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

doi:10.6023/cjoc201210040

Chin. J. Org. Chem. ›› 2013, Vol. 33 ›› Issue (05): 1035-1041.DOI: 10.6023/cjoc201210040 Previous Articles Next Articles

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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^a,b, 任杰^a, 柳闽生^c, 占昌朝^a,b, 谢宝华^b

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 发布日期:2013-01-11
通讯作者: 任杰,renjie.r@263.net;曹小华,caoxiaohua@tom.com E-mail:renjie.r@263.net;caoxiaohua@tom.com
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.

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

Cao Xiaohua^a,b, Ren Jie^a, Liu Minsheng^c, Zhan Changchao^a,b, Xie Baohua^b

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:2012-12-21 Revised:2013-01-06 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).

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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Cao Xiaohua, Ren Jie, Liu Minsheng, Zhan Changchao, Xie Baohua. Dehydration of 1,4-Butanediol to Tetrahydrofuran Catalyzed by H₆P₂W₁₈O₆₂/Diatomite[J]. Chin. J. Org. Chem., 2013, 33(05): 1035-1041.

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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

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

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