Continuous catalytic ammoniation of tetrahydrofuran to pyrrolidine: catalyst and process

doi:10.16085/j.issn.1000-6613.2017-1549

Abstract

Abstract: A kind of solid super-acid catalyst SO₄^2-/Fe₂O₃were prepared with γ-Al₂O₃as the carrier for continuous catalytic ammoniation of tetrahydrofuran to pyrrolidine. Compared with γ-Al₂O₃,HZSM-5 and other catalysts,SO₄^2-/Fe₂O₃-Al₂O₃showed a higher reaction selectivity under the same reaction conditions. The effects of the impregnating solution concentration of sulfuric acid,calcination temperature,calcination time on the performance of the catalysts were investigated which then were optimized. The result showed the optimum preparation conditions of the catalyst were calcined at 550℃ for 5h and sulfuric acid concentration of 1.0mol/L. The best reaction conditions were:350℃,NH₃/THF molar ratio of 6:1,volume velocities of 0.2h^-1,under which the conversion of tetrahydrofuran was 91.4% and the selectivity of pyrrolidine was 91.0%. Results from continuous 200h tests proved that the catalyst has high catalytic activity and good stability.

Key words: tetrahydrofuran, catalytic ammoniation, pyrrolidine, SO₄^2-/Fe₂O₃-Al₂O₃

摘要： 以γ-Al₂O₃为载体，制备负载铁系固体超强酸的SO₄^2-/Fe₂O₃-Al₂O₃催化剂应用于四氢呋喃连续催化胺化合成四氢吡咯反应，与γ-Al₂O₃、HZSM-5等催化剂相比，SO₄^2-/Fe₂O₃-Al₂O₃催化剂在相同的反应条件下可以获得更高的反应选择性。通过考察硫酸浸渍浓度、焙烧温度和焙烧时间等催化剂制备条件对反应结果的影响，以获得最佳的催化剂性能，同时对反应的工艺条件进行优化。通过实验结果可以得出，当硫酸浸渍浓度为1.0mol/L时，在550℃下焙烧5h能获得最高的催化活性。当反应温度为350℃、液时空速（LHSV）为0.2h^-1、四氢呋喃与氨气摩尔比为1∶6时，四氢呋喃转化率为91.4%，四氢吡咯选择性为91.0%。对SO₄^2-/Fe₂O₃-Al₂O₃催化剂进行200h寿命测试，表明该催化剂活性具有良好的稳定性。

关键词: 四氢呋喃, 催化胺化, 四氢吡咯, SO₄^2-/Fe₂O₃-Al₂O₃

CLC Number:

TQ032.4

ZHA Jie, QIAN Junfeng, SUN Fu'an, CHEN Shengchun, HE Mingyang, CHEN Qun. Continuous catalytic ammoniation of tetrahydrofuran to pyrrolidine: catalyst and process[J]. Chemical Industry and Engineering Progress, 2018, 37(06): 2230-2235.

查杰, 钱俊峰, 孙富安, 陈圣春, 何明阳, 陈群. 四氢呋喃连续催化胺化制备四氢吡咯催化剂及工艺[J]. 化工进展, 2018, 37(06): 2230-2235.

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