Abstract
The matching of the micro-dispersion method and the reaction kinetics is of the utmost importance for the fast and strongly exothermic nitration reaction. Taken as an example to discuss this issue, a synthesis of 3,4-dichloronitrobenzene via the nitration of o-dichlorobenzene with mixed acid of nitric acid and sulfuric acid was conducted in continuous-flow reactors in this work. Through combining the adiabatic reaction environment, the use of a micropacked-bed reactor, and introducing partial product circulation, it successfully achieved the matching of the micro-dispersion state and the reaction kinetic characteristics. The good two-phase dispersion state can be maintained throughout the micropacked-bed reactor and the reaction can be completed within 5 s with above 89% selectivity under adiabatic condition. Furthermore, the reaction activation energy was conveniently obtained by processing the temperature distribution data, providing a fundamental to realize a reliable design of the nitration reaction process with high efficiency and inherent safety.
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References
Bogdan A, McQuade DT (2009) A biphasic oxidation of alcohols to aldehydes and ketones using a simplified packed-bed microreactor. Beilstein J. Org. Chem. 5:17. https://doi.org/10.3762/bjoc.5.17
Chen P, Shen C, Qiu M, Wu J, Bai Y, Su Y (2020) Synthesis of 5-fluoro-2-nitrobenzotrifluoride in a continuous-flow millireactor with a safe and efficient protocol. J. Flow. Chem. 10(1):207–218. https://doi.org/10.1007/s41981-019-00068-3
Cheng X, Zhang S (1998) Resparch on the conventional nitration and adiabatic nitration for o-dichlorobenzene mixed acids. J. Shenyang Inst. Technol. 17(1):102–106
Cox PR, Strachan AN (1971) Two phase nitration of chlorobenzene. Chem. Eng. Sci. 26(7):1013–1018. https://doi.org/10.1016/0009-2509(71)80014-3
Du C, Wang P, Hu Y, Zhang J, Luo G (2020) Liquid-liquid mass transfer enhancement in milliscale packed beds. Ind. Eng. Chem. Res. 59(9):4048–4057. https://doi.org/10.1021/acs.iecr.9b04225
Gage JR, Guo X, Tao J, Zheng C (2012) High output continuous nitration. Org. Process. Res. Dev. 16(5):930–933. https://doi.org/10.1021/op2003425
Gutmann B, Cantillo D, Kappe CO (2015) Continuous-flow technology: a tool for the safe manufacturing of active pharmaceutical ingredients. Angew. Chem. Int. Ed. 54(23):6688–6728. https://doi.org/10.1002/anie.201409318
Halder R, Lawal A, Damavarapu R (2007) Nitration of toluene in a microreactor. Catal. Today 125(1–2):74–80. https://doi.org/10.1016/j.cattod.2007.04.002
Jiang D, Jue W (1998) 3,4-Dichloronitrobenzene synthesis process improvement. Zhejiang Chem. Ind. 29(4):25–28
von Keutz T, Cantillo D, Kappe CO (2019) Enhanced mixing of biphasic liquid-liquid systems for the synthesis of gem-dihalocyclopropanes using packed bed reactors. J. Flow. Chem. 9(1):27–34. https://doi.org/10.1007/s41981-018-0026-1
Kulkarni AA (2014) Continuous flow nitration in miniaturized devices. Beilstein J. Org. Chem. 10:405–424. https://doi.org/10.3762/bjoc.10.38
Li L, Yao C, Jiao F, Han M, Chen G (2017) Experimental and kinetic study of the nitration of 2-ethylhexanol in capillary microreactors. Chem. Eng. Process. 117:179–185. https://doi.org/10.1016/j.cep.2017.04.005
Lu YC, Zhu S, Wang K, Luo GS (2016) Simulation of the mixing process in a straight tube with sudden changed cross-section. Chin. J. Chem. Eng. 24(6):711–718. https://doi.org/10.1016/j.cjche.2016.01.011
Movsisyan M, Delbeke EIP, Berton JKET, Battilocchio C, Ley SV, Stevens CV (2016) Taming hazardous chemistry by continuous flow technology. Chem. Soc. Rev. 45(18):4892–4928. https://doi.org/10.1039/c5cs00902b
Noel T, Kuhn S, Musacchio AJ, Jensen KF, Buchwald SL (2011) Suzuki-Miyaura cross-coupling reactions in flow: multistep synthesis enabled by a microfluidic extraction. Angew. Chem. Int. Ed. 50(26):5943–5946. https://doi.org/10.1002/anie.201101480
Olah GA, Malhotra R, Narang SC (1989) Nitration: methods and mechanisms. Wiley, New York
Plutschack MB, Pieber B, Gilmore K, Seeberger PH (2017) The Hitchhiker’s guide to flow chemistry. Chem. Rev. 117(18):11796–11893. https://doi.org/10.1021/acs.chemrev.7b00183
Quadros PA, Oliveira NMC, Baptista C (2005) Continuous adiabatic industrial benzene nitration with mixed acid at a pilot plant scale. Chem. Eng. J. 108(1–2):1–11. https://doi.org/10.1016/j.cej.2004.12.022
Russo D, Tomaiuolo G, Andreozzi R, Guido S, Lapkin AA, Di Somma I (2019) Heterogeneous benzaldehyde nitration in batch and continuous flow microreactor. Chem. Eng. J. 377:120346. https://doi.org/10.1016/j.cej.2018.11.044
Sang L, Feng X, Tu J, Xie B, Luo G, Zhang J (2020) Investigation of external mass transfer in micropacked bed reactors. Chem. Eng. J. 393:124793. https://doi.org/10.1016/j.cej.2020.124793
Schöfield K (1980) Aromatic Nitration. Cambridge University, Cambridge
Sharma M, Acharya RB, Kulkarni AA (2019) Exploring the steady operation of a continuous pilot plant for the di-nitration reaction. Chem. Eng. Technol. 42(10):2241–2251. https://doi.org/10.1002/ceat.201900140
Su Y, Zhao Y, Chen G, Yuan Q (2010) Liquid-liquid two-phase flow and mass transfer characteristics in packed microchannels. Chem. Eng. Sci. 65(13):3947–3956. https://doi.org/10.1016/j.ces.2010.03.034
Su Y, Zhao Y, Jiao F, Chen G, Yuan Q (2011) The intensification of rapid reactions for multiphase systems in a microchannel reactor by packing microparticles. AICHE J. 57(6):1409–1418. https://doi.org/10.1002/aic.12367
Su Y, Chen G, Yuan Q (2011) Ideal micromixing performance in packed microchannels. Chem. Eng. Sci. 66(13):2912–2919. https://doi.org/10.1016/j.ces.2011.03.024
Tu J, Sang L, Cheng H, Ai N, Zhang J (2020) Continuous hydrogenolysis of n-diphenylmethyl groups in a micropacked-bed reactor. Org. Process. Res. Dev. 24(1):59–66. https://doi.org/10.1021/acs.oprd.9b00416
Wang W, Yu Z (2017) Continuous synthesis of 3,4-dichloronitrobenzene. Zhejiang Chem. Ind. 48(5):28–31
Wang K, Li L, Xie P, Luo G (2017) Liquid-liquid microflow reaction engineering. React. Chem. Eng. 2(5):611–627. https://doi.org/10.1039/c7re00082k
Wen Z, Jiao F, Yang M, Zhao S, Zhou F, Chen G (2017) Process development and scale-up of the continuous flow nitration of trifluoromethoxybenzene. Org. Process. Res. Dev. 21(11):1843–1850. https://doi.org/10.1021/acs.oprd.7b00291
Wen Z, Yang M, Zhao S, Zhou F, Chen G (2018) Kinetics study of heterogeneous continuous-flow nitration of trifluoromethoxybenzene. React. Chem. Eng. 3(3):379–387. https://doi.org/10.1039/c7re00182g
Yao XJ, Zhang Y, Du LY, Liu JH, Yao JF (2015) Review of the applications of microreactors. Renew. Sust. Energ. Rev. 47:519–539. https://doi.org/10.1016/j.rser.2015.03.078
Yu Z, Zhou P, Liu J, Wang W, Yu C, Su W (2016) Continuous-flow process for selective mononitration of 1-methyl-4-(methylsulfonyl)benzene. Org. Process. Res. Dev. 20(2):199–203. https://doi.org/10.1021/acs.oprd.5b00374
Yu Z, Xu Q, Liu L, Wu Z, Huang J, Lin J, Su W (2020) Dinitration of o-toluic acid in continuous-flow: process optimization and kinetic study. J. Flow. Chem. 10(2):429–436. https://doi.org/10.1007/s41981-020-00078-6
Yue J (2018) Multiphase flow processing in microreactors combined with heterogeneous catalysis for efficient and sustainable chemical synthesis. Catal. Today 308:3–19. https://doi.org/10.1016/j.cattod.2017.09.041
Zhang JS, Zhang CY, Liu GT, Luo GS (2016) Measuring enthalpy of fast exothermal reaction with infrared thermography in a microreactor. Chem. Eng. J. 295:384–390. https://doi.org/10.1016/j.cej.2016.01.100
Zhang C, Zhang J, Luo G (2020) Kinetics determination of fast exothermic reactions with infrared thermography in a microreactor. J. Flow. Chem. 10(1):219–226. https://doi.org/10.1007/s41981-019-00071-8
Acknowledgments
This work was supported by the National Natural Science Foundation of China under Grant (21422603, U1662120, 21978152).
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This work was supported by the National Natural Science Foundation of China under Grant (21422603, U1662120, 21978152).
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Article Highlights
• Study apparent reaction kinetic of the nitration of o-dichlorobenzene under various micro-dispersion methods.
• Proposed strategy combination of the adiabatic and micropacked-bed reactor for process intensification and control.
• Enable rapid determination of activation energy by the measurement of adiabatic temperature rise.
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Lan, Z., Lu, Y. Continuous nitration of o-dichlorobenzene in micropacked-bed reactor: process design and modelling. J Flow Chem 11, 171–179 (2021). https://doi.org/10.1007/s41981-020-00132-3
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DOI: https://doi.org/10.1007/s41981-020-00132-3