSO:Acetic acid is produced from methanol and carbon monoxide in presence of a hydrated tungsten oxide, preferably containing at least as much oxygen as W2O5, the catalyst being preferably maintained in the hydrated state by means of water vapour present in the reaction mixture.  The hydrated tungsten oxide may contain an admixture of one or more of the oxides of beryllium, bismuth, zinc and copper.  The reaction may be effected at 300--400 DEG  C. and at 100--300 atmospheres pressure with more than two molecules of carbon monoxide and more than one molecule of water for each molecule of methanol. The catalysts may be prepared by reacting a solution of hexahydrated ammonium tungstate with nitric acid, washing the precipitate and (1) incorporating with the precipitate nitrates of zinc, beryllium, and bismuth, drying at 165 DEG  C. and tabletting, the oxides being in the ratio 90 WO3, 10 ZnO, 0.6 BeO, 2.5 Bi2O3; (2) impregnating with a solution of copper and beryllium nitrates and further treating as above, the oxide ratios being 90 WO3, 10 CuO, 0.6 BeO; (3) adding zinc, copper and beryllium nitrates and treating as above, the oxide ratios being 90 WO3, 7 ZnO, 3 CuO, 0.6 BeO; (4) adding titanium, bismuth, and beryllium nitrates and treating as above, the oxide ratios being 90 WO3, 10 TiO2, 2.5 Bi2O3, 0.6 BeO, but in this mixture the titanium oxide may be replaced by silica or thoria; (5) adding aluminium, zinc and bismuth nitrates and treating as above, the oxide ratios being 90 WO3, 0.5 Al2O3, 10 ZnO, 2.5 Bi2O3, but in this mixture the alumina may be replaced by cerium oxide.  Examples describe the production of acetic acid using the catalyst prepared according to methods (1) and (2) above.  In the second case, where the catalyst contains no bismuth, hydrogen is added to the reaction mixture.  The reaction chambers employed are lined with silver and are capable of withstanding high pressure.  Methyl acetate and dimethyl ether may be produced with the acetic acid, and may be converted into acetic acid by known means.  Reference has been directed by the Comptroller to Specifications 254,819 and 337,014, [both in Class 2 (iii), Dyes &c.].