Research progress on reaction mechanism and catalysts for catalytic hydrodeoxygenation(HDO) of biomass oil

doi:10.16085/j.issn.1000-6613.2020-0260

Abstract

Abstract:

In this paper, the research progress on the preparation, catalytic performance and reaction mechanism of biomass oil catalytic hydrodeoxygenation catalysts in recent years are summarized. The preparation methods, catalytic performance and mechanism of noble metal catalysts, transition metal catalysts and sulfides, carbides, nitrides, phosphide catalysts were mainly discussed. The reasons for the deactivation of the hydrodeoxygenation catalyst were analyzed, and the future development of the biomass oil hydrodeoxygenation catalysts was also proposed: the application of three-dimensional ordered mesoporous (3DOM) perovskite oxide may play a role in improving the catalytic performance of the catalyst.

Key words: biomass oil, hydrodeoxygenation, catalyst, reaction mechanism, deactivation, perovskite oxide

摘要：

对近年来生物质油催化加氢脱氧催化剂的制备、催化性能和反应机理的研究进展进行了整理总结。重点对贵金属催化剂、过渡金属催化剂和硫、氮、碳、磷等金属化合物催化剂的制备方法、催化性能和作用机理进行了概述，并分析了加氢脱氧催化剂的失活原因，同时提出生物质油加氢脱氧反应催化剂的未来发展方向：三维有序大孔（3DOM）钙钛矿氧化物的应用可能在提高催化剂的催化性能有作用。

关键词: 生物质油, 加氢脱氧, 催化剂, 反应机理, 失活, 钙钛矿氧化物

CLC Number:

TQ032.4

Caixia LIAN, Ning LI, Wu JIANG, Hao MA, Han PENG. Research progress on reaction mechanism and catalysts for catalytic hydrodeoxygenation(HDO) of biomass oil[J]. Chemical Industry and Engineering Progress, 2020, 39(S1): 153-162.

练彩霞, 李凝, 蒋武, 马浩, 彭瀚. 生物质油催化加氢脱氧（HDO）反应机理及催化剂研究进展[J]. 化工进展, 2020, 39(S1): 153-162.

Figures/Tables 8

References 74

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物理性质	生物质油	重质燃料油
含水量（质量分数）/ %	15～30	0.1
pH	2.5	—
密度/g·mL^-1	1.2	0.94
热值/MJ·kg^-1	16～19	40
黏度(40℃)/Pa·s	40～100	180
固体颗粒（焦炭）（质量分数）/%	0.2～1	0.1
减压蒸馏残渣（质量分数）/%	50	1
元素质量分数/%
C	54～58	85
H	5.5～7.0	11
O	35～40	1.0
N	0～0.2	0.3
S	＜0.23	＜4

物理性质	生物质油	重质燃料油
含水量（质量分数）/ %	15～30	0.1
pH	2.5	—
密度/g·mL^-1	1.2	0.94
热值/MJ·kg^-1	16～19	40
黏度(40℃)/Pa·s	40～100	180
固体颗粒（焦炭）（质量分数）/%	0.2～1	0.1
减压蒸馏残渣（质量分数）/%	50	1
元素质量分数/%
C	54～58	85
H	5.5～7.0	11
O	35～40	1.0
N	0～0.2	0.3
S	＜0.23	＜4

Pd催化剂(质量分数)	反应物	反应条件/(℃/MPa)	转化率/%	选择性（烃类）/%	参考文献
1.92%Pd/SiO₂	苯酚	300/1	7.0	8.1	[23]
2.28%Pd/Al₂O₃	苯酚	300/1	7.5	14.2	[23]
1.83%Pd/TiO₂	苯酚	300/1	7.0	66.8	[23]
2.24%Pd/ZrO₂	苯酚	300/1	12.6	29.9	[23]
2.44%Pd/CeO₂	苯酚	300/1	9.0	4.9	[23]
2.46%Pd/CeZrO₂	苯酚	300/1	12.4	4.6	[23]
2.6%PdMS	苯酚	350/3	94.6	89.1	[26]
1.9%Pd/SBA-15	苯酚	350/3	97.5	84.9	[28]
1.0%Pd/PSSH/Al₂O	苯酚	200/4	91	46	[27]
1.0%Pd/PSSH/TiO₂	苯酚	200/4	98	78	[29]
5.0%Pd/AC	愈创木酚	330/3.4	100	90.4	[28]
1.1%Pd/ZSM-5	苯酚	150/4	>99.9	93.0	[29]
ZSM-5@Pd/Al₂O₃(1∶1)	苯酚	150/4	>99.9	98.0	[31]
3.3%Pd@MIL-101	苯甲醚	260/3	77.7	52.1	[30]
2%Pd/Nb₂O₅	木质素	250/0.5	41.8	76.1	[31]

Pd催化剂(质量分数)	反应物	反应条件/(℃/MPa)	转化率/%	选择性（烃类）/%	参考文献
1.92%Pd/SiO₂	苯酚	300/1	7.0	8.1	[23]
2.28%Pd/Al₂O₃	苯酚	300/1	7.5	14.2	[23]
1.83%Pd/TiO₂	苯酚	300/1	7.0	66.8	[23]
2.24%Pd/ZrO₂	苯酚	300/1	12.6	29.9	[23]
2.44%Pd/CeO₂	苯酚	300/1	9.0	4.9	[23]
2.46%Pd/CeZrO₂	苯酚	300/1	12.4	4.6	[23]
2.6%PdMS	苯酚	350/3	94.6	89.1	[26]
1.9%Pd/SBA-15	苯酚	350/3	97.5	84.9	[28]
1.0%Pd/PSSH/Al₂O	苯酚	200/4	91	46	[27]
1.0%Pd/PSSH/TiO₂	苯酚	200/4	98	78	[29]
5.0%Pd/AC	愈创木酚	330/3.4	100	90.4	[28]
1.1%Pd/ZSM-5	苯酚	150/4	>99.9	93.0	[29]
ZSM-5@Pd/Al₂O₃(1∶1)	苯酚	150/4	>99.9	98.0	[31]
3.3%Pd@MIL-101	苯甲醚	260/3	77.7	52.1	[30]
2%Pd/Nb₂O₅	木质素	250/0.5	41.8	76.1	[31]

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