Research progress of aromatic nitration reaction in microreactors

doi:10.11949/0438-1157.20240558

Abstract

Abstract:

As one of the most important basic reaction types in industrial production, the nitration of aromatic hydrocarbons is bound to develop towards microscale with the requirements of safe, green and efficient production of chemicals. The key concern of major research projects is how to achieve high-quality development of microscale aromatic nitration. This article comprehensively reviews and analyzes the advancements and challenges of aromatic nitration in microreactors. Starting from the study of microscale nitration reaction kinetics, the direction for the design and intensification of aromatic hydrocarbon nitration microreaction process is pointed out. It summarizes current methods for kinetic study, process intensification and safety evaluation in the nitration microreaction technology. Future development directions of the aromatic nitration in microreactors will also be prospected.

Key words: nitration, kinetics, transport process, microscale, microreactor

摘要：

芳烃的硝化反应作为工业生产中最重要的基本反应类型之一，随着化学品安全、绿色、高效生产的要求，其反应工艺向微尺度方向的发展已是必然的趋势。如何实现微尺度芳烃硝化反应的高质量发展，是重大工程前沿方向之一。本文全面综述并剖析了硝化微反应工艺的发展和面临的问题，从微尺度硝化反应动力学研究入手，为芳烃硝化微反应工艺设计及强化指明方向，并总结了当前硝化微反应工艺中的过程强化及安全性评价方法，最后对其未来发展方向进行了展望。

关键词: 硝化反应, 动力学, 传递过程, 微尺度, 微反应器

CLC Number:

TQ 052

Jing SONG, Yujun WANG, Jian DENG, Guangwen CHEN, Guangsheng LUO. Research progress of aromatic nitration reaction in microreactors[J]. CIESC Journal, 2024, 75(11): 3911-3922.

宋璟, 王玉军, 邓建, 陈光文, 骆广生. 微反应器内芳烃硝化反应研究进展[J]. 化工学报, 2024, 75(11): 3911-3922.

Figures/Tables 5

Fig.1 Reaction mechanism of aromatic nitration

Fig.2 Schematic diagram of experimental apparatus for the kinetic study of aromatics nitration at microscale[32, 34-35, 40, 46]

Fig.3 A paradigm for the kinetic study of aromatic nitration at microscale

Table 1 Summary of literatures on the kinetic study of microscale aromatic nitration

文献	硝化底物	相态	E_a/(kJ/mol)	lnA
[48]	乙酰愈创木酚	均相	139	—
[33]	2-乙基己醇	均相	42.67	—
[31]	三氟甲氧基苯	非均相	29.3（邻位）	8.75（邻位）
[31]	三氟甲氧基苯	非均相	26.9（对位）	9.64（对位）
[34-35]	对硝基甲苯	均相	50.21	58.39
[34-35]	邻硝基甲苯	均相	72.36	66.73
[46]	邻二氯苯	非均相	30.96	—
[40]	氯苯	均相	25.98	—
[32]	甲苯	非均相	28.00	100.15
[30]	硝基苯	非均相	71.23	7.81
[49]	三氟甲基苯	非均相	86.33	—

Fig.4 Several novel microreactors with excellent microdispersion and mass transfer performance[44, 54, 56-57, 63, 65]

References 72

1	Badgujar D M, Talawar M B, Mahulikar P P. Review on greener and safer synthesis of nitro compounds[J]. Propellants, Explosives, Pyrotechnics, 2016, 41(1): 24-34.
2	Patel S S, Patel D B, Patel H D. Synthetic protocols for aromatic nitration: a review[J]. ChemistrySelect, 2021, 6(6): 1337-1356.
3	Gillespie R J, Hughes E D, Ingold C K, et al. Kinetics and mechanism of aromatic nitration[J]. Nature, 1949, 163(4146): 599-600.
4	Barduhn A J, Kobe K A. Toluene nitration kinetics[J]. Industrial & Engineering Chemistry, 1956, 48(8): 1305-1315.
5	Coombes R G, Moodie R B, Schofield K. Electrophilic aromatic substitution (part Ⅰ): The nitration of some reactive aromatic compounds in concentrated sulphuric and perchloric acids[J]. Journal of the Chemical Society B: Physical Organic, 1968: 800-804.
6	Barnett J W, Moodie R B, Schofield K, et al. Electrophilic aromatic substitution (part 􀃼): Kinetics, isomer yields, and the consequences of ipso-attack in the nitration of toluene and polymethylbenzenes in aqueous sulphuric acid, and their significance for the mechanism of aromatic nitration[J]. Journal of the Chemical Society, Perkin Transactions 2, 1975(6): 648-654.
7	Sreedhar I, Singh M, Raghavan K V. Scientific advances in sulfuric acid free toluene nitration[J]. Catalysis Science & Technology, 2013, 3(10): 2499-2508.
8	Marziano N C, Traverso P G, Cimino G G. Thermodynamic nitration rates of aromatic compounds (part Ⅰ): The nitration of benzene and some benzene derivatives in aqueous sulphuric and perchloric acids. A comparison of the results referred to water as standard state[J]. Journal of the Chemical Society, Perkin Transactions 2, 1980(4): 574-578.
9	Marziano N C, Sampoli M, Pinna F, et al. Thermodynamic nitration rates of aromatic compounds (part Ⅱ): Linear description of rate profiles for the nitration of aromatic compounds in the range 40—98 wt% sulphuric acid[J]. Journal of the Chemical Society, Perkin Transactions 2, 1984(7): 1163-1166.
10	Marziano N C, Tortato C, Sampoli M. Thermodynamic nitration rates of aromatic compounds (part Ⅲ): Nitration of aromatic compounds in concentrated aqueous trifluoromethanesulphonic acid[J]. Journal of the Chemical Society, Perkin Transactions 2, 1991(3): 423-429.
11	Marziano N C, Tomasin A, Tortato C, et al. Thermodynamic nitration rates of aromatic compounds (part Ⅳ): Temperature dependence in sulfuric acid of HNO₃→NO₂ ⁺ equilibrium, nitration rates and acidic properties of the solvent [J]. Journal of the Chemical Society, Perkin Transactions 2, 1998(9): 1973-1982.
12	Wang K, Li L T, Xie P, et al. Liquid-liquid microflow reaction engineering[J]. Reaction Chemistry & Engineering, 2017, 2(5): 611-627.
13	Wang K, Luo G S. Microflow extraction: a review of recent development[J]. Chemical Engineering Science, 2017, 169: 18-33.
14	Luo G S, Du L, Wang Y J, et al. Recent developments in microfluidic device-based preparation, functionalization, and manipulation of nano- and micro-materials[J]. Particuology, 2019, 45: 1-19.
15	Kulkarni A A. Continuous flow nitration in miniaturized devices[J]. Beilstein Journal of Organic Chemistry, 2014, 10: 405-424.
16	Burns J R, Ramshaw C. A microreactor for the nitration of benzene and toluene[J]. Chemical Engineering Communications, 2002, 189(12): 1611-1628.
17	Chen Y Z, Zhao Y C, Han M, et al. Safe, efficient and selective synthesis of dinitro herbicides via a multifunctional continuous-flow microreactor: one-step dinitration with nitric acid as agent[J]. Green Chemistry, 2013, 15(1): 91-94.
18	Panke G, Schwalbe T, Stirner W, et al. A practical approach of continuous processing to high energetic nitration reactions in microreactors[J]. Synthesis, 2003(18): 2827-2830.
19	Ducry L, Roberge D M. Controlled autocatalytic nitration of phenol in a microreactor[J]. Angewandte Chemie International Edition, 2005, 44(48): 7972-7975.
20	Dummann G, Quittmann U, Gröschel L, et al. The capillary-microreactor: a new reactor concept for the intensification of heat and mass transfer in liquid-liquid reactions[J]. Catalysis Today, 2003, 79/80: 433-439.
21	Fu G, Ni L, Wei D, et al. Scale-up and safety of toluene nitration in a meso-scale flow reactor[J]. Process Safety and Environmental Protection, 2022, 160: 385-396.
22	Yang A M, Yue J C, Zheng S Q, et al. Experimental investigation of mononitrotoluene preparation in a continuous-flow microreactor[J]. Research on Chemical Intermediates, 2022, 48(10): 4373-4390.
23	Han B C, Chen Y D, Zou H W, et al. Study on characteristics of toluene/chlorobenzene nitrification in different microreactors[J]. Chemical Engineering Research and Design, 2024, 205: 343-353.
24	Fischer A, Fyles D L, Henderson G N, et al. Ipso nitration (Ⅹ Ⅹ Ⅷ): Nitration of 4-substituted toluenes: 1, 2 adducts[J]. Canadian Journal of Chemistry, 1986, 64(9): 1764-1770.
25	Hirose A, Matsui K, Sekiguchi S. Aromatic nitration (Ⅲ): Competitive nitration of toluene and benzene in carbon tetrachloride[J]. Bulletin of the Chemical Society of Japan, 1972, 45(9): 2955-2956.
26	Yan Z F, Tian J X, Du C C, et al. Reaction kinetics determination based on microfluidic technology[J]. Chinese Journal of Chemical Engineering, 2022, 41: 49-72.
27	Rahaman M, Mandal B P, Ghosh P. Nitration of nitrobenzene at high-concentrations of sulfuric acid[J]. AIChE Journal, 2007, 53(9): 2476-2480.
28	Rahaman M, Mandal B, Ghosh P. Nitration of nitrobenzene at high-concentrations of sulfuric acid: mass transfer and kinetic aspects[J]. AIChE Journal, 2010, 56(3): 737-748.
29	Ravikumar Bandaru S V, Ghosh P. Mass transfer of chlorobenzene in concentrated sulfuric acid[J]. International Journal of Heat and Mass Transfer, 2011, 54(11/12): 2245-2252.
30	Jin N, Song Y B, Yue J, et al. Heterogeneous nitration of nitrobenzene in microreactors: process optimization and modelling[J]. Chemical Engineering Science, 2023, 281: 119198.
31	Wen Z H, Yang M, Zhao S N, et al. Kinetics study of heterogeneous continuous-flow nitration of trifluoromethoxybenzene[J]. Reaction Chemistry & Engineering, 2018, 3(3): 379-387.
32	Song J, Cui Y J, Wang Y J, et al. Accurate determination of the kinetics of toluene nitration in a liquid-liquid microflow system[J]. Journal of Flow Chemistry, 2023, 13(3): 311-323.
33	Li L, Yao C Q, Jiao F J, et al. Experimental and kinetic study of the nitration of 2-ethylhexanol in capillary microreactors[J]. Chemical Engineering and Processing: Process Intensification, 2017, 117: 179-185.
34	Song J, Cui Y J, Luo G S, et al. Kinetic study of o-nitrotoluene nitration in a homogeneously continuous microflow[J]. Reaction Chemistry & Engineering, 2022, 7(1): 111-122.
35	Song J, Cui Y J, Sheng L, et al. Determination of nitration kinetics of p-nitrotoluene with a homogeneously continuous microflow[J]. Chemical Engineering Science, 2022, 247: 117041.
36	Marziano N C, Cimino G M, Passerini R C. The M_C activity coefficient function for acid-base equilibria (part Ⅰ): New methods for estimating pK_a values for weak bases[J]. J. Chem. Soc., Perkin Trans. 2, 1973(14): 1915-1922.
37	Marziano N C, Traverso P G, Passerini R C. The M_C activity coefficient function for acid-base equilibria (part Ⅱ): A critical analysis of acidity functions and the incompatibility amongst proposed empirical correlations[J]. J. Chem. Soc., Perkin Trans. 2, 1977(3): 306-309.
38	Marziano N C, Traverso P G, Tomasin A, et al. The M_C activity coefficient function for acid-base equilibria (part Ⅲ): Improvement on the M_C function by mathematical treatment[J]. J. Chem. Soc., Perkin Trans 2, 1977(3): 309-313.
39	Traverso P G, Marziano N C, Passerini R C. The M_C activity coefficient function for acid-base equilibria (part Ⅳ): Limitations of empirical relationships involving observed nitration rates and acidity functions[J]. J. Chem. Soc., Perkin Trans 2, 1977(6): 845-847.
40	Cui Y J, Song J, Du C C, et al. Determination of the kinetics of chlorobenzene nitration using a homogeneously continuous microflow[J]. AIChE Journal, 2022, 68(4): e17564.
41	Zhang J S, Wang K, Lu Y C, et al. Characterization and modeling of micromixing performance in micropore dispersion reactors[J]. Chemical Engineering and Processing: Process Intensification, 2010, 49(7): 740-747.
42	Chen Q C, Wang Y B, Du C C, et al. Micromixing performance of a miniaturized annular rotating flow mixer (MARFM)[J]. Chemical Engineering and Processing-Process Intensification, 2022, 182: 109181.
43	Chen Q C, Wang Y B, Deng J, et al. Micromixing intensification by gas introduction in a miniaturized annular rotating flow mixer (MARFM)[J]. Chemical Engineering Science, 2023, 272: 118610.
44	Song J, Cheng B, Wang Y J, et al. A microfluidic chip structure with ultra-high liquid-liquid mass transfer performance[J]. Separation and Purification Technology, 2023, 324: 124440.
45	Russo D, Tomaiuolo G, Andreozzi R, et al. Heterogeneous benzaldehyde nitration in batch and continuous flow microreactor[J]. Chemical Engineering Journal, 2019, 377: 120346.
46	Lan Z, Lu Y C. Continuous nitration of o-dichlorobenzene in micropacked-bed reactor: process design and modelling[J]. Journal of Flow Chemistry, 2021, 11(2): 171-179.
47	Du C C, Wang P C, Hu Y P, et al. Liquid-liquid mass transfer enhancement in milliscale packed beds[J]. Industrial & Engineering Chemistry Research, 2020, 59(9): 4048-4057.
48	Zhang C Y, Zhang J S, Luo G S. Kinetic study and intensification of acetyl guaiacol nitration with nitric acid-acetic acid system in a microreactor[J]. Journal of Flow Chemistry, 2016, 6(4): 309-314.
49	Guo S, Cao J Y, Liu M Q, et al. Intensification and kinetic study of trifluoromethylbenzen nitration with mixed acid in the microreactor[J]. Chemical Engineering and Processing-Process Intensification, 2023, 183: 109239.
50	Yu Z Q, Lv Y W, Yu C M, et al. A high-output, continuous selective and heterogeneous nitration of p-difluorobenzene[J]. Organic Process Research & Development, 2013, 17(3): 438-442.
51	Kulkarni A A, Kalyani V S, Joshi R A, et al. Continuous flow nitration of benzaldehyde[J]. Organic Process Research & Development, 2009, 13(5): 999-1002.
52	Knapkiewicz P, Skowerski K, Jaskólska D E, et al. Nitration under continuous flow conditions: convenient synthesis of 2-isopropoxy-5-nitrobenzaldehyde, an important building block in the preparation of nitro-substituted Hoveyda-Grubbs metathesis catalyst[J]. Organic Process Research & Development, 2012, 16(8): 1430-1435.
53	Mittal A K, Prakash G, Pathak P, et al. Continuous flow synthesis of tert-butyl nitrite and its applications as nitrating agent[J]. Organic Process Research & Development, 2024, 28(5): 1510-1514.
54	Wang K, Lu Y C, Luo G S. Strategy for scaling-up of a microsieve dispersion reactor[J]. Chemical Engineering & Technology, 2014, 37(12): 2116-2122.
55	Shao H W, Lu Y C, Wang K, et al. Liquid-liquid flow and mass transfer characteristics in micro-sieve array device with dual-sized pores[J]. Chemical Engineering Journal, 2012, 193/194: 96-101.
56	Song J, Sheng L, Cui Y J, et al. Liquid-liquid colliding micro-dispersion and general scaling laws in novel T-junction microdevices[J]. Chemical Engineering Science, 2022, 258: 117746.
57	Sheng L, Ma L, Chen Y C, et al. A comprehensive study of droplet formation in a capillary embedded step T-junction: from squeezing to jetting[J]. Chemical Engineering Journal, 2022, 427: 132067.
58	Plouffe P, Roberge D M, Sieber J, et al. Liquid-liquid mass transfer in a serpentine micro-reactor using various solvents[J]. Chemical Engineering Journal, 2016, 285: 605-615.
59	Kurt S K, Vural Gürsel I, Hessel V, et al. Liquid-liquid extraction system with microstructured coiled flow inverter and other capillary setups for single-stage extraction applications[J]. Chemical Engineering Journal, 2016, 284: 764-777.
60	Plouffe P, Roberge D M, Macchi A. Liquid-liquid flow regimes and mass transfer in various micro-reactors[J]. Chemical Engineering Journal, 2016, 300: 9-19.
61	Zhang J S, Wang K, Lin X Y, et al. Intensification of fast exothermic reaction by gas agitation in a microchemical system[J]. AIChE Journal, 2014, 60(7): 2724-2730.
62	Lin X Y, Wang K, Zhang J S, et al. Liquid-liquid mixing enhancement rules by microbubbles in three typical micro-mixers[J]. Chemical Engineering Science, 2015, 127: 60-71.
63	Chen Q C, Deng J, Luo G S. Micromixing performance and residence time distribution in a miniaturized magnetic reactor: experimental investigation and machine learning modeling[J]. Industrial & Engineering Chemistry Research, 2023, 62(8): 3577-3591.
64	Wang Y B, Tang T Y, Yan Z F, et al. Liquid-liquid dispersion and flow characteristics in a miniaturized annular rotating device[J]. Chemical Engineering Journal, 2023, 454: 140374.
65	Wang Y B, Du C C, Yan Z F, et al. Liquid-liquid flow and mass transfer characteristics in a miniaturized annular centrifugal device[J]. Chemical Engineering Journal, 2022, 431: 134264.
66	李光晓, 刘塞尔, 苏远海. 微尺度内液-液传质及反应过程强化的研究进展[J]. 化工学报, 2021, 72(1): 452-467.
	Li G X, Liu S E, Su Y H. Research progress on micro-scale internal liquid-liquid mass transfer and reaction process enhancement[J]. CIESC Journal, 2021, 72(1): 452-467.
67	Knauf T, Racoes A, Dohmen W, et al. Method for producing nitrobenzene by adiabatic nitriding: US20150175521[P]. 2015-06-25.
68	邓建, 骆广生. 一种连续绝热高温硝化甲苯制备单硝基甲苯的方法: 111004124A[P]. 2020-04-14.
	Deng J, Luo G S. A method for preparing mononitrotoluene by continuous adiabatic high-temperature nitration of toluene: 111004124A[P]. 2020-04-14.
69	邓建, 王凯, 骆广生. 面向硝基化学品安全生产的绝热连续微反应技术发展及思考[J]. 化工进展, 2023, 42(8): 3923-3925.
	Deng J, Wang K, Luo G S. Development and consideration of adiabatic continuous microreaction technology for safe production of nitro compounds[J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3923-3925.
70	Liu Y C, Jiang J C, Huang A C, et al. Hazard assessment of the thermal stability of nitrification by-products by using an advanced kinetic model[J]. Process Safety and Environmental Protection, 2022, 160: 91-101.
71	Qian Y N, Chen M M, Zhan J H, et al. Thermal runaway mechanisms and kinetics of benzene nitrification system based on microcalorimetry experiments and ReaxFF molecular dynamics simulation[J]. Thermochimica Acta, 2023, 725: 179522.
72	Yao H, Ni L, Liu Y S, et al. Process hazard and thermal risk evaluation of m-xylene nitration with mixed acid[J]. Process Safety and Environmental Protection, 2023, 175: 238-250.

[1]	Yingyu XU, Guoqiang YANG, Jing PENG, Haining SUN, Zhibing ZHANG. Research on advanced oxidation treatment of coal chemical wastewater using microinterfaces [J]. CIESC Journal, 2024, 75(S1): 283-291.
[2]	Huanjuan ZHAO, Yingxin BAO, Kang YU, Jing LIU, Xinming QIAN. Quantitative experimental study on detonation instability of multi-component [J]. CIESC Journal, 2024, 75(S1): 339-348.
[3]	Zichi YANG, Bingqi XIE, Ruixin SHI, Hong LEI, Chen CHEN, Caijin ZHOU, Jisong ZHANG. Research progress on efficient and safe gas-liquid mass transfer and reaction processes in tube-in-tube reactor [J]. CIESC Journal, 2024, 75(9): 3011-3027.
[4]	Hongbiao XU, Liang YANG, Zidong LI, Daoping LIU. Kinetics of methane hydrate formation in saline droplets/copper foam composite system [J]. CIESC Journal, 2024, 75(9): 3287-3296.
[5]	Yong DING, Wenjian LI, Zhaoyu CHEN, Lihui CAO, Xuanming LIU, Qiangqiang REN, Song HU, Jun XIANG. Aerobic pyrolysis kinetic and product characteristics of waste crystalline silicon photovo ltaic modules’ EVA [J]. CIESC Journal, 2024, 75(9): 3310-3319.
[6]	Zhenghang LUO, Jingyu LI, Weixiong CHEN, Daotong CHONG, Junjie YAN. Numerical simulation of heat transfer characteristic and bubble force analysis of low flow rate vapor condensation under rolling motion [J]. CIESC Journal, 2024, 75(8): 2800-2811.
[7]	Gang ZENG, Lin CHEN, Dong YANG, Haizhuan YUAN, Yanping HUANG. Visualization of local boundary thermal flow field of supercritical CO₂ inside a rectangular channel [J]. CIESC Journal, 2024, 75(8): 2831-2839.
[8]	Li LUO, Wenyao CHEN, Jing ZHANG, Gang QIAN, Xinggui ZHOU, Xuezhi DUAN. Alumina structure and surface property regulation for catalyzing methanol dehydration to dimethyl ether [J]. CIESC Journal, 2024, 75(7): 2522-2532.
[9]	Kehao DONG, Jingzhi ZHOU, Feng ZHOU, Haijia CHEN, Xiulan HUAI, Dong LI. Experiment of gas flow pressure drop under complex boundary conditions in ultra-thin space [J]. CIESC Journal, 2024, 75(7): 2505-2521.
[10]	Wenya WANG, Wei ZHANG, Xiaoling LOU, Ruofei ZHONG, Bingbing CHEN, Junxian YUN. Multi-microtubes formation and simulation of nanocellulose-embedded cryogel microspheres [J]. CIESC Journal, 2024, 75(5): 2060-2071.
[11]	Xiao XUE, Minjing SHANG, Yuanhai SU. Advances on continuous-flow synthesis of drugs in microreactors [J]. CIESC Journal, 2024, 75(4): 1439-1454.
[12]	Yuhang HE, Dan XIE, Yangcheng LYU. Research progress of cationic polymerization in microreactor [J]. CIESC Journal, 2024, 75(4): 1302-1316.
[13]	Yiwei FAN, Wei LIU, Yingying LI, Peixia WANG, Jisong ZHANG. Research progress on catalytic dehydrogenation of dodecahydro-N-ethylcarbazole as liquid organic hydrogen carrier [J]. CIESC Journal, 2024, 75(4): 1198-1208.
[14]	Anran XU, Kai LIU, Na WANG, Zhenyu ZHAO, Hong LI, Xin GAO. Strong wave-absorbing catalyst cooperates with microwave energy to enhance fructose dehydration to produce 5-hydroxymethylfurfural [J]. CIESC Journal, 2024, 75(4): 1565-1577.
[15]	Jiaqi WANG, Haoqi WEI, Ajing GOU, Jiaxing LIU, Xinlin ZHOU, Kun GE. Study on the formation mechanism of CO₂ hydrate under the action of nanoparticles [J]. CIESC Journal, 2024, 75(3): 956-966.