Vapor-phase Catalytic Synthesis Of 1-phenylazepane From Aniline And 1,6-hexanediol

1-phenylazepane as a very important organic raw material is widely used in the fields of medicine chemistry, material chemistry, organic synthesize and so on. There are many ways to prepare 1-phenylazepane, however, from the environmental and economic points of view, vapor phase catalytic synthesis with aniline and 1, 6-hexanediol seems to be one of the most promising routes. In the dissertation, the catalysts for the synthesis of 1-phenylazepane were investigated and the characterization method of BET, XRD, NH3-TPD and TG were used for further research. The main results are summarized as follows:1. Using orthogonal design to select the active components (CuO, Ag₂O, FeO_x, CoO, NiO, VO_x) and supports ( SiO₂, SiO₂-Al₂O₃, Al₂O₃ ). It was find that the activity and selectivity of SiO₂-Al₂O₃ and SiO₂-Al₂O₃ supported Co were the highest.2. When the reaction temperature was 290℃and the H2 of the reduced gas was 60mL/min, the yield of 1-phenylazepane was the highest3. Over CoO/SiO₂-Al₂O₃, the yield of 1-phenylazepane could be up to 83% when the CoO loading was 0.3 mmol/g-(SiO₂-Al₂O₃), and the catalyst precursor was calcined with temperature-programmed calcination method from room temperature to 700℃in 3 hours, then kept caclining for 4 hours, and was situ-reduced for 0.5 hour in the H₂ (50%)-N₂ (50%) mixed gas (H₂: 30 mL/min). The XRD results showed that the CoO/SiO₂-Al₂O₃ catalyst with a certain crystallinity of CoO was disadvantage for the synthesis of 1-phenylazepane. The BET results showed it was disadvantage for the production of 1-phenylazepane if the specific surface area was too small. The TPD results showed that CoO/SiO₂-Al₂O₃ catalyst with small amounts of acidic sites and too strong acid strength took disadvantage of the synthesis of 1-phenylazepane.4. Carrying on the life experiment of CoO/SiO₂-Al₂O₃, its life time could reach up to 40h. The XRD and TG results indicated that the reasons for deactivation of the catalyst were the sintering of CoO particles and the coke during the reaction. Adding H₂ could increase the selectivity of 1-phenylazepane and suppress the formation of coke.5. The activity of SiO₂-Al₂O₃ calcined at 800℃was high and the yield of 1-phenylazepane reached 79% with the life above 100 h.