乙炔二聚反应非水催化剂的研究

NON-AQUEOUS CATALYST FOR DIMERIZATION OF ACETYLENE

以CuCl为催化剂,分别研究了二甲基甲酰胺(DMF)、二甲亚砜、六甲基膦酰三胺溶剂和Me_2NH·HCl,Et_2NH·HCl、联苯胺盐酸盐助溶剂在乙炔-聚反应中的均相催化作用。结果表明,以DMF为溶剂、Me_2NH·HCl为助溶剂的非水催化剂的活性最高,其较佳配方为:CuCl 53g,DMF 54mL,Me_2NH·HCl 25g。乙炔-二聚反应的工艺条件为:乙炔空速320 h^(-1),反应温度67℃。与CuCl-NH_4Cl-HCl-H_2O催化体系相比,本催化体系所得乙炔转化率和乙烯基乙炔(MVA)单程收率分别提高176.3％和202.5％,MVA选择性提高9.53％,乙醛选择性降低94.4％。

The homogeneous catalysis of acetylene dimerization by using dimethyl formamide (DMF), dimethyl sulfoxide (DMSO)or hexamethyl phosphoric triamide (HPT) as solvent , and Me2NH · HC1 , Et2NH · HC1 or benzidine hydrochloride as solubilizer in the CuCl non-aqueous catalyst was studied .The results showed that the activity of the catalyst system using solvent DMF and solubilizer Me2NH · HC1 was highest and the formula was : CuCl 53 g , DMF 54 mL and Me2NH · HC1 25 g . The conditions of acetylene dimerization were : space velocity of acetylene 320 h-1, reaction temperature 67 °C .The conversion of acetylene , yield of monovinylacetylene (MVA) and selectivity of MVA increased by 176.3% ,202.5% and 9.53% , respectively , and selectivity of acetaldehyde decreased by 94.4% , as compared with those by CuCl - NH4C1 - HC1 - H2O catalyst system .