微管反应器中硝基氯苯的连续合成

doi:10.16085/j.issn.1000-6613.2021-2284

化工进展 ›› 2022, Vol. 41 ›› Issue (9): 5022-5028.DOI: 10.16085/j.issn.1000-6613.2021-2284

微管反应器中硝基氯苯的连续合成

张晓啸(), 尚振华, 张向京()

河北科技大学化学与制药工程学院，河北石家庄 050018

收稿日期:2021-11-08 修回日期:2021-12-26 出版日期:2022-09-25 发布日期:2022-09-27
通讯作者: 张向京
作者简介:张晓啸（1994—），男，硕士研究生，研究方向为制药工程。E-mail：zxx5496@163.com。
基金资助:
河北省重点研发计划(20311201D)

Continuous flow synthesis of nitrochlorobenzene in microtubular reactor

ZHANG Xiaoxiao(), SHANG Zhenhua, ZHANG Xiangjing()

School of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, Hebei, China

Received:2021-11-08 Revised:2021-12-26 Online:2022-09-25 Published:2022-09-27
Contact: ZHANG Xiangjing

摘要/Abstract

摘要：

芳香族化合物的硝化是快速、强放热反应，采用连续硝化工艺可降低间歇操作可能引起的潜在风险。本文采用可视化方法和计算流体力学（CFD）模拟研究微管内流动状况的基础上，在体积为10mL的微管反应器中进行了氯苯连续硝化反应，探究了停留时间、温度、混酸比（硝酸与硫酸的摩尔比）、相比（硝酸与氯苯的摩尔比）对反应转化率、收率、产物邻对比和选择性的影响。结果表明，氯苯和混酸两相在内径为1mm的微通道内呈现出的Taylor流流型可以强化传质传热的效率，提高宏观反应速率。在停留时间为8min、温度80℃、混酸比=1∶1.5、相比=1∶1时，产物中邻对比在0.7~0.8之间，氯苯单程转化率为81.24%，一硝基氯苯的选择性为93.77%。采用连续硝化后，反应停留时间大幅降低，一硝基氯苯的邻对比明显提高。相比于传统釜式工艺，微管反应器内连续硝化更加安全、高效。

关键词: 氯苯硝化, 微管反应器, 连续流动, 硝基氯苯

Abstract:

The nitration of aromatic compounds is a rapid and strong exothermic reaction, and continuous process can reduce the potential risk caused by batch operations. The continuous nitration of chlorobenzene was carried out in a 10mL microtubular reactor on basis of the flow condition study by the visualization method and computational fluid dynamics (CFD) simulation. Some effects on the reaction conversion, yield, o-/p-nitrochlorobenzene ratio and selectivity were investigated, such as the residence time, temperature, mixed acid ratio (the molar ratio of nitric acid to sulfuric acid) and phase ratio (the molar ratio of nitric acid to chlorobenzene). The results showed that the chlorobenzene and mixed acid phases in a microchannel with an inner diameter of 1mm exhibited the Taylor flow pattern, which can enhance the efficiency of mass and heat transfer, leading to increase the macro reaction rate. When the residence time was 8min, the temperature was 80℃, the mixed acid ratio was 1∶1.5 and the molar ratio of nitric acid to chlorobenzene was 1∶1, the ratio of o-/p-nitrochlorobenzene was between 0.7—0.8, the single-pass conversion of chlorobenzene was 81.24% and the selectivity of mononitrochlorobenzene was 93.77%. The continuous nitrification can greatly shorten the residence time and significantly improve the o-/p-nitrochlorobenzene ratio. Compared with conventional kettle process, the continuous nitration of chlorobenzene in microtubular reactor was safer and more efficient.

Key words: chlorobenzene nitration, microtubular reactor, continuous flow, nitrochlorobenzene

中图分类号:

TQ246.1

张晓啸, 尚振华, 张向京. 微管反应器中硝基氯苯的连续合成[J]. 化工进展, 2022, 41(9): 5022-5028.

ZHANG Xiaoxiao, SHANG Zhenhua, ZHANG Xiangjing. Continuous flow synthesis of nitrochlorobenzene in microtubular reactor[J]. Chemical Industry and Engineering Progress, 2022, 41(9): 5022-5028.

图/表 9

图1 氯苯硝化宏观反应历程

图2 实验流程

图3 微管内两相流动状况

图4 停留时间对反应的影响

图5 反应混合的总离子流图和各物质质谱图

图6 相比对转化率、收率的影响

图7 相比对邻对比和选择性的影响

图8 混酸比1∶1.5时温度对反应结果的影响

图9 混酸比1∶2时温度对反应结果的影响

参考文献 17

1	KULKARNI Amol A. Continuous flow nitration in miniaturized devices[J]. Beilstein Journal of Organic Chemistry, 2014, 10: 405-424.
2	DENG Renjie, YOU Kuiyi, NI Wenjin, et al. Low-temperature and highly efficient liquid-phase catalytic nitration of chlorobenzene with NO₂: remarkably improving the para-selectivity in O₂ ^-Ac₂O-Hβ composite system[J]. Applied Catalysis A: General, 2020, 594: 117468.
3	KUBA M G, PRINS R, PIRNGRUBER G D. Batch and continuous nitration of toluene and chlorobenzene with acetyl nitrate over zeolite beta[J]. Applied Catalysis A: General, 2007, 333(1): 24-29.
4	ZHANG Cun, YU Meijing, PAN Xiaoyu, et al. Regioselective mononitration of chlorobenzene using caprolactam-based Brønsted acidic ionic liquids[J]. Journal of Molecular Catalysis A: Chemical, 2014, 383/384: 101-105.
5	WISS Jacques, FLEURY Christian, FUCHS Vincent. Modelling and optimization of semi-batch and continuous nitration of chlorobenzene from safety and technical viewpoints[J]. Journal of Loss Prevention in the Process Industries, 1995, 8(4): 205-213.
6	COX P R, STRACHAN A N. Two phase nitration of chlorobenzene[J]. Chemical Engineering Science, 1971, 26(7): 1013-1018.
7	RAVIKUMAR BANDARU S V, GHOSH Pallab. Mass transfer of chlorobenzene in concentrated sulfuric acid[J]. International Journal of Heat and Mass Transfer, 2011, 54(11/12): 2245-2252.
8	VERETENNIKOV E A, LEBEDEV B A, TSELINSKII I V. Nitration of chlorobenzene with nitric acid in a continuous installation[J]. Russian Journal of Applied Chemistry, 2001, 74(11): 1872-1876.
9	姜圣坤, 韩博, 赵鑫, 等. 微通道反应器中甲苯过量连续绝热硝化制备单硝基甲苯[J]. 化工进展, 2022, 41(6): 2910-2914.
	JIANG Shengkun, HAN Bo, ZHAO Xin. Preparation of mononitrotoluene by continuous adiabatic nitration of excess toluene in microreactor[J]. Chemicals Industry and Engineering Progress, 2022, 41(6): 2910-2914.
10	MA Daofan, ZHU Chunying, FU Taotao, et al. An effective hybrid solvent of MEA/DEEA for CO₂ absorption and its mass transfer performance in microreactor[J]. Separation and Purification Technology, 2020, 242: 116795.
11	余武斌, 高建荣, 李郁锦, 等. 微通道反应器内氯苯硝化反应研究[J]. 精细化工, 2010, 27(1): 97-100.
	YU Wubin, GAO Jianrong, LI Yujin, et al. Study on the nitration of chlorobenzene in microreactor[J]. Fine Chemicals, 2010, 27(1): 97-100.
12	ZHANG J S, WANG K, TEIXEIRA A R, et al. Design and scaling up of microchemical systems: a review[J]. Annual Review of Chemical and Biomolecular Engineering, 2017, 8: 285-305.
13	WANG Xiaoda, WANG Yongming, LI Fan, et al. Scale-up of microreactor: effects of hydrodynamic diameter on liquid-liquid flow and mass transfer[J]. Chemical Engineering Science, 2020, 226: 115838.
14	Marwah AL-AZZAWI, MJALLI Farouq S, HUSAIN Afzal, et al. A review on the hydrodynamics of the liquid-liquid two-phase flow in the microchannels[J]. Industrial & Engineering Chemistry Research, 2021, 60(14): 5049-5075.
15	ETMINAN Amin, MUZYCHKA Yuri S, POPE Kevin. A review on the hydrodynamics of Taylor flow in microchannels: experimental and computational studies[J]. Processes, 2021, 9(5): 870.
16	SHARIKOV F Y, SHARIKOV Y V, BELOKHVOSTOV V M, et al. A calorimetric study of the kinetics of chlorobenzene mononitration with nitric acid[J]. Russian Journal of Applied Chemistry, 2001, 74(11): 1877-1879.
17	金范龙, 包力, 戴传波, 等. 氯苯硝化工艺条件的研究[J]. 吉林化工学院学报, 1997, 14(3): 24-26.
	JIN Fanlong, BAO Li, DAI Chuanbo, et al. On the technological conditions of nitration of chlorobenzene[J]. Journal of Jilin Institute of Chemical Technology, 1997, 14(3): 24-26.

[1]	周亚, 杨春. 生物电化学系统对4-氯硝基苯的降解[J]. 化工进展, 2018, 37(01): 375-380.
[2]	王升华, 罗博文, 于威振, 周志元, 马怡然, 邵立冬, 辛志玲. 连续流动状态下纳米碳管负载镍催化剂催化苯乙炔选择加氢反应[J]. 化工进展, 2016, 35(10): 3201-3206.

微管反应器中硝基氯苯的连续合成

Continuous flow synthesis of nitrochlorobenzene in microtubular reactor

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 17

相关文章 2

编辑推荐

Metrics

本文评价