NaAlCl_(4)/ZSM-5@γ-Al_(2)O_(3)核壳复盐催化剂的制备及其歧化性能  

Preparation and disproportionation properties of NaAlCl_(4)/ZSM-5@γ-Al_(2)O_(3) core-shell catalyst

作　　者：徐文媛 黄鸿坤 沈蒙莎 程永兵 陈曦 杨绍明 XU Wenyuan;HUANG Hongkun;SHEN Mengsha;CHENG Yongbing;CHEN Xi;YANG Shaoming(School of Materials Science and Engineering,East China Jiaotong University,Nanchang 330013,China)

机构地区：[1]华东交通大学材料科学与工程学院,南昌330013

出　　处：《复合材料学报》2022年第10期4602-4609,共8页Acta Materiae Compositae Sinica

基　　金：国家自然科学基金(22162010,21872049)。

摘　　要：针对氯硅烷残留物的危害性和资源化利用,通过歧化反应将副产物制备成经济效益更高的二甲基二氯硅烷。由田菁胶为粘结剂,以γ-Al_(2)O_(3)为壳,对ZSM-5分子筛表面进行修饰,构筑ZSM-5@γ-Al_(2)O_(3)核壳载体;然后,通过高温浸渍负载法,将NaAlCl_(4)负载在ZSM-5@γ-Al_(2)O_(3)核壳载体表面。综合研究了不同Si/Al摩尔比的ZSM-5分子筛、不同NaAlCl_(4)负载比例和AlCl_(3)溶液浸渍时间对歧化制备反应二甲基二氯硅烷的影响。采用XRD、SEM、SEM-EDS、BET和FTIR对样品进行表征分析,结果表明,当温度为200℃,硅铝摩尔比为50,复盐NaAlCl_(4)比例为8wt%,AlCl_(3)浸渍时间为3 h时,催化剂活性达到最佳,产率为71.81%。通过NaAlCl_(4)复盐负载ZSM-5@γ-Al_(2)O_(3)核壳表面,改善单一催化成分性能不稳定,提高催化效率,再分配氯硅烷副产品甲基三氯硅烷(M1)和三甲基氯硅烷(M3),得到商业价值较高的二甲基二氯硅烷(M2),实现变废为宝。In view of the harmness and resource utilization of chlorosilane residues, the by-products are prepared into dimethyldichlorosilane with higher economic benefit through disproportionation reaction. The ZSM-5@γ-Al_(2)O_(3)core-shell carrier was constructed by modifying the surface of ZSM-5 molecular sieve with Tianjing gum as the binder and γ-Al_(2)O_(3)as the shell. NaAlClwas loaded on the surface of ZSM-5@γ-Al_(2)O_(3)core-shell carrier by hightemperature impregnation loading method. The effect of ZSM-5 molecular sieve with different Si/Al molar ratios on the disproportionation preparation of dimethyldichlorosilane, the effect of different NaAlClloading ratios and the impregnation time of AlClsolution on the reaction of disproportionation preparation of dimethyldichlorosilane were investigated comprehensively, and the samples were characterized by XRD, SEM, SEM-EDS, BET and FTIR.The results show that the catalyst activity reach the optimum with 71.81% yield when the temperature is 200°C, the silica-alumina molar ratio is 50, the compound salt NaAlClratio is 8wt%, and the AlClimpregnation time is 3 h.The NaAlClcompound salt loading on the surface of the ZSM-5@γ-Al_(2)O_(3)core-shell catalyst shows the improved catalytic efficiency and enhanced performance instability compared with single catalytic component. Further redistribution chlorosilane by-products methyl trichlorosilane(M1) and trimethylchlorosilane(M3) synthesis can obtain high commercial value dimethyl dichlorosilane(M2), so as to realize the transformation of waste into treasure.

关 键 词：NaAlCl_(4) ZSM-5 γ-Al_(2)O_(3) 核壳 歧化 二甲基二氯硅烷 催化剂 

分 类 号：T-19[一般工业技术]