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2013 , Vol. 33 >Issue 05: 1035 - 1041

DOI: https://doi.org/10.6023/cjoc201210040

研究论文

硅藻土负载Dawson型磷钨酸催化1,4-丁二醇环化脱水合成四氢呋喃

  • 曹小华 ,
  • 任杰 ,
  • 柳闽生 ,
  • 占昌朝 ,
  • 谢宝华
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  • a 浙江工业大学化学工程与材料学院 杭州 310014;
    b 九江学院化学与环境工程学院 九江 332005;
    c 南京晓庄学院生物化工与环境工程学院 南京 211171

收稿日期: 2012-12-21

  修回日期: 2013-01-06

  网络出版日期: 2013-01-11

基金资助

国家自然科学基金(No. 21161009)、江西省自然科学基金(Nos. 20122BAB213001, 20114BAB213002)、江西省教育厅科技(Nos. GJJ10626, GJJ11613)资助项目.

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Dehydration of 1,4-Butanediol to Tetrahydrofuran Catalyzed by H6P2W18O62/Diatomite

  • Cao Xiaohua ,
  • Ren Jie ,
  • Liu Minsheng ,
  • Zhan Changchao ,
  • Xie Baohua
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  • a College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014;
    b College of Chemical and Environmental Engineering, Jiujiang University, Jiujiang 332005;
    c School of Biochemical and Environmental Engineering, Nanjing Xiaozhuang University, Nanjing 211171

Received date: 2012-12-21

  Revised date: 2013-01-06

  Online published: 2013-01-11

Supported by

Project supported by the National Natural Science Foundation of China (No. 21161009), the Natural Science Foundation of Jiangxi Province (Nos. 20114BAB213002, 20122BAB213001), the Science and Technology Foundation of Educational Commission of Jiangxi Province (Nos. GJJ10626, GJJ11613).

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摘要

利用硅藻土为载体, 用浸渍法制备了H6P2W18O62/硅藻土复合催化剂, 采用FT-IR, XRD, SEM, EDS, TG和Py-IR对其进行表征. 以1,4-丁二醇液相环化脱水制备四氢呋喃反应为探针, 考察其酸催化性能, 并对反应条件进行优化, 同时还考察了催化剂的重复使用性能. 催化剂兼具有Brönsted和Lewis酸性, 当负载量为40%时磷钨酸在硅藻土表面单层覆盖, 因而显示最大的总酸量, 表现出最高的催化活性, 在催化剂用量(以1,4-丁二醇质量计)3.2%, 反应温度180 ℃, 反应时间45 min, 四氢呋喃产率可达97.1%. 催化剂重复使用5次, 产率仍可达62.9%. UV-Vis, TG和Py-IR方法表征结果表明, 活性组分溶脱流失及结焦使催化剂酸中心减小是催化剂失活的原因. 与传统酸性催化剂相比, 采用H6P2W18O62/硅藻土作为反应催化剂不仅提高了反应产率(高于浓硫酸), 简化了工艺流程, 无酸腐蚀和污染问题, 且催化剂无需处理可重复使用多次.

关键词： 硅藻土; 磷钨酸; Dawson型; 四氢呋喃; 催化活性

本文引用格式

曹小华 , 任杰 , 柳闽生 , 占昌朝 , 谢宝华 . 硅藻土负载Dawson型磷钨酸催化1,4-丁二醇环化脱水合成四氢呋喃[J]. 有机化学, 2013 , 33(05) : 1035 -1041 . DOI: 10.6023/cjoc201210040

Abstract

Diatomite supported Dawson-type phosphotungstic acid catalysts with diferent loadings were prepared by the incipient impregnation method and characterized by FT-IR, UV-Vis, XRD, SEM, EDS, TG and Py-IR. Their catalytic behaviors were investigated via the cyclodehydration of 1,4-butanediol to synthesize tetrahydrofuran. The reaction conditions for tetrahydrofuran synthesis were optimized, and the stability of H6P2W18O62/Diatomite in the cyclodehydration reaction was investigated. The catalysts showed both Brönsted and Lewis acidity, and the catalyst with 40% H6P2W18O62 loading had the highest total acidity and catalytic activity because of the monolayer coverage of the active species. 97.1% yield of tetrahydrofuran could be obtained under the reaction conditions of 180 ℃ for 45 min, catalyst amount 3.2% of 1,4-butanediol. These catalysts could be recycled and still exhibited catalytic activity with a yield of 62.9% after five cycle reactions. It was found by means of UV-Vis, TG-DTA and Py-IR that the catalyst deactivation was due to the dissolution of H6P2W18O62 and decrease of the acid sites, which was caused by coking on catalyst surface. Compared with using sulfuric acid as catalyst, the present procedure is a green productive technology characterized by process simplification, higher yield and no corrosion for facilities. Moreover, the H6P2W18O62/Diatomite can be used for many times.

Key words： diatomite; phosphotungstic acid; dawson-type; tetrahydrofuran; catalytic behavior

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