Raney镍-质子型离子液体体系催化木质素平台分子加氢脱氧制备烷烃

doi:10.11949/0438-1157.20230547

化工学报 ›› 2023, Vol. 74 ›› Issue (9): 3697-3707.DOI: 10.11949/0438-1157.20230547

• 离子液体与绿色过程专栏 • 上一篇下一篇

Raney镍-质子型离子液体体系催化木质素平台分子加氢脱氧制备烷烃

杨绍旗¹(), 赵淑蘅¹, 陈伦刚², 王晨光³, 胡建军¹(), 周清⁴, 马隆龙²()

^1.河南农业大学机电工程学院，河南郑州 450002
^2.东南大学能源与环境学院，江苏南京 211189
^3.中国科学院广州能源研究所，广东广州 510640
^4.中国科学院绿色过程制造创新研究院，北京 100190

收稿日期:2023-06-07 修回日期:2023-09-01 出版日期:2023-09-25 发布日期:2023-11-20
通讯作者: 胡建军,马隆龙
作者简介:杨绍旗（1989—），男，博士，讲师，sqyang@henau.edu.cn
基金资助:
中国博士后科学基金项目(2020M682939);中国科学院绿色过程制造创新研究院自主部署项目联合基金项目(IAGM2020C21);河南农业大学高层次人才专项支持基金项目(30501331)

Hydrodeoxygenation of lignin-derived compounds to alkanes in Raney Ni-protic ionic liquid system

Shaoqi YANG¹(), Shuheng ZHAO¹, Lungang CHEN², Chenguang WANG³, Jianjun HU¹(), Qing ZHOU⁴, Longlong MA²()

^1.College of Mechanical & Electrical Engineering, Henan Agricultural University, Zhengzhou 450002, Henan, China
^2.School of Energy and Environment, Southeast University, Nanjing 211189, Jiangsu, China
^3.Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^4.Innovation Academy for Green Manufacture, Chinese Academy of Sciences, Beijing 100190, China

Received:2023-06-07 Revised:2023-09-01 Online:2023-09-25 Published:2023-11-20
Contact: Jianjun HU, Longlong MA

摘要/Abstract

摘要：

木质素是生物质组成中唯一的芳香类化合物组分，高效转化木质素制备烷烃对于生物质全组分利用具有重要意义。通过设计合成质子型醇胺类离子液体，并与Raney镍催化剂建立催化体系，考察了其对于木质素衍生酚及醚类化合物加氢脱氧制备环烷烃的反应特性和规律。研究证明，Raney镍协同二乙醇胺三氟甲烷磺酸盐（[2-HDEA]OTf）催化体系具有最优的催化木质素衍生酚类和醚类化合物加氢脱氧效果。在反应温度130℃，时间15 h，氢气压力3 MPa条件下，木质素衍生酚类及醚类化合物转化率>99.0%，目标产物环烷烃产率>80.0%。Raney镍催化剂表现出与Rh/C等贵金属相近的催化效果，离子液体阴离子结构（OTf）在催化脱氧过程中起关键性作用。

关键词: 木质素, 离子液体, Raney镍, 加氢脱氧, 烷烃

Abstract:

Lignin is the only aromatic compounds in biomass. Efficient conversion of lignin to alkane is of great significance for the full utilization of biomass. In this work, the reaction characteristics and rules of lignin-derived phenols and ethers hydrodeoxygenation (HDO) to cycloalkanes are investigated under the catalytic system of Raney Ni coupling with synthesized protic alcoholamine ionic liquids (ILs). The research proves that Raney Ni combining with diethanolamine trifluoromethane sulfonate ([2-HDEA]OTf) has the best catalytic effect on HDO of lignin-derived phenolic and ether compounds. The conversion of lignin derived phenols and ethers are >99.0%, and the cycloalkane yields of the target product are >80.0% at 130℃ for 15 h with 3 MPa H₂ pressure. Raney Ni catalyst shows similar catalytic effect to noble metals such as Rh/C, and the ionic liquid anion structure (OTf) plays a key role in the catalytic deoxidation process. The catalytic system is recycled five times with phenol as the substrate to test its stability.

Key words: lignin, ionic liquids, Raney Ni, hydrodeoxygenation, alkanes

中图分类号:

TQ 032.4

杨绍旗, 赵淑蘅, 陈伦刚, 王晨光, 胡建军, 周清, 马隆龙. Raney镍-质子型离子液体体系催化木质素平台分子加氢脱氧制备烷烃[J]. 化工学报, 2023, 74(9): 3697-3707.

Shaoqi YANG, Shuheng ZHAO, Lungang CHEN, Chenguang WANG, Jianjun HU, Qing ZHOU, Longlong MA. Hydrodeoxygenation of lignin-derived compounds to alkanes in Raney Ni-protic ionic liquid system[J]. CIESC Journal, 2023, 74(9): 3697-3707.

图/表 9

图1 二苯醚在不同催化体系中加氢脱氧转化过程

Fig.1 Hydrodeoxidation conversion of diphenyl ether in different catalytic systems

图2 离子液体结构

Fig.2 Structures of ionic liquids

表1 不同离子液体和金属催化剂对苯酚加氢脱氧的活性研究

Table 1 Catalytic activity of different ILs and metal catalysts for HDO of phenol

编号	催化剂	离子液体（IL）	转化率/%	产率/%
编号	催化剂	离子液体（IL）	转化率/%	1a	1b	1c
1	Raney镍	[2-HDEA]OTf	100	93.1	0	1.6
2		[2-HDEA]OAc	89.0	5.7	45.3	0
3		[2-HDEA]Cl	100	14.1	55.6	0
4		[2-HDEA]H₂PO₄	98.4	9.6	41.5	0
5		[2-HDEA]mesy	88.2	5.1	10.3	0
6	—	[2-HDEA]OTf	0	0	0	0
7	Raney钴		91.0	10.5	41.1	0
8	Rh/C		100	96.4	0	2.5
9^①	Rh/C	[BHEM]TfO	100	93.3	0	2.3
10^②	Rh/SBA-15	[Bmim]PF₆	100	76.2	0	4.8
11^③	Rh NPs	[Bmim]PF₆	100	90.0	0	10.0

图3 苯酚加氢脱氧反应条件优化

Fig.3 The optimization of reaction conditions for phenol HDO process

图4 苯酚加氢脱氧转化过程分析

Fig.4 The reaction pathway analysis of phenol HDO processes

图5 [2-HDEA]OTf催化环己醇和环己酮反应GC-MS结果分析

Fig.5 GC-MS of cyclohexanol and cyclohexanone conversion results

表2 木质素衍生平台分子转化结果

Table 2 The lignin-derived compounds conversion results

编号	温度/℃	转化率/%
1	130	>99.0
2	130	>99.0
3	150	>99.0
4	130	>99.0
5	150	>99.0
6	130	>99.0
7	130	>99.0
8	150	>99.0
9	150	>99.0
10	150	>99.0
11	150	>99.0
12	150	>99.0

图6 Raney镍/[2-HDEA]OTf催化体系循环实验

Fig.6 Recycling test of the Raney Ni/[2-HDEA]OTf catalytic system

图7 循环实验回收催化体系表征分析

Fig.7 Characterization of recycled catalytic system

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Raney镍-质子型离子液体体系催化木质素平台分子加氢脱氧制备烷烃

Hydrodeoxygenation of lignin-derived compounds to alkanes in Raney Ni-protic ionic liquid system

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