Study On Catalytic Amination Of Alcohols And Phenols

Amines are important intermediates for organic chemical industry. A large number of drugs, herbicides, pesticides, dyes, and other chemicals contain amino groups are originated from reactions with such intermediates. On the basis of consulting a large amount of literatures and comparing the different routes synthesizing amines, the methods of preparing amines by catalytic animating the corresponding alcohols or phenols were studied in the works. The catalysts and reaction conditions for the animation were studied and optimized, which offered the fundamental data to make the synthesis process industrialization.In this paper, the catalysts for amination were prepared to synthesize the N,N-dimethylpropylamine, the morpholine, the propylamine and the n-octylamine.The catalyst, Cu-Ni-Zn loaded on active Al2O3 pre-treated with phosphoric acid, with good activity, selectivity and stability was prepared, with the active compounds of Cu/Ni/Zn=18-19/9-10/7-9 (Wt%). The impregnation method was employed for loading the active components, which made it easy to be produced in large scale. With the catalyst prepared, the conditions of dimethylamination of 1 -propanol at the fix-bed reactor were reviewed, at temperature of 210 , pressure of 0.3MPa, hydrogen flux of 100ml/min, LWSH of 0.3h-1 for 1-propanol, 2 mole ratio for (CH3)2NH/1-propanol, nearly all 1-propanol was reacted with 90% to product N,N-dimethylpropylamine. 40 hours reaction operation shows the catalyst with good stability.The catalyst of Cu-Ni on active Al2O3 prepared was also used to synthezied morpholine, propylamine and n-octylamine amination. The catalyst has good stability at temperature as high as 250 , it can be applied to both gas and liquid reaction. The conditions of amination of 1-octanol at the liquid-phase reactor were reviewed as, 1-octanol (65g), NH3 (30g) and catalyst (6.5g) were added to a high pressure autoclave then kept stirring for 10h at 190 . Under this condition nearly all 1-octanolwere reacted with the yield of 53% for n-octylamine.The animation of resorcinol were also studied in this work and the conditions of synthesizing m-aminophenol and m-(N,N-dimethyl aniino) phenol were studied and optimized.Resorcinol(55g), H2O (71g), NH3 (20g) and ammonia molybdate (17.5g) were added to a high pressure autoclave then kept stirring for 6h at 200 . During the time, the pressure was decreased from 3.0MPa to 2.4MPa. Under this condition nearly all resorcinol were reacted with the 84.4% yield of m-aminophenol.Resorcinol (110g), (CH3)2NH (45g) and phosphate (5.5g) were added to a high pressure autoclave then kept stirring for 5h at 200 . During the time, the pressure was decreased from 1.5MPa to 1.1MPa.Under this condition nearly all resorcinol were reacted with the 67.9% yield for m-(N,N-dimethyl amino) phenol.