Liquid Phase Hydrogenation of Maleic Anhydride over Ni/TiO2 Catalysts with Different TiO2 Polymorphs†

doi:10.7503/cjcu20150138

Abstract

Abstract:

Ni/TiO₂ catalysts with anatase and rutile titania as supports were prepared via the incipient impregnation method and were applied in the liquid phase hydrogenation of maleic anhydride. All catalysts were characterized by N₂ physical adsorption-desorption, H₂-temperature programmed reduction(H₂-TPR), X-ray diffraction(XRD), H₂-temperature programmed desorption(H₂-TPD) and X-ray photoelectron spectroscopy(XPS). The evaluation results show that the activity of C=O hydrogenation of catalyst with anatase TiO₂ as support was significantly higher than that with rutile TiO₂ as support. The higher activity of C=O hydrogenation was attributed to a higher concentration of the oxygen vacancies produced during the reduction process. Oxygen vacancies could promote the hydrogenation of C=O group by accepting lone pair of electrons of oxygen in C=O group.

Key words: Anatase TiO2, Ni-based catalyst, Liquid phase hydrogenation of maleic anhydride, Succinic anhydride, γ-Butyrolactone

CLC Number:

O643.36

TrendMD:

MENG Zhiyu, ZHANG Yin, ZHAO Lili, ZHANG Hongxi, ZHAO Yongxiang. Liquid Phase Hydrogenation of Maleic Anhydride over Ni/TiO₂Catalysts with Different TiO₂ Polymorphs^†[J]. Chem. J. Chinese Universities, 2015, 36(9): 1779.

Figures/Tables 13

Scheme 1 Process of hydrogenation of maleic anhydride

Table 1 Textural properties of catalysts

Catalyst	S_BET/(m²·g^-1)	Pore volume/(cm³·g^-1)	Average pore diameter/nm	Average Ni crystalline size/nm
A-TiO₂	30	0.26	34.0
R-TiO₂	30	0.23	30.3
12.5%Ni/A-TiO₂	22	0.20	35.0	13.5
12.5%Ni/R-TiO₂	25	0.27	41.5	15.1

Fig.1 H2-TPR profiles of prepared Ni/TiO2 catalysts and mechanical mixture a. 12.5%Ni/A-TiO2; b. 12.5%Ni/R-TiO2; c. 12.5%Ni-A-TiO2; d. 12.5%Ni-R-TiO2.

Table 2 H2 consumption of the catalysts

Catalyst	Actual consumption of H₂/ (μmol·g^-1)	Theoretical consumption of H₂/ (μmol·g^-1)
12.5%Ni/A-TiO₂	4446	2485
12.5%Ni/R-TiO₂	4075	2485
12.5%Ni-A-Ti	2927	2485
12.5%Ni-R-Ti	2871	2485

Fig.2 XRD patterns of 12.5%Ni/A-TiO2(a) and 12.5%Ni/R-TiO2(b)

Fig.3 XPS spectra for Ti2p of 12.5%Ni/A-TiO2(a) and 12.5%Ni/R-TiO2(b)

Table 3 Fitting results of XPS data of 12.5%Ni/TiO2 catalysts

Catalyst	E_g/eV		n_Ti(Ⅲ)/[n_Ti(Ⅳ)+ n_Ti(Ⅲ)](%)
Catalyst	Ti(Ⅲ $) 2 p 32$		Ti(Ⅳ) $2 p 32$
12.5%Ni/A-TiO₂	456.9	458.1	30.2
12.5%Ni/R-TiO₂	457.0	458.2	14.6

Table 3 Fitting results of XPS data of 12.5%Ni/TiO2 catalysts

Catalyst	E_g/eV		n_Ti(Ⅲ)/[n_Ti(Ⅳ)+ n_Ti(Ⅲ)](%)
Catalyst	Ti(Ⅲ $) 2 p 32$		Ti(Ⅳ) $2 p 32$
12.5%Ni/A-TiO₂	456.9	458.1	30.2
12.5%Ni/R-TiO₂	457.0	458.2	14.6

Fig.4 H2-TPD profiles of 12.5%Ni/A-TiO2(a) and 12.5%Ni/R-TiO2(b)

Fig.5 In situ DRIFTS spectra of cyclohexanone adsorbed on 12.5%Ni/A-TiO2(a) and 12.5%Ni/R-TiO2(b)

Table 4 Effect of hydrogen pressure on catalytic performance of catalysts for maleic anhydride hydrogenationa

Catalyst	Hydrogen pressure/MPa	Conversion of MA(%)	Selectivity(%)		TO $F b CO$ /s^-1
Catalyst	Hydrogen pressure/MPa	Conversion of MA(%)	GBL		SA
12.5%Ni/A-TiO₂	3	99.9	45.2	54.8	0.98
	4	100	51.5	48.5	1.12
	5	100	60.0	40.0	1.30
12.5%Ni/R-TiO₂	3	100	17.9	82.1	0.35
	4	100	24.5	75.5	0.48
	5	100	32.9	67.1	0.64

Table 4 Effect of hydrogen pressure on catalytic performance of catalysts for maleic anhydride hydrogenationa

Catalyst	Hydrogen pressure/MPa	Conversion of MA(%)	Selectivity(%)		TO $F b CO$ /s^-1
Catalyst	Hydrogen pressure/MPa	Conversion of MA(%)	GBL		SA
12.5%Ni/A-TiO₂	3	99.9	45.2	54.8	0.98
	4	100	51.5	48.5	1.12
	5	100	60.0	40.0	1.30
12.5%Ni/R-TiO₂	3	100	17.9	82.1	0.35
	4	100	24.5	75.5	0.48
	5	100	32.9	67.1	0.64

Table 5 Effect of reaction temperature on catalytic performance of catalysts for maleic anhydride hydrogenationa

Catalyst	T/K	Conversion of MA(%)	Selectivity(%)		TO $F b CO$ /s^-1
Catalyst	T/K	Conversion of MA(%)	GBL		SA
12.5%Ni/A-TiO₂	453	99.3	31.9	68.1	0.69
	483	100	60.0	40.0	1.30
	513	100	62.8	37.2	1.36
12.5%Ni/R-TiO₂	453	100	9.3	90.7	0.18
	483	100	32.9	67.1	0.64
	513	100	33.1	66.9	0.64

Table 5 Effect of reaction temperature on catalytic performance of catalysts for maleic anhydride hydrogenationa

Catalyst	T/K	Conversion of MA(%)	Selectivity(%)		TO $F b CO$ /s^-1
Catalyst	T/K	Conversion of MA(%)	GBL		SA
12.5%Ni/A-TiO₂	453	99.3	31.9	68.1	0.69
	483	100	60.0	40.0	1.30
	513	100	62.8	37.2	1.36
12.5%Ni/R-TiO₂	453	100	9.3	90.7	0.18
	483	100	32.9	67.1	0.64
	513	100	33.1	66.9	0.64

Scheme 2 Proposed sorption structure of maleic anhydride on Ni/TiO2

Fig.6 Effect of run times on catalytic performance of catalysts for MA conversion(a, b) and GBL selectivity(c, d)a, c. 12.5%Ni/A-TiO2; b, d. 12.5%Ni/R-TiO2.

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Liquid Phase Hydrogenation of Maleic Anhydride over Ni/TiO₂Catalysts with Different TiO₂ Polymorphs^†

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