摘要
有机硅材料具有防潮、耐腐蚀、耐高低温、无毒无味以及生理惰性等优异的性能,已被广泛应用于各个领域。有机硅单体的生产过程会产生约7%的副产物,以成分复杂及工业价值低的有机氯硅烷高沸物为主,因其易燃、有刺激性气味和具有强的腐蚀性,对环境及人体健康有重大危害。随着有机硅单体产能日益增加,有机氯硅烷高沸物的有效利用成为一个亟待解决的难题。高沸物的再利用主要是通过制备有机硅下游产品和裂解制备有机硅单体来实现,而后者需要在催化剂存在的条件下将高沸物中含有的Si-Si键和Si-C-Si断裂,并选用合适的封端剂将其转化成甲基氯硅烷单体。目前,路易斯酸、有机胺、过渡金属元素、活性炭和分子筛等是催化裂解的主要催化剂,各自工艺的操作条件及催化性能迥异。高沸物的裂解率最高可以达到99%以上,但由于生产工艺复杂、操作成本高等问题的限制,严重阻碍了其工业推广与应用。本文归纳了有机氯硅烷高沸物催化裂解材料的研究进展,分别对铝基化合物、有机胺或季铵盐、过渡金属及其化合物、分子筛或活性炭和金属磷酸盐等催化剂展开介绍,概括了以上各类催化剂的研究现状及面临的问题,并对其发展前景进行了合理的分析与讨论,以期为制备出高效、可工业化的有机氯硅烷高沸物裂解催化剂提供参考。
Organosiliconmaterials are widely applied in various fields due to their excellent properties,including moisture-proof,corrosion resistance,high and low temperature resistance,non-toxic and physiological inertia.However,the production process of organosilicon monomers will produce about 7%by-products,and they are mainly composed of organochlorosilane high-boiling residues with complex composition and low commercial value.Inflammable,pungent and strong corrosive organochlorosilane high-boiling residues are greatly harmful to our health and environment.With the increasing productivity of organosilicon monomer,the efficient utilization of organochlorosilane high-boiling residues has become a diffcult problem to be solved urgently.The recycle of organochlorosilane high-boiling residues is mainly achieved through the synthesis of organosilicon downstream products and organosilicon monomers by catalytic cracking method.The catalytic cracking process needs to break the Si-Si bond and Si-C-Si bond in the presence of catalysts and convert high-boiling residues into methylchlorosilane monomers by selecting a suitable blocking reagent.Lewis acids,organic amines,transition metal elements,activated carbon and molecular sieves are main catalysts for catalytic cracking,and their operating conditions and catalytic performance are different.The cracking ratio of organochlorosilane high-boiling residues can reach more than 99%.Nevertheless,the high operation cost and complex production technology limit the further industrial application and popularization.This review article offers a retrospection of research works with respect to the catalytic cracking materials for organochlorosilane high-boi-ling residues,and the materials include aluminum-based compounds,organic amines or quaternary ammonium salts,transition metals,molecular sieves or activated carbon and metallic phosphate catalysts.We have summarized the research status and problems of the above catalysts and analyzed the development prospects.It is expected to provide an available summary for development prospect of catalytic cracking industrialization.
作者
韦岳长
赖可溱
熊靖
李远锋
吴彤彤
WEI Yuechang;LAI Kezhen;XIONG Jing;LI Yuanfeng;WU Tongtong(State Key Laboratory of Heavy Oil Processing,College of Science,China University of Petroleum,Beijing 102249,China)
出处
《材料导报》
EI
CAS
CSCD
北大核心
2021年第21期21022-21027,21036,共7页
Materials Reports
基金
国家重点研发计划(2019YFC1907601)。
关键词
有机氯硅烷高沸物
催化裂解
催化剂
工业化
organochlorosilane high-boiling residues
catalytic cracking
catalyst
industrialization
