文献类型：期刊文献

中文题名：HZSM-5分子筛催化异丁烯直接胺化反应的机理

英文题名：Mechanism of Direct Amination of Isobutene on HZSM-5 Molecular Sieve

作者：马云飞[1];金杏妹[1];郭世卓[2];舒兴田[3];舒怡[1]

机构：[1]华东理工大学化学与分子工程学院,上海200237;[2]上海石油化工股份有限公司化工研究所,上海200540;[3]中国石油化工股份有限公司石油化工科学研究院,北京100083

年份：2006

卷号：35

期号：8

起止页码：720

中文期刊名：石油化工

外文期刊名：Petrochemical Technology

收录：CSTPCD;;EI(收录号：20064210188107);Scopus;北大核心:【北大核心2004】；CSCD:【CSCD2011_2012】；

基金：中国石油化工股份有限公司基础研究资助项目(X502037)

语种：中文

中文关键词：异丁烯;胺化;叔丁胺;反应机理;HZSM-5分子筛;催化剂;过渡应答

外文关键词：isobutene ; amination; tert-butylamine; reaction mechanism; HZSM-5 molecular sieve; catalyst; transient response

摘要：采用HZSM-5分子筛催化剂,在固定床微反装置上考察了原料气加料顺序对异丁烯直接胺化反应的影响。用过渡应答技术对原料异丁烯、氨及产物叔丁胺在催化剂表面的吸附行为进行了研究,用热分析、原位红外光谱表征了催化剂在不同反应条件下的吸附性能。研究结果表明,在该反应体系中,催化剂表面氨的吸附占主导地位,异丁烯直接胺化反应经由以下机理:氨优先吸附于催化剂表面的B酸中心,形成铵正离子;而后与气相中的异丁烯反应,生成中间物种叔丁基正离子;叔丁基正离子与气相的或化学吸附的氨作用生成叔丁胺。
Effects of feeding order of different feedstocks on direct amination of isobutene to tertbutylamine over HZSM-5 molecular sieve catalyst in fixed-bed microreactor were studied. The adsorption behaviors of isobutene, ammonia and tert-butylamine on surface of the catalyst were investigated by means of transient response method. The adsorption properties of catalyst under different reaction conditions were studied by thermal analysis and in-situ IR. At amination temperature the preferential feeding order is ： feeding ammonia to the system first, followed by mixture of ammonia and isobutene. Surface of catalyst is mainly occupied by ammonia. The amination mechanism is inferred as follows ：firstly, ammonia is adsorbed on B-acid sites of the catalyst, then the chemisorbed ammonium cations react with gaseous isobutene and ten-butyl cations form as intermediate species, and finally the cations react with gaseous or chemisorbed ammonia to produce tert-butylamine.