不同晶型TiO2负载镍催化剂催化顺酐液相加氢

doi:10.7503/cjcu20150138

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (9): 1779.doi: 10.7503/cjcu20150138

不同晶型TiO₂负载镍催化剂催化顺酐液相加氢

孟志宇, 张因(), 赵丽丽, 张鸿喜, 赵永祥()

山西大学化学化工学院, 精细化学品教育部工程研究中心, 太原 030006

收稿日期:2015-02-09 出版日期:2015-09-10 发布日期:2015-07-06
作者简介:联系人简介: 赵永祥, 男, 博士, 教授, 主要从事多相催化方面的研究. E-mail:yxzhao@sxu.edu.cn; 张因, 女, 博士, 讲师, 主要从事多相催化方面的研究. E-mail:sxuzhy@sxu.edu.cn
基金资助:
国际科技合作专项项目(批准号: 2013DFA40460)、国家自然科学基金青年基金(批准号21303097)、山西省十二五科技重大专项项目(批准号: 201111010101)和山西省自然科学基金(批准号2013011010-4)资助

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

MENG Zhiyu, ZHANG Yin^*(), ZHAO Lili, ZHANG Hongxi, ZHAO Yongxiang^*()

Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China

Received:2015-02-09 Online:2015-09-10 Published:2015-07-06
Contact: ZHANG Yin,ZHAO Yongxiang E-mail:sxuzhy@sxu.edu.cn;yxzhao@sxu.edu.cn
Supported by:
† Supported by the International S&T Cooperation Program of China(No.2013DFA40460), the National Natural Science Foundation for Young Scientists of China(No.21303097), the Special Foundation for Major Science and Technology in Shanxi Province “12nd-5-Year Plan”, China(No.201111010101) and the Natural Science Foundation of Shanxi Province, China(No.2013011010-4)

摘要/Abstract

摘要：

分别以锐钛矿相TiO₂和金红石相TiO₂为载体, 采用等体积浸渍法制备了Ni/TiO₂催化剂, 考察了其催化顺酐液相加氢性能. 采用氮气吸附-脱附、氢气程序升温还原(H₂-TPR)、 X射线衍射(XRD)、氢气程序升温脱附(H₂-TPD)及X射线光电子能谱(XPS)等技术对催化剂进行了表征. 催化剂评价结果表明, 以锐钛矿型TiO₂为载体催化剂的C=O加氢活性明显高于以金红石型TiO₂为载体的催化剂. 这主要是由于在还原过程中锐钛矿型TiO₂较易被还原, 产生了较高浓度的氧缺陷位, 该氧缺陷位可通过接受C=O中O的孤对电子来活化C=O, 促使其与H₂发生加氢反应, 进而使催化剂表现出较高的C=O加氢活性.

关键词: 锐钛矿型TiO2, Ni基催化剂, 顺酐液相加氢, 丁二酸酐, γ-丁内酯

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

中图分类号:

O643.36

TrendMD:

孟志宇, 张因, 赵丽丽, 张鸿喜, 赵永祥. 不同晶型TiO₂负载镍催化剂催化顺酐液相加氢. 高等学校化学学报, 2015, 36(9): 1779.

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

图/表 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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不同晶型TiO₂负载镍催化剂催化顺酐液相加氢

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

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