邻甲酚液相原位加氢反应

doi:10.7503/cjcu20140464

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (12): 2654.doi: 10.7503/cjcu20140464

邻甲酚液相原位加氢反应

李雁斌^1,², 徐莹^2,³, 马隆龙^1,^2,³(), 张琦^2,³, 王铁军^2,³, 陈冠益¹, 张丽敏²

1. 天津大学环境学院生物质能研究中心, 内燃机燃烧学国家重点试验室, 天津 300072
2.中国科学院广州能源研究所, , 广州 510640
3. 中国科学院可再生能源重点实验室, 广州 510640

收稿日期:2014-05-19 出版日期:2014-12-10 发布日期:2014-11-29
作者简介:联系人简介: 马隆龙, 男, 博士, 研究员, 博士生导师, 主要从事生物质高效利用研究. E-mail:mall@ms.giec.ac.cn
基金资助:
国家自然科学基金(批准号: 51106108, 51036006)、中国科学院重点部署项目(批准号: KGZD-EW-304-3)和中国科学院广州能源研究所所长创新基金(批准号: y307r91001)资助

Research on in situ Hydrogenation of o-Cresol over Ni/CMK-3 Catalysts^†

LI Yanbin^1,², XU Ying^2,³, MA Longlong^1,^2,^3,^*(), ZHANG Qi^2,³, WANG Tiejun^2,³, CHEN Guanyi¹, ZHANG Limin²

1. Faculty of Environmental Science and Engineering, State Key Lab of International Combustion Engine,Tianjin University, Tianjin 300072, China
2. Guangzhou Institute of Energy Conversion,Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China
3. Key Laboratory of Renewable Energy,Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China

Received:2014-05-19 Online:2014-12-10 Published:2014-11-29
Contact: MA Longlong E-mail:mall@ms.giec.ac.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.51106108, 51036006), the Deployment Project of Chinese Academy of Sciences(No.KGZD-EW-304-3) and the Innovation Foundation of Guangzhou Institute of Energy Conversion, China(No.y307r91001)

摘要/Abstract

摘要：

以Ni/CMK-3为催化剂, 采用BET比表面积、 X射线衍射和氢气程序升温还原对催化剂进行了表征. 考察了不同Ni负载量、反应温度、反应初始压力及反应时间条件下, 甲醇水相重整制氢与邻甲酚原位加氢的耦合反应. 结果表明, 当Ni负载量为20%、反应温度为230 ℃、反应前冷压为0.1 MPa、水-甲醇-模型化合物摩尔比为50:15:1及反应9 h时, 邻甲酚转化率最高为45.4%. 分别对比了甲醇、甲酸、甘油和异丙醇作为供氢溶剂对原位加氢反应的影响, 其中以甲酸为供氢溶剂时, 邻甲酚的转化率最高达82.2%. 对比了甲酚3种同分异构体原位加氢的效果, 发现邻甲酚和间甲酚的反应效果相差不大, 而对甲酚的转化率则远低于邻甲酚和间甲酚. 对20%Ni/CMK-3在原位加氢实验中的使用寿命进行了考察.

关键词: 原位加氢, 邻甲酚, CMK-3镍基催化剂

Abstract:

In situ hydrogenation was studied by means of Ni loading, temperature, initial pressure, and reaction time over Ni/CMK-3 catalysts. The catalysts were characterized by X-ray diffraction(XRD), H₂ temperature programmed reduction(H₂-TPR) and N₂ adsorption-desorption isotherms. The results revealed that the optimal conditions were confirmed as follow: Ni loading of 20%(mass fraction), reaction temperature of 230 ℃, initial pressure of 0.1 MPa, reaction time of 9 h for in situ hydrogenation. The maximum conversion of o-cresol in optimal condition was determined as 47.56%. Compared with the effect of hydrogen donor solvents, formic acid was the best of four kinds of solvents. The comparsion of cresol isomers, recyclability of Ni/CMK-3 were also discussed.

Key words: In situ hydrogenation, o-Cresol, Nickel-based CMK-3 catalyst

中图分类号:

O643.3

TrendMD:

李雁斌, 徐莹, 马隆龙, 张琦, 王铁军, 陈冠益, 张丽敏. 邻甲酚液相原位加氢反应. 高等学校化学学报, 2014, 35(12): 2654.

LI Yanbin, XU Ying, MA Longlong, ZHANG Qi, WANG Tiejun, CHEN Guanyi, ZHANG Limin. Research on in situ Hydrogenation of o-Cresol over Ni/CMK-3 Catalysts^†. Chem. J. Chinese Universities, 2014, 35(12): 2654.

图/表 16

Table 1 Textural and structural properties of the catalysts

Catalyst	Specific surface area/(m²·g^-1)	Average pore size/nm	Pore volume/(cm³·g^-1)
CMK-3	1128.026	3.411	0.781
20%Ni/CMK-3	984.706	3.399	0.752
SBA-15	674.972	6.419	0.907
20%Ni/SBA-15	558.942	6.581	0.964

Fig.1 Small-angle XRD patterns of SBA-15(a) and CMK-3(b)

Fig.2 H2-TPR profiles of 20%Ni/CMK-3(a) and 20%Ni/SBA-15(b)

Fig.3 TEM images of CMK-3 (A) Horizontal direction; (B) vertical direction.

Fig.4 SEM images of the CMK-3(A) and 20%Ni/CMK-3(B)

Fig.5 Selectivity() and conversion(■,▼) under different Ni loadings

Fig.6 Selectivity() and conversion(▼,■) at different temperatures

Fig.7 Effect of different initial pressure on in situ hydrogenation of o-cresol

Fig.8 Effect of different reaction time on in situ hydrogenation of o-cresol

Table 2 Catalytic effect contrast of Ni/CMK-3 catalsts

Reaction time/h	Conversion of methanol(%)	Selectivity of methane(%)	Reaction time/h	Conversion of methanol(%)	Selectivity of methane(%)
3	5.41	3.19	9	11.21	7.06
6	7.47	4.57	12	12.45	9.52

Table 3 Effects of hydrogen-donor solvents on catalystic performance

Hydrogen donor solvent	Conversion of o-cresol(%)	Selectivity of product(%)		Real hydrogen yield/mol
Hydrogen donor solvent	Conversion of o-cresol(%)	2-Methyl cyclohexanol	2-Methyl cyclohexanone	Real hydrogen yield/mol
Isopropyl alcohol	26.72	15.63	83.22	0.008
Methanol	53.49	36.73	63.20	0.031
Glycerol	64.41	32.14	36.81	0.026
Formic acid	82.24	39.45	60.48	0.041

Fig.9 Effect of different molar ratios of water/methanol on selectivity of product() and conversion of o-cresol

Table 4 Comparsion of the effect on three isomers

Reactant	Conversion of reactant(%)	Selectivity of product(%)		Conversion of methanol(%)
Reactant	Conversion of reactant(%)	2-Methylcyclohexanol	2-Methylcyclohexanone	Conversion of methanol(%)
o-Cresol	45.03	36.73	63.20	10.34
m-Cresol	43.79	39.45	60.48	11.09
p-Cresol	27.62	33.48	65.71	11.62

Table 5 Testing effect of CMK-3 reaction life

Reaction times	Conversion of o-cresol(%)	Selectivity of product(%)		Conversion of methanol(%)
Reaction times	Conversion of o-cresol(%)	2-Methyl cyclohexanol		2-Methyl cyclohexanone
1	45.03	36.73	63.20	10.34
2	40.79	34.17	65.71	8.41
3	25.86	39.45	60.48	2.48
4	6.82	11.37	88.44	0.92

Fig.10 XRD patterns of 20%Ni/CMK-3 before(a) and after reaction one time(b)

Fig.11 SEM images of the catalysts after reaction (A) After first reaction; (B) after second reaction; (C) after third reaction; (D) after fourth reaction.

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邻甲酚液相原位加氢反应

Research on in situ Hydrogenation of o-Cresol over Ni/CMK-3 Catalysts^†

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邻甲酚液相原位加氢反应

Research on in situ Hydrogenation of o-Cresol over Ni/CMK-3 Catalysts†

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Research on in situ Hydrogenation of o-Cresol over Ni/CMK-3 Catalysts^†