Metal salts with highly electronegative cations as efficient catalysts for the liquid-phase nitration of benzene by NO<sub>2</sub> to nitrobenzene

doi:10.1007/s11705-017-1625-3

Front. Chem. Sci. Eng.

2017, Vol. 11

Issue (2) : 205-210 https://doi.org/10.1007/s11705-017-1625-3

RESEARCH ARTICLE

Metal salts with highly electronegative cations as efficient catalysts for the liquid-phase nitration of benzene by NO₂ to nitrobenzene

Shenghui Zhou¹, Kuiyi You^1,²(

), Zhengming Yi^1,², Pingle Liu^1,², Hean Luo^1,²(

)

¹. School of Chemical Engineering, Xiangtan University, Xiangtan 411105, China
². National & Local United Engineering Research Center for Chemical Process Simulation and Intensification, Xiangtan University, Xiangtan 411105, China

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Abstract

Metal salts with highly electronegative cations have been used to effectively catalyze the liquid-phase nitration of benzene by NO₂ to nitrobenzene under solvent-free conditions. Several salts including FeCl₃, ZrCl₄, AlCl₃, CuCl₂, NiCl₂, ZnCl₂, MnCl₂, Fe(NO₃)₃·9H₂O, Bi(NO₃)₃·5H₂O, Zr(NO₃)₄·5H₂O, Cu(NO₃)₂·6H₂O, Ni(NO₃)₂·6H₂O, Zn(NO₃)₂·6H₂O, Fe₂(SO₄)₃, and CuSO₄ were examined and anhydrous FeCl₃ exhibited the best catalytic performance under the optimal reaction conditions. The benzene conversion and selectivity to nitrobenzene were both over 99%. In addition, it was determined that the metal counterion and the presence of water hydrates in the salt affects the catalytic activity. This method is simple and efficient and may have potential industrial application prospects.

Keywords metal salts electronegativity nitrobenzene NO₂ catalytic nitration

Corresponding Author(s): Kuiyi You,Hean Luo

Just Accepted Date: 28 February 2017 Online First Date: 17 April 2017 Issue Date: 12 May 2017

Cite this article:

Shenghui Zhou,Kuiyi You,Zhengming Yi, et al. Metal salts with highly electronegative cations as efficient catalysts for the liquid-phase nitration of benzene by NO₂ to nitrobenzene[J]. Front. Chem. Sci. Eng., 2017, 11(2): 205-210.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-017-1625-3
https://academic.hep.com.cn/fcse/EN/Y2017/V11/I2/205

Fig.1 Effect of various metal chlorides on the benzene nitration reaction. Reaction conditions: 75 °C, reaction time 4 h, molar ratio of benzene (0.03 mol) to NO₂ 1 : 5, amount of catalyst 0.3 mmol (1 mol-% of benzene)

Fig.2 Effect of various metal nitrates on the benzene nitration reaction. Reaction conditions: 75 °C, reaction time 4 h, molar ratio of benzene (0.03 mol) to NO₂ 1 : 5, amount of catalyst 0.3 mmol (1 mol-% of benzene)

Fig.3 Scheme 1Possible nitration reaction pathway for benzene over metal salt catalysts

Fig.4 Comparison of various iron(III) and copper(II) salts on the benzene nitration reaction. Reaction conditions: 75 °C, reaction time 4 h, molar ratio of benzene (0.03 mol) to NO₂ 1 : 5, amount of catalyst 0.3 mmol (1 mol-% of benzene)

Fig.5 Effect of anhydrous and hydrated metal chloride salts on the benzene nitration reaction. Reaction conditions: 75 °C, reaction time 4 h, molar ratio of benzene (0.03 mol) to NO₂ 1 : 5, amount of catalyst 0.3 mmol (1 mol-% of benzene)

Fig.6 Effects of (A) reaction temperature, (B) molar ratio, (C) reaction time and (D) amount of catalyst on the catalytic nitration of benzene

Fig.7 Recycle and reuse of the FeCl₃ catalyst in the benzene nitration reaction. Reaction conditions: 100 °C, reaction time 4 h, molar ratio of benzene (0.03 mol) to NO₂ 1 : 5, amount of catalyst 0.06 g

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