磷酸铈对磷化镍催化苯酚转移加氢的促进作用

doi:10.7503/cjcu20190573

高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (4): 765.doi: 10.7503/cjcu20190573

磷酸铈对磷化镍催化苯酚转移加氢的促进作用

孟繁星¹,遇治权¹,景文文¹,王瑶^1,²,孙志超¹,王安杰^1,^2,^*()

^1. 大连理工大学精细化工国家重点实验室, 大连 116024
^2. 辽宁省省级高校石油化工技术与装备重点实验室, 大连 11602

收稿日期:2019-11-05 出版日期:2020-04-10 发布日期:2020-02-21
通讯作者: 王安杰 E-mail:ajwang@dlut.edu.cn
基金资助:
国家自然科学基金(21972014, 21473017, 21603024, U1508205);中央高校基本科研业务费(DUT19GJ205);科技部国家重点研发计划项目(批准号: )资助.(2016YFE0109800)

Promoting Effect of Cerous Phosphate on the Phenol Catalytic Transfer Hydrogenation over Nickel Phosphide Catalyst ^†

MENG Fanxing¹,YU Zhiquan¹,JING Wenwen¹,WANG Yao^1,²,SUN Zhichao¹,WANG Anjie^1,^2,^*()

^1. State Key Laboratory of Fine Chemical, Dalian University of Technology, Dalian 116024, China
^2. Liaoning Key Laboratory of Petrochemical Technology and Equipment, Dalian 116024, China

Received:2019-11-05 Online:2020-04-10 Published:2020-02-21
Contact: Anjie WANG E-mail:ajwang@dlut.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(21972014, 21473017, 21603024, U1508205);the Fundamental Research Funds for the Central Universities, China(DUT19GJ205);the National Key Research and Development Project, China(2016YFE0109800)

摘要/Abstract

摘要：

通过氢气原位程序升温还原法制备了一系列不同Ce/Ni摩尔比的CePO₄-Ni₃P及Ni₃P催化剂, 考察了其在苯酚催化转移加氢反应的催化性能. 研究了Ce/Ni摩尔比、供氢溶剂、反应温度和反应时间对催化剂性能的影响, 并初步考察了苯酚转移加氢的反应动力学. 研究结果表明, CePO₄的加入能显著提升体相Ni₃P催化苯酚转移加氢的转化率, 且Ce/Ni摩尔比为0.2时促进作用最显著; 在所考察的供氢溶剂中异丙醇展现出最好的性能; 使用CePO₄(0.2)-Ni₃P作为反应催化剂, 异丙醇作为供氢溶剂, 220 ℃下反应6 h, 苯酚转化率和环己醇选择性分别可达93.1%和92.0%.

关键词: 磷化镍, 磷酸铈, 转移加氢, 苯酚, 异丙醇

Abstract:

A series of CePO₄-Ni₃P and Ni₃P catalysts with various Ce/Ni molar ratio were prepared by in-situ H₂ temperature-programmed reduction, and utilized to catalyze the transfer hydrogenation of phenol. The effects of Ce/Ni molar ratio, hydrogen donors, reaction temperature and reaction time on the catalytic perfor-mance were investigated. What’s more, the reaction kinetic parameters were calculated. The reaction results showed that the addition of CePO₄ could significantly improve the phenol conversion. The promoting effect was the most obvious when the Ce/Ni molar ratio was 0.2. 2-Propanol exhibited the best catalytic activity among all the screened solvents. A high cyclohexanol selectivity of 92.0% and phenol conversion of 93.1% could be obtained at 220 ℃ for 6 h over the CePO₄(0.2)-Ni₃P catalyst using 2-propanol as the hydrogen donor and solvent.

Key words: Ni₃P, CePO₄, Transfer hydrogenation, Phenol, 2-Propanol

中图分类号:

O643

TrendMD:

孟繁星, 遇治权, 景文文, 王瑶, 孙志超, 王安杰. 磷酸铈对磷化镍催化苯酚转移加氢的促进作用. 高等学校化学学报, 2020, 41(4): 765.

MENG Fanxing, YU Zhiquan, JING Wenwen, WANG Yao, SUN Zhichao, WANG Anjie. Promoting Effect of Cerous Phosphate on the Phenol Catalytic Transfer Hydrogenation over Nickel Phosphide Catalyst ^†. Chem. J. Chinese Universities, 2020, 41(4): 765.

图/表 11

Fig.1 XRD patterns of Ni3P and CePO4(x)-Ni3P catalysts

Fig.2 TEM images of Ni3P(A) and CePO4(x)-Ni3P catalysts with various Ce/Ni ratios of 0.05(B), 0.1(C), 0.2(D,F) and 0.3(E)

Fig.3 NH3-TPD curves of CePO4(x)-Ni3P and Ni3P catalysts

Table 1 Physical properties of Ni3P and CePO4(x)-Ni3P catalysts

Catalyst	Crystallite size^a/nm	Particle size^b/nm	Relative acid amount^c
Ni₃P	68.2	84.5	1
CePO₄(0.05)-Ni₃P	29.3	29.3	10.6
CePO₄(0.1)-Ni₃P	27.5	27.7	16.6
CePO₄(0.2)-Ni₃P	26.9	24.3	17.6
CePO₄(0.3)-Ni₃P	10.4	21.2	19.4

Table 2 Effect of Ce/Ni molar ratio on the catalytic performance*

Catalyst	Conversion(%)	Selectivity(%)
Catalyst	Conversion(%)	Cyclohexanone	Cyclohexanol
Ni₃P	68.8	7.1	92.9
CePO₄(0.05)-Ni₃P	83.1	7.6	92.4
CePO₄(0.1)-Ni₃P	85.1	8.0	92.0
CePO₄(0.2)-Ni₃P	87.7	8.0	92.0
CePO₄(0.3)-Ni₃P	83.3	10.3	89.7

Fig.4 XPS spectra of CePO4(0.2)-Ni3P in Ni2p(A), P2p(B) and Ce3d(C) regions

Table 3 Effect of hydrogen donors on the catalytic performance*

Hydrogen donor	Conversion(%)	Selectivity(%)
Hydrogen donor	Conversion(%)	Cyclohexanone	Cyclohexanol
Methanol	2.0	49.5	50.5
Ethanol	5.9	27.0	73.0
n-Propanol	18.4	18.8	81.2
2-Propanol	87.7	8.0	92.0
2-Butanol	72.3	11.6	88.4
1,2-Propanediol	25.2	34.1	65.9
Glycerol	1.3	48.9	51.1

Scheme 1 Reaction network for catalytic transfer hydrogenation of phenol

Fig.5 Plots of -ln(1-x) as a function of reaction time(A) and Arrhenius plot for phenol transfer hydrogenation over CePO4(0.2)-Ni3P(B)

Fig.6 Plots of -ln(1-x) as a function of reaction time(A) and Arrhenius plot for phenol transfer hydrogenation over Ni3P(B)

Table 4 Effect of hydrogen donors on the catalytic performance*

Catalyst	Temperature/℃	10³Rate constant/ min^-1	E_a/ (kJ·mol^-1)
CePO₄(0.2)-Ni₃P	180	4.16	27.9
	200	5.74
	220	7.56
Ni₃P	180	1.64	62.3
	200	3.25
	220	6.28

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磷酸铈对磷化镍催化苯酚转移加氢的促进作用

Promoting Effect of Cerous Phosphate on the Phenol Catalytic Transfer Hydrogenation over Nickel Phosphide Catalyst ^†

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磷酸铈对磷化镍催化苯酚转移加氢的促进作用

Promoting Effect of Cerous Phosphate on the Phenol Catalytic Transfer Hydrogenation over Nickel Phosphide Catalyst †

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Promoting Effect of Cerous Phosphate on the Phenol Catalytic Transfer Hydrogenation over Nickel Phosphide Catalyst ^†