无机原料制备的大晶粒TS-1分子筛的表征及催化环己酮肟化反应性能评价

以硅溶胶为硅源、三氯化钛为钛源合成大晶粒TS-1分子筛，并用其催化环己酮肟化反应。采用XRD，XRF， FT-IR，SEM，TEM和低温N2吸-脱附等方法对催化反应前后催化剂的结构进行表征，结果表明，反应前后催化剂结构没有明显变化，说明该分子筛具有较好的稳定性。采用淤浆床反应器，在环己酮质量空速6 h-1、温度75 ℃的条件下，将制备的TS-1分子筛用于催化环己酮肟化反应，在运转时间190 h内，环己酮转化率和环己酮肟选择性分别达到99.0%和96.0%，说明所制备的大晶粒TS-1分子筛不仅具有与有机原料制备的TS-1分子筛相当的催化活性，而且稳定性更好。该分子筛还具有良好的分离和再生性能，再生分子筛的催化性能可以达到新鲜分子筛的水平。

CHARACTERIZATION AND PERFORMANCE EVALUATION OF LARGE CRYSTAL SIZE TS-1 MOLECULAR SIEVE PREPARED FROM INORGANIC MATERIALS FOR AMMOXIMATION OF CYCLOHEXANONE

In this paper, a large crystal size TS-1 molecular sieve was synthesized using inorganic silica sol and TiCl3 as silicon source and titanium source respectively. The synthesis of cyclohexanone oxime by ammoximation of cyclohexanone was carried out over the prepared TS-1 molecular sieve in a continuous slurry reactor at 75 oC and WHSV of 6 h-1. The fresh and used TS-1 molecular sieve samples were characterized by XRD, XRF, FT-IR, SEM, TEM and N2 adsorption-desorption methods. It was found that the structure of TS-1 molecular sieve samples prior and post to catalytic reaction was basically unchanged. Within running 190 h, the conversion of cyclohexanone and the selectivity of cyclohexanone oxime maintained around 99.0% and 96.0%, respectively, which indicated that the catalytic activity and stability of the prepared large crystal size TS-1 molecular sieve was similar, or even better than that of TS-1 molecular sieve prepared from organic materials. Furthermore, this TS-1 molecular sieve could be easily separated from the reaction mixture, and after regeneration its catalytic performance was close to that of fresh one.