CO<sub>2</sub>催化制备高附加值多碳含氧化合物的研究进展

李永恒; 吴冲冲; 王文波; 辛靖; 米晓彤; 杨国明; 苏梦军; 张斯然; 李洪宝

doi:10.1016/S1872-5813(23)60404-9

CO₂催化制备高附加值多碳含氧化合物的研究进展

doi: 10.1016/S1872-5813(23)60404-9

中海油化工与新材料科学研究院, 北京, 102209

基金项目: 中国海洋石油集团有限公司科技项目（KJGG-2022-12-CCUS-030401，030402）资助

详细信息

通讯作者:
Tel: +086-010-89913170, E-mail: liyh90@cnooc.com.cn

中图分类号: O643.36
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- 被引次数: 0
出版历程
- 收稿日期: 2023-10-24
- 修回日期: 2023-11-27
- 录用日期: 2023-11-27
- 网络出版日期: 2023-12-13
- 刊出日期: 2024-04-03

Research progress on CO₂ catalytic conversion to value-added oxygenates

CNOOC Institute of Chemicals & Advanced Materials, Beijing 102209, China

Funds: The project was supported by CNOOC Science and Technology Projects (KJGG-2022-12-CCUS-030401，030402)

摘要

摘要: 将温室气体CO₂通过化学反应路径制备高附加值多碳含氧化合物如乙醇、乙酸、丙醛、丙酸、丁醇等具有挑战性。由于C−C偶联反应的复杂性和成键的不可控性，导致合成多碳高值含氧化合物困难。本工作总结了近期在连续流固定床条件下CO₂催化合成高附加值多碳含氧化合物的研究进展。首先归纳了CO₂加氢路径下可能的反应机理；其次总结了CO₂直接加氢（一步法、串联法）、CO₂与轻烃重整、CO₂氢甲酰化等不同反应路径下具有潜力的催化剂，包括金属碳化物、碱金属修饰的Cu、Fe、Co、Rh等单金属或二元金属制备多碳高值含氧化合物的特点，并进一步阐述了不同催化剂上的作用机制。最后对目前存在的问题和未来可能的解决方案进行了讨论和展望。
- 二氧化碳转化 /
- 多碳含氧化合物 /
- 一步法 /
- 串联催化
Abstract: Chemical conversion of greenhouse gas CO₂ into value-added oxygenates such as ethanol, acetic acid, propanal, propionic acid, butanol, etc. is challenging due to the complexity of C−C coupling and the uncontrollable bonding. In this review, recent research progresses on the synthesis of multi-carbon oxygenates from CO₂ in fixed bed reactor are provided. Firstly, the reaction mechanisms of CO₂ hydrogenation are summarized. Then, the potential catalysts applied in one-step or tandem CO₂ hydrogenation, dry reforming with light hydrocarbons and hydroformylation were introduced over metal carbides, alkali metal modified single or binary metal catalysts such as Cu, Fe, Co, Rh, etc. The reaction mechanism over different catalysts were further elaborated. Finally, the problems and outlook are discussed.
- CO₂ conversion /
- multi-carbon oxygenates /
- one-step method /
- tandem catalysis

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FIG. 3074. FIG. 3074.

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图 1 温度对CO₂加氢制备化学品的平衡转化率的影响^[2]

Figure 1 Influence of temperature on equilibrium of CO₂ hydrogenation to chemicals^[2] (with permission from Science China Press)

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图 2 二氧化碳催化转化制含氧化合物的不同反应路径和产品

Figure 2 The different reaction paths and products of CO₂ catalytic conversion to oxygenates

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图 3 CO插入机理^[21]

Figure 3 Mechanism of CO insertion^[21] (with permission from Elsevier)

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图 4 CO₂加氢反应网络总结^[22]

Figure 4 Reaction networks of CO₂ hydrogenation^[22] (with permission from Wiley)

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图 5 CO₂加氢反应的热力学分析^[26]

Figure 5 Thermodynamic analyses of CO₂ hydrogenation^[26] (with permission from Elsevier)

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图 6 0.1K-CMZF和4.6K-CMZF催化剂的原位红外谱图和不同中间产物峰强度^[32]

Figure 6 In-situ DRIFTS spectra and dynamic IR peak intensities of gaseous of CO₂ hydrogenation over 0.1K-CMZF ((a), (b)) and 4.6K-CMZF ((c), (d)) catalyst^[32] (with permission from American Chemical Society)

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图 7 InFe/K-Al₂O₃催化剂上的CO₂加氢制多碳醇反应机理示意图^[35]

Figure 7 Reaction mechanism of higher alcohols formation from CO₂ hydrogenation over InFe/K-Al₂O₃ catalyst^[35] (with permission from American Chemical Society)

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图 8 不同载体上Co₂O在CO₂加氢催化反应中的稳定性^[34]

Figure 8 Stability mechanism of supported Co₂C in CO₂ hydrogenation to ethanol^[34] (with permission from Elsevier)

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图 9 K修饰Ni-Zn双金属碳化物的CO₂加氢催化性能和K-Ni₁Zn₃-450催化剂不同处理时间下的XRD谱图^[22]

Figure 9 Catalytic performance of K modified Ni-Zn carbide for CO₂ hydrogenation and the XRD patterns of K-Ni₁Zn₃-450 at different time on stream^[22] (with permission from Wiley)

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图 10 Na-Rh@S-1催化剂二氧化碳加氢转化的反应机理^[8]

Figure 10 Proposed reaction mechanism for CO₂ hydrogenation over Na-Rh@S-1 catalysts^[8] (with permission from American Chemical Society)

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图 11 Pd₂Ce@Si₁₆催化剂的纳米反应器富水模型和对CO₂加氢制乙醇的催化反应机制^[49]

Figure 11 Proposed reaction mechanism and model of in-situ generated water enriched in nano reactor over Pd₂Ce@Si₁₆ catalyst for CO₂ hydrogenation^[49] (with permission from American Chemical Society)

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图 12 Cs修饰的Cu-Fe-Zn多功能催化剂用于CO₂加氢制备多碳醇的催化反应路径^[9]

Figure 12 Illustration for the reaction pathways of CO₂ hydrogenation over the Cs promoted Cu-Fe-Zn catalysts^[9] (with permission from American Chemical Society)

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图 13 CZA/K-CMZF双功能催化剂不同装填方式对CO₂加氢转化性能的影响及反应中的协同效应^[6]

Figure 13 Effect of packed manners on the catalytic performance and the proximity effect for CO₂ hydrogenation over multifunctional CZA/K-CMZF catalyst^[6] (with permission from American Chemical Society)

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图 14 催化剂不同装填方式对CO₂加氢转化性能的影响及Na-Fe@C/K-CuZnA催化剂上的反应网络l^[61]

Figure 14 Effect of intimacy modes on the catalytic performance for CO₂ hydrogenation over different catalysts and the reaction network via the Na-Fe@C/K-CuZnAl multifunctional catalyst^[61] (with permission from American Chemical Society)

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图 15 CO₂转化为乙酸和丙酸的合理反应机制^[24]

Figure 15 Plausible reaction mechanism for the conversion of CO₂ to acetic and propionic acids^[24] (with permission from American Chemical Society)

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图 16 CO₂还原合成氢甲酰化原料CO和H₂的反应路径^[67]

Figure 16 Proposed mechanism for hydrosilane reduction of CO₂ to CO and H₂^[67] (with permission from American Chemical Society)

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图 17 CO₂与烷烃涉及反应的热力学分析以及不同反应器内的产物平衡^[16]

Figure 17 Diagram of standard Gibbs free energy change (ΔG⁰) of reactions for CO₂ and ethane and the equilibrium species distribution within two reactors^[16] (with permission from Springer Nature)

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表 1 金属碳化物催化剂催化CO₂加氢制多碳醇性能比较

Table 1 Catalytic performance comparison for CO₂ Hydrogenation to C₂₊ alcohols over typical metal carbide catalysts

Catalyst	Reaction temp./ ℃	Reaction pressure/ MPa	H₂/ CO₂	WHSV/ (mL·g⁻¹·h⁻¹)	CO₂ conversion/ %	Selectivity/C%^a					C₂₊OH/ ROH/ %	C₂₊OH STY/ (mg·g⁻¹·h⁻¹)	Stability/ h	Ref.
Catalyst	Reaction temp./ ℃	Reaction pressure/ MPa	H₂/ CO₂	WHSV/ (mL·g⁻¹·h⁻¹)	CO₂ conversion/ %	CO	CH₄+ C₂₊H_x	CH₃OH	C₂₊OH	other oxy.	C₂₊OH/ ROH/ %	C₂₊OH STY/ (mg·g⁻¹·h⁻¹)	Stability/ h	Ref.
10Mn₁K-FeC^b	300	3	3	6000	40.5	33.4	55.9	0.2	10.5	0	92.9	−	100	[31]
4.6K-CuMgZnFe	320	5	3	6000	30.4	30.6	52.4	1.3	15.9	0	89.8	69.6	100	[32]
Na-ZnFe@C^b	320	5	3	9000	38.4	7.6	68.1	1.7	22.6	~ 0	90.5	158.1	528	[33]
Na–Co/SiO₂	250	5	3	4000	18.82	29.05	61.41	0.85	8.69	0	87.5	−	300	[34]
Na–Co/Si₃N₄	250	5	3	4000	17.75	39.16	51.65	0.75	8.44	0	88.5	−	300	[34]
4K-Ni₁Zn₃−300^b	350	3	3	4800	29.7	47.9	42.5	0.5	6.7	1.3	90	62.7	80	[22]
^a: C% represents the carbon atoms concentration of given product to the total carbon-containing products, ^b: C₂₊OH/ROH fraction (%) was calculated according to the carbon atoms concentration of MeOH to C₂₊OH.

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表 2 金属活性位催化剂催化二氧化碳加氢制乙醇性能比较

Table 2 Catalytic performance comparison for CO₂ hydrogenation to C₂₊ alcohols over different metallic catalysts

Active metal	Catalyst	Reaction temp./ ℃	Reaction pressure/ MPa	H₂/ CO₂	WHSV/ (mL·g⁻¹·h⁻¹)	CO₂ conversion/ %	Selectivity/C%					ROH/ C₂₊OH/ C%	C₂₊OH STY/ (mg·g⁻¹·h⁻¹)	Ref.
Active metal	Catalyst	Reaction temp./ ℃	Reaction pressure/ MPa	H₂/ CO₂	WHSV/ (mL·g⁻¹·h⁻¹)	CO₂ conversion/ %	CO	CH₄+ C₂₊H_x	CH₃OH	C₂₊OH	other oxy.	ROH/ C₂₊OH/ C%	C₂₊OH STY/ (mg·g⁻¹·h⁻¹)	Ref.
Rh	Na-Rh@S-1	250	5	3	6000	10	32	~ 24.8	~ 25.2	~ 18	0	~ 41.7	72 ^b	[8]
	Rh-VO_x/MCM-41	250	3	3	6000^a	12.1	20.1	48.3	7.5	24.1	0	76.3	47.9	[45]
	RhFeLi/TiO₂	250	5	3	6000^a	15.7	12.5	53.9	2.2	31.3	0.1	93.4	145.3	[46]
	Rh-Li/SiO₂	240	5	3	6000	7	15.7	63.5	5.2	15.5	0	74.9	33.1	[47]
	Rh-Fe/SiO₂	260	5	3	6000	26.7	19.7	34.7	29.4	16	0	35.2	130.3	[48]
Pd	Pd₂Ce@Si₁₆	240	3	3	3000	5.9	~ 0	~ 0	~ 1	98.7	0	~ 99	252^c	[49]
	Pd/Fe₃O₄	250	3	3	8000	1.4	~ 0	~ 0	2	98	0	98	440^c	[50]
In	2.5K₅Co-In₂O₃	380	4	3	2250	36	81	6.5	1.5	11.2	0	88.1	170	[51]
Co	Ir/Co(A)-Na₂O/SiO₂	220	2.1	3	2000^a	7.6	38.5	45.3	7.8	7.9	0	50.3		[52]
	Co/La₄Ga₂O₉	280	3.5	3	3000	9.6	10.8	52.2	13.7	23.3	0	62.9	34.5	[53]
	Ga(0.4)CuCo	220	3	3	6000	17.8	2.3	45.4	27.5	24.8	0	47.4	1.4 ^d	[54]
Fe	FeNaS-0.6	320	3	3	8000	32	20.7	66.5	0.16	12.6	0	98.8	78.5	[55]
Cu	Cu@Na-Beta	300	1.3	3	12000	7.9	30.5	~ 0	~ 0	69.5	0	~ 100	258	[23]
CuFe	KFeCu/α-ZrO₂	320	4	3	3000	30	30	49	1.4	19.6	0	93.3	59.1	[56]
^a: GHSV of given catalyst, ^b: C₂₊OH STY per unit mass of active metal (mmol·g⁻¹·h⁻¹), ^c: C₂₊OH STY per unit mass of active metal (mmol·g⁻¹·h⁻¹), ^d: C₂₊OH STY per unit mass of catalyst (mmol·g⁻¹·h⁻¹).

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表 3 串联催化剂催化CO₂加氢制多碳醇性能比较

Table 3 Catalytic performance comparison for CO₂ hydrogenation to C₂₊ alcohols over different tandem catalysts

Catalyst	Reaction temp./ ℃	Reaction pressure/ MPa	H₂/ CO₂	WHSV/ (mL·g⁻¹·h⁻¹)	CO₂ conversion/ %	Selectivity/C%					C₂₊OH/ ROH/ %	C₂₊OH STY/ (mmol·g⁻¹·h⁻¹)	Ref.
Catalyst	Reaction temp./ ℃	Reaction pressure/ MPa	H₂/ CO₂	WHSV/ (mL·g⁻¹·h⁻¹)	CO₂ conversion/ %	CO	CH₄+ C₂₊H_x	CH₃OH	C₂₊OH	other oxy.	C₂₊OH/ ROH/ %	C₂₊OH STY/ (mmol·g⁻¹·h⁻¹)	Ref.
Cs-Cu_0.8Fe₁Zn₁	330	5	3	4500	36.6	~ 20.3	58	0.9	19.8	0	93.8	1.47	[9]
NaFe@KCuZnAl^a	320	5	3	4500	39.2	9.4	49.4	4.2	37	0	~ 86.5	6.6	[61]
MnCuK-Fe₅C₂/CuZnAlZr^a	300	3	3	6000	42.1	22.7	60.6	1.2	15.5	0	89.7	3.8	[62]
Co₂C\|\|CuZnAl	250	5	3	12000	20.7	~ 21	~ 57	~ 3.6	~ 18.4	0	~ 84.5	1.6	[63]
^a: C₂₊OH/ROH fraction(%) was calculated according to the carbon atoms concentration of MeOH to C₂₊OH.

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