酚类加氢脱氧催化剂研究进展

doi:10.16085/j.issn.1000-6613.2018-1987

摘要/Abstract

摘要：

酚类加氢脱氧（HDO）是石油、煤基液体燃料和生物质油转化利用中的重要过程，催化剂在其中起关键作用。酚类加氢脱氧催化剂包括过渡金属硫化物、还原态金属催化剂、磷化物、碳化物和氮化物等。本文从活性、选择性、稳定性和催化机理等方面介绍了各类催化剂的研究进展。过渡金属硫化物重点介绍了负载的CoMoS催化剂和非负载的MoS₂，其中晶态MoS₂具有优异的活性和选择性。还原态金属介绍了负载的非贵金属（Ni、Mo和Co）、贵金属（Rh、Ru、Pd和Pt）和双金属（NiRu、Ni-Fe、Mo-Pt和Pd-X）等催化剂，并对不同的金属催化剂进行了比较。磷化物重点介绍了SiO₂负载的Ni₂P、MoP和CoP，Ni₂P/SiO₂具有很高的催化活性和选择性。碳化物主要是Mo₂C催化剂，其具有较高的芳环类产物选择性。氮化物主要是Mo₂N催化剂，其加氢脱氧活性仍有待提高。各类催化剂大多存在稳定性欠缺的问题，过渡金属硫化物主要是提高催化剂对水的稳定性，还原态金属必须重视杂质尤其是硫引起的中毒问题，可考虑与脱硫催化剂组合使用，磷化物应关注积炭和颗粒团聚。

关键词: 酚类, 加氢, 加氢脱氧, 催化剂, 生物质, 煤焦油

Abstract:

Hydrodeoxygenation (HDO) of phenols is an essential process in the conversion of crude oil, coal-based liquid fuel and bio-oil. Catalysts play a key role in this process. The HDO catalysts for phenols include the transition metal sulfides, the reduced metal catalysts, the metal phosphides, carbides and nitrides. Recent research on these catalysts was summarized in terms of the activity, selectivity, stability and catalytic mechanism. The supported CoMoS catalysts and unsupported MoS₂ were introduced emphatically as the transition metal sulfides. The crystalline MoS₂ had excellent activity and selectivity. The catalysts of the supported non-noble metals (Ni, Mo and Co), noble metals (Rh, Ru, Pd and Pt) and bimetals (NiRu，Ni-Fe，Mo-Pt and Pd-X) were introduced. The performance of different metal catalysts was compared. The catalysts of Ni₂P，MoP and CoP supported on SiO₂ were introduced as the metal phosphides, among which the Ni₂P/SiO₂ exhibited the highest catalytic activity and selectivity. In the metal carbides, Mo₂C had a high selectivity to the aromatics, while the HDO activity of the Mo₂N should be improved. The stability of all catalysts is not good enough. As to the transition metal sulfides, the stability to water should be strengthened. For the reduced metal catalysts, the impurities, especially sulfur, should be considered. The reduced metal catalysts were suggested to be used together with the desulfurization catalysts. In the case of the metal phosphides, more attention should be paid to the carbon deposition and particle agglomeration.

Key words: phenols, hydrogenation, hydrodeoxygenation, catalysts, biomass, coal tar

中图分类号:

邱泽刚,尹婵娟,李志勤,冯跃阔. 酚类加氢脱氧催化剂研究进展[J]. 化工进展, 2019, 38(08): 3658-3669.

Zegang QIU,Chanjuan YIN,Zhiqin LI,Yuekuo FENG. Recent advances in hydrodeoxygenation catalysts for phenols[J]. Chemical Industry and Engineering Progress, 2019, 38(08): 3658-3669.

图/表 7

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催化剂类别	催化剂组成	反应物	溶剂	反应条件			转化率/%	主要产物及选择性/%	参考文献
催化剂类别	催化剂组成	反应物	溶剂	温度/℃	压力/MPa	时间/h	转化率/%	主要产物及选择性/%	参考文献
过渡金属硫化物催化剂	CoMoS/γ-Al₂O₃	苯酚	正十二烷	300	5	4	27	苯37	[30]^①
		4-甲基酚					22	甲苯60
	MoS₂	苯酚	正十四烷	300	4	6	约100	环己烷99.63	[33]^①
	Co-MoS₂	4-甲基酚	十氢萘	180	3	8	97.6	甲苯98.4	[34]^①
	无定形MoS₂	4-甲基酚	正十二烷	300	4	6	84	甲苯85.7	[36]^①
	Ni掺杂的无定形MoS₂	苯酚	正十二烷	300	3	2	70	环己烷约90	[37]^①
还原态金属催化剂	Ni/SiO₂	2-甲氧基苯酚	十氢萘	120	2	2	100	环己醇99.9	[45]^①
	Co/Al₂O₃	苯酚	正十二烷	300	3	4	100	环己烷、苯、环己烯	[49]^①
	Mo/纳米γ-Al₂O₃	苯甲醚	无	450	—	6.0h^-1③	70	苯酚75、苯25	[51]^②
	Pd/SA Pd，Pt/C	苯酚	正十六烷	300 —	3 3	1 1	99 99	环己烷99 环己醇99	[54]^①
	Pd/t-ZrO₂	苯酚	无	300	常压	—	90	苯80	[57]^②
	Pd/Nb₂O₅	苯酚	无	400	0.1	—	10	苯99.6	[58]^②
	Ni₅-Fe₁/CNT	2-甲氧基苯酚	无	300	3	6.0h^-1③	96.8	环己烷83.4	[63]^②
	Ni₁-Fe₅/CNT						47.2	苯酚83.3
	Mo-Pt/TiO₂	2-甲氧基苯酚	正十二烷	285	4	—	94	环己烷57.7	[65]^②
磷化物、碳化物和氮化物	Ni₂P /SiO₂	苯甲醚	无	300	—	1.8h^-1③	97	环己烷92.6	[74]^②
				400	—		100	苯96.4
	Ni₂P/SiO₂	2-甲氧基苯酚	无	350	常压	2.0h^-1③	8	苯95、苯酚3	[75]^②
	CoP/SiO₂	苯酚	辛烷	300	3	0.42h^-1③	99	环己烷90	[76]^①
	MoC _x /C	2-甲氧基苯酚	—	300	0.5	2	99	苯酚76、邻甲基苯酚8、苯3	[79]^①
	Mo₂N/活性炭	2-甲氧基苯酚	正癸烷	300	5	＜4.5	＜12	邻苯二酚、苯酚	[80]^①

催化剂类别	催化剂组成	反应物	溶剂	反应条件			转化率/%	主要产物及选择性/%	参考文献
催化剂类别	催化剂组成	反应物	溶剂	温度/℃	压力/MPa	时间/h	转化率/%	主要产物及选择性/%	参考文献
过渡金属硫化物催化剂	CoMoS/γ-Al₂O₃	苯酚	正十二烷	300	5	4	27	苯37	[30]^①
		4-甲基酚					22	甲苯60
	MoS₂	苯酚	正十四烷	300	4	6	约100	环己烷99.63	[33]^①
	Co-MoS₂	4-甲基酚	十氢萘	180	3	8	97.6	甲苯98.4	[34]^①
	无定形MoS₂	4-甲基酚	正十二烷	300	4	6	84	甲苯85.7	[36]^①
	Ni掺杂的无定形MoS₂	苯酚	正十二烷	300	3	2	70	环己烷约90	[37]^①
还原态金属催化剂	Ni/SiO₂	2-甲氧基苯酚	十氢萘	120	2	2	100	环己醇99.9	[45]^①
	Co/Al₂O₃	苯酚	正十二烷	300	3	4	100	环己烷、苯、环己烯	[49]^①
	Mo/纳米γ-Al₂O₃	苯甲醚	无	450	—	6.0h^-1③	70	苯酚75、苯25	[51]^②
	Pd/SA Pd，Pt/C	苯酚	正十六烷	300 —	3 3	1 1	99 99	环己烷99 环己醇99	[54]^①
	Pd/t-ZrO₂	苯酚	无	300	常压	—	90	苯80	[57]^②
	Pd/Nb₂O₅	苯酚	无	400	0.1	—	10	苯99.6	[58]^②
	Ni₅-Fe₁/CNT	2-甲氧基苯酚	无	300	3	6.0h^-1③	96.8	环己烷83.4	[63]^②
	Ni₁-Fe₅/CNT						47.2	苯酚83.3
	Mo-Pt/TiO₂	2-甲氧基苯酚	正十二烷	285	4	—	94	环己烷57.7	[65]^②
磷化物、碳化物和氮化物	Ni₂P /SiO₂	苯甲醚	无	300	—	1.8h^-1③	97	环己烷92.6	[74]^②
				400	—		100	苯96.4
	Ni₂P/SiO₂	2-甲氧基苯酚	无	350	常压	2.0h^-1③	8	苯95、苯酚3	[75]^②
	CoP/SiO₂	苯酚	辛烷	300	3	0.42h^-1③	99	环己烷90	[76]^①
	MoC _x /C	2-甲氧基苯酚	—	300	0.5	2	99	苯酚76、邻甲基苯酚8、苯3	[79]^①
	Mo₂N/活性炭	2-甲氧基苯酚	正癸烷	300	5	＜4.5	＜12	邻苯二酚、苯酚	[80]^①

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