2-氯-5-三氟甲基吡啶和3-三氟甲基吡啶的制备

doi:10.11949/j.issn.0438-1157.20151013

化工学报 ›› 2015, Vol. 66 ›› Issue (12): 4843-4849.DOI: 10.11949/j.issn.0438-1157.20151013

• 催化、动力学与反应器 • 上一篇下一篇

2-氯-5-三氟甲基吡啶和3-三氟甲基吡啶的制备

董青青¹, 于万金², 胡猛¹, 林胜达², 刘武灿², 张建君², 程党国¹, 陈丰秋¹

1 浙江大学化学工程与生物工程学院, 浙江杭州 310027;
2 浙江省化工研究院, 国家ODS替代品工程技术研究中心, 浙江省化工新材料重点实验室, 浙江杭州 310023

收稿日期:2015-06-29 修回日期:2015-09-09 出版日期:2015-12-05 发布日期:2015-12-05
通讯作者: 陈丰秋
基金资助:
浙江省博士后科研择优资助项目(BSH1402061)。

Production of 2-chloro-5-trifluoromethylpyridine and 3-trifluoromethylpyridine

DONG Qingqing¹, YU Wanjin², HU Meng¹, LIN Shengda², LIU Wucan², ZHANG Jianjun², CHENG Dangguo¹, CHEN Fengqiu¹

1 College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China;
2 Zhejiang Research Institute of Chemical Industry, ODS Substitutes National Engineering Research Center, Zhejiang Key Laboratory of New Chemical Materials, Hangzhou 310023, Zhejiang, China

Received:2015-06-29 Revised:2015-09-09 Online:2015-12-05 Published:2015-12-05
Supported by:
supported by the Postdoctor Foundation of Zhejiang (BSH1402061).

摘要/Abstract

摘要：

研究了以3-甲基吡啶、氟化氢和氯气为原料在流化床反应器中一步法气相氯氟化反应制备2-氯-5-三氟甲基吡啶和3-三氟甲基吡啶的工艺,并对催化剂进行了筛选和考评,发现CrO-Al、CrCl-Al的活性较佳。以CrO-Al为催化剂,空速为288 h^-1,温度为300℃时,2-氯-5-三氟甲基吡啶和3-三氟甲基吡啶的总收率最高,为66.6%,且失活催化剂在350℃,氮气和空气的体积比为1:1的混合气体下再生后,其催化活性基本可以恢复,2-氯-5-三氟甲基吡啶和3-三氟甲基吡啶的总收率均保持在66%左右。根据实验结果提出了反应机理和结焦机理。对催化剂进行了BET、TG和NH₃-TPD表征,发现催化剂失活的主要原因是积炭覆盖了催化剂表面以及孔道,使催化剂强酸中心大量减少所致。

关键词: 3-甲基吡啶, 2-氯5-三氟甲基吡啶, 3-三氟甲基吡啶, 流化床, 催化剂, 活性, 再生

Abstract:

2-Chloro-5-trifluoromethylpyridine and 3-trifluoromethylpyridine are produced by β-picoline reacting with chlorine and hydrogen fluoride in a fluidized-bed reactor. The total yield of 2-chloro-5- trifluoromethylpyridine and 3-trifluoromethylpyridine reaches 66.6% over the CrO-Al catalyst at a space velocity of 288 h^-1 and temperature of 300℃. The reactivity of the deactivated catalysts is recovered after regeneration at 350℃ with mixed gas of nitrogen and air at volume ratio of 1:1. The total yield is around 66% with regenerated catalysts under the condition of 288 h^-1 and 300℃. According to the reaction result, the mechanism of one-step chlorofluorination reaction is proposed, dehydrochlorination-condensation of intermediate products accounted for coking. The results of BET, TG and NH₃-TPD characterizations indicate that the deactivation of the catalysts is caused by the carbonaceous by-products which cover the surface and pores of the catalyst.

Key words: 2-chloro-5-trifluoromethylpyridine, 3-trifluoromethylpyridine, β-picoline, fluidized-bed, catalyst, reactivity, regeneration

中图分类号:

TQ032.4

董青青, 于万金, 胡猛, 林胜达, 刘武灿, 张建君, 程党国, 陈丰秋. 2-氯-5-三氟甲基吡啶和3-三氟甲基吡啶的制备[J]. 化工学报, 2015, 66(12): 4843-4849.

DONG Qingqing, YU Wanjin, HU Meng, LIN Shengda, LIU Wucan, ZHANG Jianjun, CHENG Dangguo, CHEN Fengqiu. Production of 2-chloro-5-trifluoromethylpyridine and 3-trifluoromethylpyridine[J]. CIESC Journal, 2015, 66(12): 4843-4849.

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2-氯-5-三氟甲基吡啶和3-三氟甲基吡啶的制备

Production of 2-chloro-5-trifluoromethylpyridine and 3-trifluoromethylpyridine

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