Page 139 - 《精细化工》2020年 第10期

第 37 卷第 10 期 精 细 化 工 Vol.37, No.10
2020 年 10 月 FINE CHEMICALS Oct. 2020

催化与分离提纯技术
NH 处理的 HY 分子筛催化甲醛异
3

丁烯 Prins 缩合反应

*
刘 瑶，徐禄禄，张维萍
（大连理工大学 化工学院 精细化工国家重点实验室，辽宁 大连 116024）

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摘要：对 HY 分子筛进行高温 NH 3 处理，制备了一系列含氮样品。利用 XRD、元素分析、 Si MAS NMR、NH 3 -TPD、
CO 2 -TPD 和 TG 等技术对 NH 3 处理后样品的结构、酸碱性和反应后积碳量进行了深入表征。考察了其催化甲醛
与异丁烯经 Prins 缩合制 3-甲基-3-丁烯-1-醇（MBO）的催化性能，评价了反应条件及不同气氛氮化催化剂对反
应性能的影响。结果表明，在 230 ℃、4 h 条件下，以含水体积分数为 5%的氨气为氮源制备的催化剂（用量 5%，
以多聚甲醛的质量为基准，下同）对 MBO 的选择性达到 89%，产率达到 82%。并且反应后积碳量从未氮化 HY
催化剂上的 27.0%显著下降到氮化催化剂上的 4.3%。样品的酸性和碱性表征结果表明，NH 3 处理后的 Y 分子筛
酸量减少而中等强度的碱量增加，从而抑制了副反应进行，提高了 MBO 的选择性，降低了积碳量。
关键词：Y 分子筛；氮化；碱催化；3-甲基-3-丁烯-1-醇；Prins 缩合反应；催化技术
中图分类号：TQ426.6 文献标识码：A 文章编号：1003-5214 (2020) 10-2069-07

Formaldehyde and isobutene condensation via Prins reaction

on HY zeolites treated with NH 3

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LIU Yao, XU Lulu, ZHANG Weiping
（State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian
116024, Liaoning, China）

Abstract: A series of nitrogen-containing samples were prepared by treating HY zeolites with NH 3 at high
temperature. Their structures, acidity and basicity as well as the coke contents after reaction were
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characterized by means of XRD, elemental analysis, Si MAS NMR, NH 3 -TPD, CO 2 -TPD and TG
techniques. Their catalytic performances in the formaldehyde-isobutene Prins condensation to prepare
3-methyl-3-buten-1-ol (MBO) were evaluated. The effects of reaction conditions and samples nitridated
under different atmosphere on the catalytic performances were investigated. The results showed that under
the conditions of 230 ℃ and 4 h, for the catalyst (dosage was 5%, based on the mass of paraformaldehyde,
the same below) prepared with NH 3 containing 5% volume fraction water treatment, the selectivity and
yield of MBO were up to 89% and 82%, respectively. Moreover, the coke content of HY zeolite after
reaction was 27.0%, while that of the nitridated sample was only 4.3%. The acidity and basicity
characterization results of the samples indicated that NH 3 treatment led to the decrease of the acidic sites
and increase of the medium-strong basic sites of Y zeolite, which inhibited the side reactions and enhanced
MBO selectivity. Meanwhile, the coke content decreased obviously on the nitridated sample due to its
fewer acid sites and appropriate amount of basic sites.
Key words: Y zeolite; nitridation; base catalysis; 3-methyl-3-buten-1-ol; Prins condensation; catalysis technology

3-甲基-3-丁烯-1-醇（MBO）是一种重要的精细 等领域具有很好的应用前景 [1-5] 。甲醛与异丁烯的
化学品中间体，在香料、高分子材料、药物和建筑 Prins 缩合反应是合成 MBO 的主要途径。目前，该

收稿日期：2020-04-20; 定用日期：2020-06-28; DOI: 10.13550/j.jxhg.20200332
基金项目：国家自然科学基金（21673027）
作者简介：刘 瑶（1994—），女，硕士生。联系人：张维萍（1972—），男，教授，E-mail：wpzhang@dlut.edu.cn。