乙烷和二氧化碳催化转化的研究进展

doi:10.11949/0438-1157.20220518

摘要/Abstract

摘要：

CO₂与乙烷反应是实现碳减排目标、利用非常规能源的重要手段，符合国家重大需求和国际学术前沿。其中，二氧化碳通过“活性氧”机理、“晶格氧”机理以及“反应耦合”机理促进乙烷的活化。通过催化剂设计选择性地断裂C—H/C—C键，可以实现反应定向地按照两条路径进行——乙烷干重整反应（DRE）和乙烷氧化脱氢（ODH）。综述了DRE和ODH两类反应的热力学、反应物活化机制和催化剂研究进展，分析了催化剂均存在产物选择性低、易烧结、积炭问题的主要影响因素以及催化剂设计和改进策略，并对该研究未来的发展方向进行展望。

关键词: CO₂, 乙烷, 催化剂, 选择性, 干重整, 氧化脱氢

Abstract:

The reaction of CO₂ with ethane is an important means to achieve carbon emission reduction goals and utilize unconventional energy, which is in line with major national needs and international academic frontiers. Carbon dioxide promotes the activation of ethane through “active oxygen” mechanism, “lattice oxygen” mechanism and “reaction coupling” mechanism. Through catalyst design to selectively break the C—H/C—C bonding, the reaction can proceed in two directions, dry reforming of ethane (DRE) and oxidative dehydrogenation to ethylene (ODH). This work reviews the thermodynamics, reactants activation mechanism and catalyst research progress of these two routes, analyzing the principal factors that arise the problems of low product selectivity, sintering and carbon deposition, as well as the design and improvement strategy. At last, we look ahead to the development direction of this research field.

Key words: carbon dioxide, ethane, catalyst, selectivity, dry reforming, oxidative dehydrogenation

中图分类号:

TQ 028.8

郭丹, 方雨洁, 许一寒, 李致远, 黄守莹, 王胜平, 马新宾. 乙烷和二氧化碳催化转化的研究进展[J]. 化工学报, 2022, 73(8): 3406-3416.

Dan GUO, Yujie FANG, Yihan XU, Zhiyuan LI, Shouying HUANG, Shengping WANG, Xinbin MA. Research progress of the catalytic conversion of ethane and carbon dioxide[J]. CIESC Journal, 2022, 73(8): 3406-3416.

图/表 10

图1 乙烷重整与氧化脱氢反应示意图

Fig.1 Schematic diagram of ethane reforming and oxidative dehydrogenation reaction

图2 乙烷干重整和乙烷氧化脱氢反应Gibbs自由能随温度的变化[7]

Fig.2 The variation of Gibbs free energy with temperature for dry reforming of ethane and oxidative dehydrogenation of ethane[7]

图3 乙烷分子活化机理[33]

Fig.3 Activation mechanism of ethane[33]

图4 负载型单金属催化剂DRE的反应性能[17,31]以及载体酸碱性对Ni基催化剂性能的影响[35]

Fig.4 The catalytic performance of DRE on supported single-metal catalyst[17,31] and influence of support acidity and alkalinity on performance of Ni-based catalyst[35]

表1 典型乙烷干重整双金属催化剂研究进展

Table 1 Research progress of typical bimetallic catalysts for DRE

活性组分	载体	负载量（质量分数）	反应温度/K	空速/ (ml/(g∙h))	转化率/%		CO选择性/%	反应时间/10^-4s	文献
活性组分	载体	负载量（质量分数）	反应温度/K	空速/ (ml/(g∙h))	CO₂	C₂H₆	CO选择性/%	反应时间/10^-4s	文献
NiPt	CeO₂	1.51%Ni,1.67%Pt	873	24000	53.4	22.8	92.8	3.4~4.2	[6]
NiPt	TiO₂	1.51%Ni,1.67%Pt	873	24000	27.9	11.1	85.5	3.4~4.2	[6]
NiPt	γ-Al₂O₃	1.51%Ni,1.67%Pt	873	24000	26.5	9.2	93.0	3.4~4.2	[6]
NiPt	SiO₂	1.51%Ni,1.67%Pt	873	24000	28.2	9.2	97.0	3.4~4.2	[6]
PdCo	CeO₂	1%Pd,9%Co	923	18000	31.5	31.0	82.0	>1.2	[17]
PdNi	CeO₂	1%Pd,1%Ni	923	18000	53.0	39.8	86.0	>1.2	[17]
PdCu	CeO₂	1%Pd,1%Cu	923	18000	13.0	12.5	51.0	>1.2	[17]
NiFe	CeO₂-C₂ (25 nm)	4.0%Ni,1.6%Fe	873	24000	8.0	3.9	53.0	4.3	[28]
NiFe	CeO₂	0.48%Ni,1.51%Fe	873	150000	41.3	16.7	98.6	4.0~4.7	[40]
NiFe	SiO₂	0.5%Ni,1.4%Fe	873	24000	0.9	0.4	—	4.0~4.7	[27]
NiFe	ZrO₂	0.5%Ni,1.4%Fe	873	24000	5.6	2.6	37.9	4.0~4.7	[27]
NiFe	CeO₂	2%Ni,5.6%Fe	873	24000	13.1	3.5	67.7	4.0~4.7	[27]

图5 负载型双金属催化剂对DRE反应的催化性能 [5, 40]

Fig.5 The catalytic performance of supported bimetallic catalysts for DRE reaction [5, 40]

图6 载体酸碱性对乙烷干重整反应的影响[35]

Fig.6 The influence of carrier acidity and alkalinity on DRE reaction[35]

表2 CO2-ODH反应催化剂性能

Table 2 Performance of CO2-ODH catalysts

催化剂	反应温度/K	空速/(ml/(g·h))	$X C O 2$ /%	$X C 2 H 6$ /%	$S C 2 H 4$ /%	反应时间/h	文献
CrO _x /Al₂O₃	873	48000	—	6.9	96	2	[54]
CrO _x /ZrO₂	873	48000	—	10	91	2	[54]
CrO _x /Ce _x Zr_1-_x O₂	873	48000	—	2.8	77	2	[54]
Cr/TiO₂-ZrO₂	973	9000	—	48.5	95	—	[55]
(K-Ca)₅₀/(Cr₁₀/H-ZSM-5)₅	973	—	18	17	96	—	[56]
Mo₂C	873	24000	—	12	20	2	[57]
1%(质量) Fe/Mo₂C	873	24000	—	8	71	2	[57]

表2 CO2-ODH反应催化剂性能

Table 2 Performance of CO2-ODH catalysts

催化剂	反应温度/K	空速/(ml/(g·h))	$X C O 2$ /%	$X C 2 H 6$ /%	$S C 2 H 4$ /%	反应时间/h	文献
CrO _x /Al₂O₃	873	48000	—	6.9	96	2	[54]
CrO _x /ZrO₂	873	48000	—	10	91	2	[54]
CrO _x /Ce _x Zr_1-_x O₂	873	48000	—	2.8	77	2	[54]
Cr/TiO₂-ZrO₂	973	9000	—	48.5	95	—	[55]
(K-Ca)₅₀/(Cr₁₀/H-ZSM-5)₅	973	—	18	17	96	—	[56]
Mo₂C	873	24000	—	12	20	2	[57]
1%(质量) Fe/Mo₂C	873	24000	—	8	71	2	[57]

图7 Co负载量对CoO x /SiO2催化剂性能的影响[59]

Fig.7 The effect of Co loading on the performance of CoO x /SiO2[59]

图8 CO2-ODH反应催化剂催化机理示意图[30]

Fig.8 The catalytic mechanism of the CO2-ODH catalysts[30]

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