Preparation and performance of Zn/H-ZSM-5 catalyst for catalytic amination of allyl alcohol to 3-picoline

doi:10.3969/j.issn.0438-1157.2014.03.020

CIESC Journal ›› 2014, Vol. 65 ›› Issue (3): 905-911.DOI: 10.3969/j.issn.0438-1157.2014.03.020

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Preparation and performance of Zn/H-ZSM-5 catalyst for catalytic amination of allyl alcohol to 3-picoline

MA Tianqi, WEI Tianyu, PIAN Yanjie, ZHANG Yuecheng, ZHAO Jiquan

School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China

Received:2013-06-13 Revised:2013-12-11 Online:2014-03-05 Published:2014-03-05
Supported by:
supported by the National Natural Science Foundation of China (20976034), the Natural Science Foundation for Young Scientists of Hebei Province (B2009000009) and the Foundation for Innovative Talents of Hebei Province (CPRC012).

丙烯醇催化氨化合成3-甲基吡啶催化剂的制备及性能

马天奇, 魏天宇, 骈岩杰, 张月成, 赵继全

河北工业大学化工学院, 天津 300130

通讯作者: 张月成
作者简介:马天奇（1989—），男，硕士研究生。
基金资助:
国家自然科学基金项目（20976034）；河北省自然科学基金青年基金项目（B2009000009）；河北省高校百名优秀创新人才支持计划项目（CPRC012）。

Abstract

Abstract: H-ZSM-5 supported zinc catalysts were prepared by impregnation method, and their catalytic performances for amination of allyl alcohol to 3-picoline were evaluated in a fixed-bed reactor. It is found that the catalyst Zn₁₂/H-ZSM-5(80) (H-ZSM-5 with 80 silicon/aluminum (Si/Al) ratio and zinc loading of 12%) shows the best performance among all the studied catalysts. 97.8% conversion of allyl alcohol and 37.9% selectivity toward 3-picoline are obtained on this catalyst using reaction conditions: atmospheric pressure, at 420℃, ammonia/allyl alcohol mole ratio 3:1 and gas hour space velocity 300 h^-1. The characterization results, obtained by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and FT-IR of absorbed pyridine, indicate that zinc on Zn₁₂/H-ZSM-5(80) is Zn²⁺, there is Lewis acid on HZSM-5. In 3-picoline formation, ZnO provides active sites of dehydrogenation reaction, and addition and cyclization reactions are mainly catalyzed by the Lewis acid.

Key words: allyl alcohol, 3-picoline, molecular sieves, catalysis, amination, Zn₁₂/H-ZSM-5(80), fixed-bed

摘要： 采用浸渍法制备了一系列H-ZSM-5分子筛负载过渡金属锌催化剂，在固定床反应器上考察了这些催化剂对丙烯醇催化氨化合成3-甲基吡啶的催化性能。通过对H-ZSM-5的硅铝比、锌负载量对催化剂催化性能影响的考察，发现硅铝比为80、锌负载量为12%时得到的催化剂Zn₁₂/H-ZSM-5（80）的催化性能最佳。在常压、反应温度420℃、氨醇摩尔比3：1、空速300 h^-1条件下，丙烯醇在该催化剂上的转化率和3-甲基吡啶的选择性分别达到97.8%和37.9%。利用X射线衍射（XRD）、X射线光电子能谱（XPS）以及吡啶吸附红外对催化剂进行了表征，结果表明，Zn₁₂/H-ZSM-5（80）上负载的Zn²⁺为L酸；在丙烯醇生成3-甲基吡啶的反应过程中催化剂的脱氢活性物种为氧化锌，而加成和环合反应则主要是由催化剂中的L酸催化实现的。

关键词: 丙烯醇, 3-甲基吡啶, 分子筛, 催化(作用), 氨化, Zn₁₂/H-ZSM-5(80), 固定床

CLC Number:

TQ032.4

MA Tianqi, WEI Tianyu, PIAN Yanjie, ZHANG Yuecheng, ZHAO Jiquan. Preparation and performance of Zn/H-ZSM-5 catalyst for catalytic amination of allyl alcohol to 3-picoline[J]. CIESC Journal, 2014, 65(3): 905-911.

马天奇, 魏天宇, 骈岩杰, 张月成, 赵继全. 丙烯醇催化氨化合成3-甲基吡啶催化剂的制备及性能[J]. 化工学报, 2014, 65(3): 905-911.

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Preparation and performance of Zn/H-ZSM-5 catalyst for catalytic amination of allyl alcohol to 3-picoline

丙烯醇催化氨化合成3-甲基吡啶催化剂的制备及性能

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