Activation Process on Ni-Fe Catalyst and the Hydrogenation of Dinitrotoluene†

doi:10.7503/cjcu20140091

Abstract

Abstract:

Ni-Fe catalysts were prepared via Fe substitution in a NiCl₂ solution and used in the liquid phase hydrogenation of dinitrotoluene(DNT) to toluenediamine(TDA). The influences of activation time of treatment by acid solution on the catalytic performance and the microstructure of Ni-Fe catalysts were investigated. The results showed that during acid activation treatment, Fe₂(OH)₃Cl formed in the substitution process and part of iron component are removed on the solid catalyst. With increasing of activation time, the content of Fe element decrease gradually and the content of Ni element increased gradually on the catalysts. With the activation time increased from 0 to 2 h, the dispersion of Ni active species and the H₂ chemical absorption increase, and the catalytic activity is enhanced gradually. The 2 h-activated Ni-Fe catalyst exhibited the highest performance with the DNT conversion of 99.9% and the TDA selectivity of 99.8%. Further increasing activation time from 2 h to 4 h, the catalytic activity began to decrease. In addition, it is found that TDA is formed step by step from four kinds of intermediates which are found during the progress of dinitrotoluene hydrogenations.

Key words: Dnitrotoluene, Toluenediamine, Ni-Fe, Catalyst, Liquid phase hydrogenation

CLC Number:

O643.38

TrendMD:

YU Zhihui, YAN Ze, FAN Hui, LI Zhong. Activation Process on Ni-Fe Catalyst and the Hydrogenation of Dinitrotoluene^†[J]. Chem. J. Chinese Universities, 2014, 35(10): 2227.

Figures/Tables 9

References 25

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Catalyst	2θ/(°)	FWHM/(°)	Particle size/nm
Ni-Fe-0.5	44.23	0.668	12.70
Ni-Fe-1	44.19	0.639	13.31
Ni-Fe-2	44.30	0.817	11.38
Ni-Fe-3	44.23	0.603	14.06
Ni-Fe-4	44.06	0.564	15.04

Catalyst	2θ/(°)	FWHM/(°)	Particle size/nm
Ni-Fe-0.5	44.23	0.668	12.70
Ni-Fe-1	44.19	0.639	13.31
Ni-Fe-2	44.30	0.817	11.38
Ni-Fe-3	44.23	0.603	14.06
Ni-Fe-4	44.06	0.564	15.04

Catalyst	Content of Fe(%, mass fraction)	Content of Ni(%, mass fraction)	Total content(%, mass fraction)	Molar ratio of Ni/Fe
Ni-Fe-0.5	10.02	47.11	57.13	4.47
Ni-Fe-1	5.62	50.62	56.24	8.57
Ni-Fe-2	5.86	56.85	62.71	9.23
Ni-Fe-3	5.96	65.48	71.44	10.45
Ni-Fe-4	6.08	69.72	75.80	10.91

Catalyst	Content of Fe(%, mass fraction)	Content of Ni(%, mass fraction)	Total content(%, mass fraction)	Molar ratio of Ni/Fe
Ni-Fe-0.5	10.02	47.11	57.13	4.47
Ni-Fe-1	5.62	50.62	56.24	8.57
Ni-Fe-2	5.86	56.85	62.71	9.23
Ni-Fe-3	5.96	65.48	71.44	10.45
Ni-Fe-4	6.08	69.72	75.80	10.91

Catalyst	Chemical-absorption/ (mmol·g^-1)	Dispersion degree of Ni(%)	Chemical-desorption temperature/℃		Relative content(%)
Catalyst	Chemical-absorption/ (mmol·g^-1)	Dispersion degree of Ni(%)	Peak 2	Peak 3	Peak 2	Peak 3
Ni-Fe-0.5	0.0530	15.2	250.21	308.81	52.7	47.3
Ni-Fe-1	0.0938	27.2	258.71	316.32	48.8	51.2
Ni-Fe-2	0.2277	66.0	281.78	328.00	66.9	33.1
Ni-Fe-3	0.1080	31.4	270.75	310.57	50.7	49.3
Ni-Fe-4	0.1051	30.4	275.70	326.96	56.9	43.1