双金属催化剂在生物质焦油催化蒸汽重整领域的研究进展

doi:10.16085/j.issn.1000-6613.2023-1152

摘要/Abstract

摘要：

综述了双金属催化剂在生物质焦油及其模型化合物催化蒸汽重整领域的研究现状，梳理了常用双金属催化剂的类型及不同催化剂催化焦油重整的性能，总结了影响双金属催化剂性能的主要因素，探讨了焦油催化重整的反应机理，并阐释了催化剂失活-再生反应机制。文中指出：双金属催化剂丰富的活性位点和双金属之间的协同作用促进了催化剂性能的提升，双金属活性相和载体之间适宜的相互作用增强了催化剂的稳定性；双金属催化剂在焦油蒸汽重整方面具有潜在的应用前景。目前双金属催化剂的活性、稳定性仍然无法满足焦油催化重整的产业化应用需求。下一步需开发催化剂的精准调控技术，深入阐释其催化反应机理，为焦油催化蒸汽重整产业化发展提供技术指导。

关键词: 生物质焦油, 催化重整, 蒸汽重整, 双金属催化剂, 再生

Abstract:

This review assessed the status of bimetallic catalysts in catalytic steam reforming of biomass tar and related model compounds. The types of common bimetallic catalysts and their performance in catalytic reforming of biomass tar were investigated; the factors affecting bimetallic catalyst performance were summarized; the reaction mechanism of catalytic tar reforming was outlined; and the catalyst deactivation and regeneration reaction mechanisms were clarified. The rich active sites and the synergistic interaction between bimetal catalysts promote the improvement of catalyst performance, and the appropriate interaction between bimetal active phase and support enhances the stability of the catalyst. Bimetallic catalysts have potential applications in the steam reforming of tar. At present, the activity and stability of bimetallic catalysts still cannot meet the needs of industrial applications of tar catalytic reforming. In the next step, it is necessary to develop the precise regulation technology of the catalyst and deeply explain its catalytic reaction mechanism, so as to provide technical guidance for the industrial development of tar catalytic steam reforming.

Key words: biomass tar, catalytic reforming, steam reforming, bimetallic catalyst, regeneration

中图分类号:

TQ426.82

胡婷霞, 赵立欣, 姚宗路, 霍丽丽, 贾吉秀, 谢腾. 双金属催化剂在生物质焦油催化蒸汽重整领域的研究进展[J]. 化工进展, 2024, 43(8): 4354-4365.

HU Tingxia, ZHAO Lixin, YAO Zonglu, HUO Lili, JIA Jixiu, XIE Teng. Research progress of bimetallic catalysts in catalytic steam reforming of biomass tar[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4354-4365.

图/表 9

图1 蒸汽重整流程图

表1 焦油重整涉及的主要反应方程式

反应类型	方程式	∆H/kJ·mol^-1	序号
裂解	$C x H y O z t a r → m C O + n C O 2 + p H 2 + q C H 4$	—	(1)
加氢重整	$C n H m t a r + H 2 → C O + H 2 + C H 4 + … + 焦炭$	—	(2)
干法重整	$C n H m t a r + n C O 2 → 2 n C O + m 2 H 2$	—	(3)
蒸汽重整	$C x H y O z t a r + H 2 O → C O + H 2$	—	(4)
波多反应	$C + C O 2 ⇌ 2 C O$	+172	(5)
水-汽转换	$C O + H 2 O ⇌ C O 2 + H 2$	+41	(6)
甲烷重整	$C H 4 + C O 2 ⇌ 2 C O + 2 H 2$	+260	(7)
甲烷重整	$C H 4 + H 2 O ⇌ C O + 3 H 2$	+206	(8)
甲烷化	$C O + 3 H 2 ⇌ C H 4 + H 2 O$	-206	(9)
甲烷化	$C O + 4 H 2 ⇌ C H 4 + 2 H 2 O$	-164	(10)

表1 焦油重整涉及的主要反应方程式

反应类型	方程式	∆H/kJ·mol^-1	序号
裂解	$C x H y O z t a r → m C O + n C O 2 + p H 2 + q C H 4$	—	(1)
加氢重整	$C n H m t a r + H 2 → C O + H 2 + C H 4 + … + 焦炭$	—	(2)
干法重整	$C n H m t a r + n C O 2 → 2 n C O + m 2 H 2$	—	(3)
蒸汽重整	$C x H y O z t a r + H 2 O → C O + H 2$	—	(4)
波多反应	$C + C O 2 ⇌ 2 C O$	+172	(5)
水-汽转换	$C O + H 2 O ⇌ C O 2 + H 2$	+41	(6)
甲烷重整	$C H 4 + C O 2 ⇌ 2 C O + 2 H 2$	+260	(7)
甲烷重整	$C H 4 + H 2 O ⇌ C O + 3 H 2$	+206	(8)
甲烷化	$C O + 3 H 2 ⇌ C H 4 + H 2 O$	-206	(9)
甲烷化	$C O + 4 H 2 ⇌ C H 4 + 2 H 2 O$	-164	(10)

图2 催化反应机理图

表2 Ni-Fe催化剂用于催化焦油及其模型化合物重整的性能

活性双金属	载体	合成方法	反应条件		模型化合物转化率/%	碳形成速率	参考文献
活性双金属	载体	合成方法	温度/℃	S/C	模型化合物转化率/%	碳形成速率	参考文献
Ni Fe	LaNi_0.8Fe_0.2O₃	溶胶-凝胶法	650	3.4	甲苯：53.1	—	[20]
Ni Fe	Fe₂O₃-Al₂O₃	浸渍法	650	1.0~4.0	甲苯90（26h）	18.3mg·g_cat^-1·h^-1	[21]
Ni Fe	橄榄石	热熔融法	苯酚：800 萘：900	—	苯酚：100 萘：80	苯酚<4% 萘<50%	[22]
Ni Fe	LaNi_0.8Fe_0.2O₃	溶胶-凝胶法	650	1.0	甲苯：90	5mg·g_cat^-1·h^-1	[25]
Ni Fe	Carbo HSP	共沉淀法、浸渍法	600~800	—	100	—	[26]
Ni Fe	坡缕石、MgO-Al₂O₃、La_0.8Ca_0.2CrO₃和La_0.8Ca_0.2CrO₃/MgO-Al₂O₃	浸渍法	700~900	—	萘和甲苯：57~86	5.5~15.5mmol·g_cat^-1	[27]
Ni Fe	Gd-CeO₂包覆的球形MgO-Al₂O₃	浸渍法	700	—	萘：80	2.5mmol·g_cat^-1	[24]
Ni Fe	Mg/Al类水滑石	浸渍法	600	1.7	苯酚：83.2	—	[28]
Ni Fe	稻壳炭	浸渍法	600~900	—	重油：92.3	—	[29]
Ni Fe	水热炭	浸渍法、水热炭化	500~900	—	—	2.8%~3.9%	[30]

图3 Ni/Fe2O3-Al2O3和Ni/Mg/Al水滑石负载单原子分散Pd修饰Ni金属颗粒的甲苯蒸汽重整反应机理[21, 33]

表3 Ni-Co催化剂用于催化焦油及其模型化合物重整的性能

活性双金属	载体	合成方法	反应条件		模型化合物转化率/%	碳形成速率	参考文献
活性双金属	载体	合成方法	温度/℃	S/C	模型化合物转化率/%	碳形成速率	参考文献
Ni Co	Al₂O₃	共浸渍	650	3.4	甲苯：100	—	[34]
Ni Co	CeO₂负载的Al₂O₃	浸渍法	700	4	正十二烷：89	—	[35]
Ni Co	ZrO₂	初期湿润浸渍	600	1.5	苯酚：53.5	31~75 mg·g $c a t - 1$	[36]

表3 Ni-Co催化剂用于催化焦油及其模型化合物重整的性能

活性双金属	载体	合成方法	反应条件		模型化合物转化率/%	碳形成速率	参考文献
活性双金属	载体	合成方法	温度/℃	S/C	模型化合物转化率/%	碳形成速率	参考文献
Ni Co	Al₂O₃	共浸渍	650	3.4	甲苯：100	—	[34]
Ni Co	CeO₂负载的Al₂O₃	浸渍法	700	4	正十二烷：89	—	[35]
Ni Co	ZrO₂	初期湿润浸渍	600	1.5	苯酚：53.5	31~75 mg·g $c a t - 1$	[36]

表4 其他镍基双金属催化剂用于催化焦油及其模型化合物性能

活性双金属	载体	合成方法	反应条件		焦油及其模型化合物转化率/%	碳形成速率	参考文献
活性双金属	载体	合成方法	温度/℃	S/C	焦油及其模型化合物转化率/%	碳形成速率	参考文献
Ni Cu	MgO-Al₂O₃	共浸渍	550	0.38	雪松木热解焦油100	3.1%（反应15min）	[39]
Ni Cu	MgO-Al₂O₃	共浸渍	850	1.1	1-甲基萘：100	5.7%（反应10min）	[41]
Ni Cu	SiO_2p	氨蒸发	600	0.5	纤维素热解焦油	$0.45 % · g c a t - 1 · h - 1$	[38]
Ni Ir	MgAl₂O₄	初期湿润浸渍法	850		苯：78 萘：78		[45]
Ni Pt	La_0.7Sr_0.3AlO_3-_δ	柠檬酸络合和浸渍	600		59.1	$8 m g C · g c a t - 1$ （反应3h后）	[43]
Ni Pd	Mg(Ni, Al)O	共沉淀	600~900		生物质焦油：80	1.4%（反应120min）	[46]
Ni Re	炭	浸渍法	500~900		桉树木屑热解焦油：100	$1.5 m m o l · g c a t - 1$ （反应18h）	[47]

表4 其他镍基双金属催化剂用于催化焦油及其模型化合物性能

活性双金属	载体	合成方法	反应条件		焦油及其模型化合物转化率/%	碳形成速率	参考文献
活性双金属	载体	合成方法	温度/℃	S/C	焦油及其模型化合物转化率/%	碳形成速率	参考文献
Ni Cu	MgO-Al₂O₃	共浸渍	550	0.38	雪松木热解焦油100	3.1%（反应15min）	[39]
Ni Cu	MgO-Al₂O₃	共浸渍	850	1.1	1-甲基萘：100	5.7%（反应10min）	[41]
Ni Cu	SiO_2p	氨蒸发	600	0.5	纤维素热解焦油	$0.45 % · g c a t - 1 · h - 1$	[38]
Ni Ir	MgAl₂O₄	初期湿润浸渍法	850		苯：78 萘：78		[45]
Ni Pt	La_0.7Sr_0.3AlO_3-_δ	柠檬酸络合和浸渍	600		59.1	$8 m g C · g c a t - 1$ （反应3h后）	[43]
Ni Pd	Mg(Ni, Al)O	共沉淀	600~900		生物质焦油：80	1.4%（反应120min）	[46]
Ni Re	炭	浸渍法	500~900		桉树木屑热解焦油：100	$1.5 m m o l · g c a t - 1$ （反应18h）	[47]

图4 催化剂蒸汽重整过程中焦炭形成机理[16]

表5 催化剂失活和再生过程涉及的主要反应方程式

反应类型	方程式	序号
炭沉积	$C n H m t a r → C + C x H y (s m a l l e r t a r) + g a s$	(11)
	$C n H m t a r → m / 2 H 2 + n C$	(12)
	$2 C O → 2 C + O 2$	(13)
	$2 C O → C O 2 + C$	(14)
	$C + 12 O 2 → C O (O 2 再生)$	(15)
	$C + 2 H 2 → C H 4 (H 2 再生)$	(16)
	$C + H 2 O → C O + H 2 (H 2 O 再生)$	(17)
	$C + 2 H 2 O → C H 4 + C O 2 (H 2 O 再生)$	(18)
中毒	$M O x + x H 2 S → M S x + x H 2 O$	(19)
中毒	$M + x H 2 S → M S x + x H 2$	(20)
	$M S x + x H 2 → M + x H 2 S (H 2 再生)$	(21)
	$M S x + 32 x O 2 → M O x + x S O 2 (O 2 再生)$	(22)
	$M S x + x H 2 O → M O x + x H 2 S (H 2 O 再生)$	(23)
结构破坏	$M + 12 O 2 → M O$	(24)
	$M + H 2 O → M O + 2 H +$	(25)
	$2 M + C O 2 → 2 M O + C$	(26)
	$M + C O 2 → M O + C O$	(27)
	$M O + H 2 → M + H 2 O (H 2 再生)$	(28)

表5 催化剂失活和再生过程涉及的主要反应方程式

反应类型	方程式	序号
炭沉积	$C n H m t a r → C + C x H y (s m a l l e r t a r) + g a s$	(11)
	$C n H m t a r → m / 2 H 2 + n C$	(12)
	$2 C O → 2 C + O 2$	(13)
	$2 C O → C O 2 + C$	(14)
	$C + 12 O 2 → C O (O 2 再生)$	(15)
	$C + 2 H 2 → C H 4 (H 2 再生)$	(16)
	$C + H 2 O → C O + H 2 (H 2 O 再生)$	(17)
	$C + 2 H 2 O → C H 4 + C O 2 (H 2 O 再生)$	(18)
中毒	$M O x + x H 2 S → M S x + x H 2 O$	(19)
中毒	$M + x H 2 S → M S x + x H 2$	(20)
	$M S x + x H 2 → M + x H 2 S (H 2 再生)$	(21)
	$M S x + 32 x O 2 → M O x + x S O 2 (O 2 再生)$	(22)
	$M S x + x H 2 O → M O x + x H 2 S (H 2 O 再生)$	(23)
结构破坏	$M + 12 O 2 → M O$	(24)
	$M + H 2 O → M O + 2 H +$	(25)
	$2 M + C O 2 → 2 M O + C$	(26)
	$M + C O 2 → M O + C O$	(27)
	$M O + H 2 → M + H 2 O (H 2 再生)$	(28)

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