二氧化碳加氢制长链线性α-烯烃铁基催化剂研究进展

王晨; 张建利; 高新华; 赵天生

doi:10.1016/S1872-5813(22)60058-6

二氧化碳加氢制长链线性α-烯烃铁基催化剂研究进展

doi: 10.1016/S1872-5813(22)60058-6

宁夏大学省部共建煤炭高效利用与绿色化工国家重点实验室化学化工学院, 宁夏银川 750021

基金项目: 宁夏重点研发计划东西部合作项目(2017BY063)和宁夏自然科学基金项目(2022AAC02014)资助

详细信息

通讯作者:
E-mail：zhaots@nxu.edu.cn

中图分类号: O643.36
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出版历程
- 收稿日期: 2022-06-06
- 修回日期: 2022-08-17
- 录用日期: 2022-08-18
- 网络出版日期: 2022-09-05
- 刊出日期: 2023-01-10

Research progress on iron-based catalysts for CO₂ hydrogenation to long-chain linear α-olefins

State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry & Chemical Engineering, Ningxia University, Yinchuan 750021, China

Funds: The project was supported by the East-West Cooperation Project, Key R&D Plan of Ningxia (2017BY063) and Natural Science Foundation of Ningxia (2022AAC02014).

摘要

摘要: 长链线性α-烯烃(linear α-olefins, LAOs)是重要的化工原料，目前，主要通过石油化工路线获得。随着全球温升影响加剧，CO₂控制与资源化利用技术研究受到持续关注。费托合成(Fischer-Tropsch synthesis, FTS)反应产生一定比例的LAOs，提供了制取LAOs可供选择的技术路线。本综述围绕CO₂加氢制LAOs过程，结合其反应途径，分析了Fe基催化剂的研究进展，包括助催化剂和载体的作用，阐述了Fe基催化剂上链增长机理和影响LAOs选择性的关键因素，总结了该反应面临的挑战、可能的解决思路，对高效Fe基催化剂研究进行了展望。
- CO₂加氢 /
- 费托合成 /
- 长链线性α-烯烃 /
- 铁基催化剂
Abstract: Long-chain linear α-olefins (LAOs) are important industrial chemicals, which are mainly obtained from petrochemical process. With the increased impact of the greenhouse effect globally, research on CO₂ control and mitigation has attracted much attention. Fischer-Tropsch synthesis (FTS) provides an alternative route to obtain LAOs. In this paper, research progress on iron-based catalysts including the roles of promoters and supports for the process of CO₂ hydrogenation to LAOs are analyzed. Key factors affecting the selectivity of LAOs are discussed. Challenges and possible solutions of the reaction are summarized, and an outlook for designing high-efficient iron-based catalysts is thus presented.
- CO₂ hydrogenation /
- Fischer-Tropsch synthesis /
- long-chain linear α-olefins /
- iron-based catalysts

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图 1 CO₂加氢生成烯烃机理

Figure 1 Mechanism for CO₂ hydrogenation to olefins

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图 2 FeCoMnK/BeO催化剂上CO₂加氢制烯烃反应机理^[25]

Figure 2 Mechanism of CO₂ hydrogenation to olefins on FeCoMnK/BeO^[25](with permission from Elsevier)

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图 3 Fe₅C₂催化剂上（a）CO₂加氢活性与产物选择性和（b）反应路径^[27]

Figure 3 (a) CO₂ hydrogenation activity and product selectivity and (b) reaction pathways on Fe₅C₂^[27](with permission from Elsevier)

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图 4 Fe基催化剂上CO₂加氢链增长过程^[30]

Figure 4 Chain propagation of CO₂ hydrogenation to olefins on Fe-based catalysts^[30](with permission from Elsevier)

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图 5 链增长几率随碳数变化^[34]

Figure 5 Chain growth probability with carbon number^[34]

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图 6 CO₂加氢过程的再吸附机理^[29]

Figure 6 Readsorption mechanism in CO₂ hydrogenation^[29](with permission from Elsevier)

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图 7 CO₂加氢链增长与链终止^[37]

Figure 7 Chain propagation and termination in CO₂ hydrogenation^[37](with permission from Elsevier)

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图 8 不同K助剂对Fe/C催化CO₂加氢制长链烯烃的影响(a) 产物分布, (b) 含碳K助剂之间的相互转化过程, (c) 反应后催化剂中的Fe₅C₂含量, (d) 不同接触距离的Fe/C-K₂CO₃催化性能 (a:d50, b:TEM)^[44]

Figure 8 Effect of different K promoters on Fe/C for CO₂ hydrogenation to LAOs (a) product distribution, (b) interconversion of carbonaceous K-promoters, (c) Fe₅C₂ content of used catalysts, (d) catalytic performance on Fe/C-K₂CO₃ with different proximity (a:d50, b: estimated by TEM)^[44](with permission from ACS Publications)

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图 9 Na-Fe₂O₃催化CO₂加氢制烯烃 (a) 时空收率、链增长因子、O/P值和(b) CH₄、C₂–C₇烷烃、C₂–C₇烯烃产率与Na含量关系, (c) Na助剂在Fe、C物种演变中的作用^[46]，Fe₅C₂-ZnO-Na催化CO₂加氢制烯烃，(d) Na促进作用机制, (e) Na含量对催化性能的影响^[47]

Figure 9 CO₂ hydrogenation to olefins on Na-Fe₂O₃ (a) FTY, chain growth probability, O/P value and (b) CH₄, ${\rm{C}}^0_2 -{\rm{C}}^0_7 $, ${\rm{C}}^=_2 -{\rm{C}}^=_7 $ yields as a function of Na content, (c) role of Na promoter in the evolution of iron and carbon species^[46], CO₂ hydrogenation to olefins on Fe₅C₂-ZnO-Na, (d) promotion mechanism of Na, (e) effect of Na content on catalytic performance^[47](with permission from Elsevier)

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图 10 Zn助剂对Fe基催化剂CO₂加氢制LAOs影响：(a) Fe₅C₂-ZnO在CO₂加氢过程中结构变化^[53]，(b) Fe₂O₃和Fe2Zn1催化稳定性^[54]

Figure 10 Effect of Zn promoter on Fe-based catalysts for CO₂ hydrogenation to LAOs: (a) structure evolution of Fe₅C₂-ZnO during CO₂ hydrogenation^[53] (b) catalytic stability of Fe₂O₃and Fe2Zn1^[54](with permission from Elsevier and ACS Publications)

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图 11 (a) Fe-Zn-Al^[60]和(b) FeAlO_x催化作用机制^[61]

Figure 11 Catalytic mechanism of (a) Fe-Zn-Al^[60] and (b) FeAlO_x^[61](with permission from ACS Publications)

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图 12 Fe/C-Bio催化剂上CO₂加氢制LAOs反应路径^[62]

Figure 12 Reaction pathways of CO₂ hydrogenation to LAOs on Fe/C-Bio^[62]

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图 13 （a）不同载体负载Fe₅C₂催化加氢性能（b）Fe₅C₂和K/a-Al₂O₃混合方式影响^[71]

Figure 13 (a) Catalytic activity of supported Fe₅C₂ (b) effect of integration manner between Fe₅C₂ and K/a-Al₂O₃^[71](with permission from ACS Publications)

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图 14 ((a)–(b)) 不同载体负载FeNa的CO₂加氢催化性能^[36]，Fe/ZrO₂催化剂的(c) 粒径效应和(d) 催化性能^[73]

Figure 14 ((a)–(b)) Catalytic performance on various supported FeNa^[36], (c) effect of particle size and (d) catalytic performance on Fe/ZrO₂^[73](with permission from Elsevier and ACS Publications)

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图 15 不同形貌Fe/CeO₂催化剂的TEM照片^[80]

Figure 15 TEM images of Fe/ceria^[80] (a): nanoparticles; (b): nanorods; (c): nanocubes

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图 16 FeK/SWNTs和FeK/MWNTs催化CO₂加氢（a）产物选择性（(b)、(c)）链增长因子^[88]

Figure 16 (a) Product selectivity, ((b), (c)) chain growth probability on FeK/SWNTs and FeK/MWNTs for CO₂ hydrogenation^[88](with permission from ACS Publications)

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表 1 Fe基催化剂CO₂加氢制LAOs性能

Table 1 Performance of Fe-based catalysts for CO₂ hydrogenation to LAOs

Catalyst	Reaction conditions				CO₂ conv. /%	CO sel. /%	Hydrocarbon distribution/%			LAOs sel. /%	Ref.
Catalyst	H₂/CO₂	t/℃	p/MPa	GHSV/(mL·g⁻¹·h⁻¹)	CO₂ conv. /%	CO sel. /%	CH₄	${\rm{C}}^=_2 -{\rm{C}}^=_4 $	${\rm{C}}^=_{5+} $	LAOs sel. /%	Ref.
Fe-K₂CO₃	3	320	1	2400	32.4	21.4	12.7	26.5	60.8	71.8	[44]
Fe-Zn-Na	3	330	1.5	15000	43.5	9.2	11.5	16.6	60.7	89.3	[53]
Fe-Mn-Na	3	340	2	12000	35	18.1	10.7	31.7	39.5	−	[57]
Fe-Cu-Na	3	300	1	1800	16.7	31.4	2.4	28.9	64.9	−	[59]
Fe-Zn-Al	3	350	1.5	15000	39.1	22.5	16	24.7	45.6	88.7	[60]
FeAlO_x	1	330	3.5	2000	20.2	16.8	5.4	11.7	66.8	78.4	[61]
Fe/C-bio	3	320	3	2400	31	23.2	11.8	24.4	50.3	80	[62]
Fe-K/Al₂O₃	3	320	3	3600	24.1	23.4	7.5	21.9	40.4	−	[71]
FeK/SWNTs	3	340	2	9000	52.7	9.6	13.5	30.7	39.8	−	[88]

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表 2 碱金属对Fe/ZrO₂催化CO₂加氢影响^[43]

Table 2 Effect of alkali metals on Fe/ZrO₂ for CO₂ hydrogenation^[43](with permission from Elsevier)

Alkali metal	CO₂ conv. /%	Selectivity/%			Hydrocarbon distribution/%
Alkali metal	CO₂ conv. /%	CO	HC	CH₄	${\rm{C}}^=_2 - {\rm{C}}^=_4 $	${\rm{C}}^0_2 - {\rm{C}}^0_4 $	${\rm{C}}^=_{5+} $	${\rm{C}}^0_{5+} $
−	32	25	75	70	0.1	29	0.4	0.5
Li⁺	26	42	56	68	1.4	30	0.1	0.5
Na⁺	39	21	59	21	49	8.8	15	6.2
K⁺	43	15	66	18	44	9.2	19	9.8
Rb⁺	31	15	68	19	43	8.0	19	11
Cs⁺	39	16	67	26	43	9.6	14	7.4

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