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

doi:10.11949/0438-1157.20230547

Abstract

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

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

CLC Number:

TQ 032.4

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.

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.

Figures/Tables 9

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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

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

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