Quantum Chemistry Calculation on the Mechanism of Benzylamine Denitrogenation in Supercritical Water

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Abstract The denitrogenation mechanism of benzylamine in supercritical water was studied by experiment and quantum chemistry calculation. The quantum chemistry calculation was performed by Gaussian09 software package at M06/6-311G(d,p) and M06-2X/6-311+G(d,p) levels. Results show that the denitrogenation process of benzylamine is conform to concerted reaction mechanism instead of the free radical one. Two-step dehydrogenation, which is first presented, is the main dehydrogenation reaction of benzylamine. The energy barrier of this two-step dehydrogenation reaction is 181.4 kJ·mol^-1, which is 118.7 kJ·mol^-1 lower than that of traditional one step dehydrogenation reaction. Benzaldehyde derived from the dehydrogenation reaction was reacted with benzylamine, and generating benzylidenebenzylamine (BBA). The degradation process was continued through the reaction of BBA with supercritical water. Besides, the supercritical water molecules have a significant catalytic effect on the denitrogenation process of benzylamine, as shown by comparing the energy barrier of the reactions with and without water catalyst.

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	Articles by authors
	Lu Qianwen
	He Fan
	Li Yonghong
	Miao Zhenyu
	Sun Hongwei

Keywords： denitrogenation； benzylamine； supercritical water； quantum chemistry calculation

Received 2020-07-03;

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Lu Qianwen, He Fan, Li Yonghong, Miao Zhenyu, Sun Hongwei.Quantum Chemistry Calculation on the Mechanism of Benzylamine Denitrogenation in Supercritical Water[J] Chemcial Industry and Engineering, 2021,V38(3): 84-94

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