Advances in modified Fischer-Tropsch synthesis catalysts for CO/CO2 hydrogenation to higher alcohols

doi:10.16085/j.issn.1000-6613.2023-1068

Abstract

Abstract:

Carbon monoxide/ carbon dioxide (CO/CO₂) hydrogenation to higher alcohols (C₂₊OH), as the important part in C₁ chemistry, is one of the most essential approaches to convert the non-petroleum carbon resources such as coal, natural gas, biomass and CO₂ into liquid fuels and value-added chemicals. The short route, high atom economy and operational feasibility endow this process great potential to convert CO/CO₂ to C₂₊OH. The modified Fischer-Tropsch synthesis (FTS) catalysts are one of the most prospective candidates for CO/CO₂ hydrogenation to C₂₊OH, but the application of these catalysts is still limited by the low space time yield, the wide product distribution and poor catalytic stability, as well as the complicated reaction pathways. Thus, the development of efficient and stable catalysts is crucial but still challenging. Herein, the optimal reaction conditions for CO/CO₂ hydrogenation to C₂₊OH were obtained on the basis of thermodynamics, and the reaction pathways of CO/CO₂ hydrogenation on the modified FTS catalysts were clarified. Subsequently, the progress of iron or cobalt-based catalysts in CO/CO₂ hydrogenation to C₂₊OH were reviewed, including the impact of precursors, promoters, the metal-support interaction on the catalytic performance, and the construction strategies of highly selective and stable catalysts were emphasized. In the future, it is crucial to clarify the catalytic mechanism through advanced characterizations and theoretical calculations, as well as to improve the space time yield of C₂₊OH and to enhance the stability via regulating the surface structure precisely.

Key words: syngas, carbon dioxide, higher alcohols, hydrogenation, catalyst

摘要：

一氧化碳/二氧化碳（CO/CO₂）加氢制低碳醇（C₂₊OH）是碳一化学的重要组成部分，是将煤、天然气、生物质、CO₂等非石油资源转化为液体燃料和高附加值化学品的重要途径。该过程具有工艺路线短、原子经济性高、操作可行性强等优点，是颇具前景的合成路线。改性的费托合成催化剂是该体系最具潜力的催化剂之一，但仍存在低碳醇时空收率不理想、反应网络复杂、产物分布难以调控及稳定性差等问题，高效稳定催化剂的开发极具挑战。本文首先从热力学上分析了CO/CO₂加氢反应制低碳醇适宜的工艺条件；其次，对改性费托合成催化剂上CO/CO₂加氢制低碳醇的反应路径进行了解析，并据此提出催化剂的设计思路。随后，介绍了铁基和钴基催化剂的研究现状，详细阐述了前体结构、助剂、金属-载体相互作用等因素对催化剂性能的影响机制，重点分析了高性能催化剂的构建策略。后续可借助于先进表征技术和理论计算进一步加深对反应机理的认识，并通过催化剂结构的精细调控，获取低碳醇时空收率和催化剂稳定性的提升策略。

关键词: 合成气, 二氧化碳, 低碳醇, 加氢, 催化剂

CLC Number:

TQ426

ZENG Zhuang, LI Kezhi, YUAN Zhiwei, DU Jintao, LI Zhuoshi, WANG Yue. Advances in modified Fischer-Tropsch synthesis catalysts for CO/CO₂ hydrogenation to higher alcohols[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3061-3079.

曾壮, 李柯志, 苑志伟, 杜金涛, 李卓师, 王悦. CO/CO₂ 加氢制低碳醇改性费托合成催化剂研究进展[J]. 化工进展, 2024, 43(6): 3061-3079.

Figures/Tables 20

过程	反应	ΔG^⊖（25℃）/kJ·mol^-1	ΔH^⊖（25℃）/kJ·mol^-1
甲醇合成	$C O + 2 H 2 ⇌ C H 3 O H$	-25.1	-90.5
	$C O 2 + 3 H 2 ⇌ C H 3 O H + H 2 O$	3.5	-49.3
乙醇合成	$2 C O + 4 H 2 ⇌ C 2 H 5 O H + H 2 O$	-221.1	-253.6
	$2 C O 2 + 6 H 2 ⇌ C 2 H 5 O H + 3 H 2 O$	-32.4	-86.7
甲烷化	$C O + 3 H 2 ⇌ C H 4 + H 2 O$	-141.9	-205.8
	$C O 2 + 4 H 2 ⇌ C H 4 + 2 H 2 O$	-113.5	-165.0
WGS反应	$C O + H 2 O ⇌ C O 2 + H 2$	-28.6	-41.1
RWGS反应	$C O 2 + H 2 ⇌ C O + H 2 O$	28.6	41.1

过程	反应	ΔG^⊖（25℃）/kJ·mol^-1	ΔH^⊖（25℃）/kJ·mol^-1
甲醇合成	$C O + 2 H 2 ⇌ C H 3 O H$	-25.1	-90.5
	$C O 2 + 3 H 2 ⇌ C H 3 O H + H 2 O$	3.5	-49.3
乙醇合成	$2 C O + 4 H 2 ⇌ C 2 H 5 O H + H 2 O$	-221.1	-253.6
	$2 C O 2 + 6 H 2 ⇌ C 2 H 5 O H + 3 H 2 O$	-32.4	-86.7
甲烷化	$C O + 3 H 2 ⇌ C H 4 + H 2 O$	-141.9	-205.8
	$C O 2 + 4 H 2 ⇌ C H 4 + 2 H 2 O$	-113.5	-165.0
WGS反应	$C O + H 2 O ⇌ C O 2 + H 2$	-28.6	-41.1
RWGS反应	$C O 2 + H 2 ⇌ C O + H 2 O$	28.6	41.1

催化剂	反应条件				CO转化率 /%	选择性/%		收率/%	时空收率^③/g·g^-1·h^-1		参考文献
催化剂	温度/℃	压力/MPa	H₂/CO比	空速/h^-1	CO转化率 /%	总醇	低碳醇	低碳醇	总醇	低碳醇	参考文献
CNF-2-0.005^①	275	5	1.5	32000^②	11	47	37	4.1	0.670	0.530	[22]
Au-Fe-10	260	3	1	4800	20.0	52.5	31.7	6.3	0.268	0.195	[23]
Co₁Fe₂	260	3	1	9600^②	9.9	51.2	38.5	3.8	0.206	0.143	[24]
CoFe-300-0.25	260	3	2	10800^②	24.3	34.0	31.0	7.5	0.281	0.243	[25]
S₂-CuFeMg-cat	300	4	2	2000	56.9	49.1	32.8	18.7	0.280	0.187	[26]
CuFe@HHSS^①	300	3	2	5000	65.1	46.6	约27.7	18.0	0.118	0.070	[27]
Cu₄Fe₁	260	1	2	2400^②	53.2	29.8	27.1	14.4	0.201	0.183	[11]
3DOM Cu₂Fe₁	200	4.8	1	2000	12.9	47.6	45.0	5.8	0.230	0.218	[28]
Cu_5.2Fe_4.8	350	5.5	2	6000	70.5	12.4	7.2	5.1	0.177	0.102	[29]
CF0.5	260	4	2	5000	18.0	20.8	10.0	1.8	0.050	0.024	[30]
Cu-Fe/SiO₂ (WI)	250	3	2	6000^②	14.0	26.8	8.47	1.2	0.104	0.033	[31]
2Ca-Fe	190	4	2	1800^②	22.2	37.8	—	—	0.039	—	[32]

催化剂	反应条件				CO转化率 /%	选择性/%				收率/%	时空收率 /g·g^-1·h^-1		参考文献
催化剂	温度/℃	压力/MPa	H₂/CO比	空速/h^-1	CO转化率 /%	甲醇	低碳醇	烃类	CO₂	低碳醇	总醇	低碳醇	参考文献
Co₁Ga_0.6-ZnAl-LDO/γ-Al₂O₃	260	3	2	2000	43.5	4.2	54.8	39.9	0.61	23.8	—	—	[44]
0.6Na-Co/AC	220	3	2	2000^②	12.8	3.8	27.0	56.6	12.6	3.5	—	—	[45]
Co1Mn/AC	220	3	2	2000	29.1	1.6	19.8	76.2	2.4	5.8	0.047	0.043	[46]
Co/MnO_x@quasi-MOF-74	230	3	2	15000^②	10.5	3.8	33.9	62.4	0.0	3.6	0.206^③	0.185	[47]
Co_4.7Mo@C	275	3	2	15000^②	48	2.3	9.6	67.0	21.1	4.6	0.123	0.099	[48]
(Cu₁Co₂)₂Al/CNT	230	3	2	3900^②	45.4	2.1	60.8	35.3	1.8	27.6	0.149	0.137	[49]
Co₃Cu-11%CNT(h型)	300	5	1	7200^②	38.5	5.0	57.9	20.7	5.0	22.3	0.683	0.611	[50]
CoCu/5%GE-LFO^①	300	3	2	3900^②	49.7	9.7	47.2	35.2	7.9	23.5	—	—	[51]
(Cu₁Co₂)₂Al-Red^①	250	3	2	3900^②	51.8	1.7	44.1	51.3	2.9	22.8	—	—	[52]
Co₃Cu₁/KIT-6	270	3	2	14400^②	62.9	15.6	30.6	53.1	0.8	19.2	—	—	[53]
Co_2.5Cu₁-773	270	3	1	4800^②	45.3	9.8	31.8	55.5	2.9	14.4	—	—	[9]
CuCoMn	270	2.5	2	7500	29.7	13.7	32.5	51.9	0.4	9.7	—	—	[54]
15Cu5Co@MCN^①	220	2	1	4000^②	20.4	20.2	29.8	38.3	11.7	6.1	0.080	0.048	[55]
Cu_0.25Co_0.75	250	3	2	3900	71.3	2.6	11.2	86.2	—	8.0	0.148	0.121	[56]

催化剂	反应条件				CO₂转化率 /%	选择性/%					收率/%	参考文献
催化剂	温度/℃	压力/MPa	H₂/CO₂比	空速/h^-1	CO₂转化率 /%	甲醇	低碳醇	甲烷	C₂₊烃	CO	低碳醇	参考文献
(K₂O)_5%CuZnFeZrO₂	320	3	3	3600	25.5	12.3	11.0	23.6（所有烃）		53.1	2.81	[77]
FeNaS-0.6^①	320	3	3	8000^②	32.0	0.2	12.6	10.3	56.2	20.7	4.03	[78]
4.6K-CuMgZnFe	320	5	3	6000^②	30.4	1.3	15.9	9.7	42.7	30.6	4.83	[10]
Cs-Cu_0.8Fe_1.0Zn_1.0	330	5	3	4500^②	36.6	0.9	19.8	11.8	46.9	20.6	7.25	[79]
K/Cu-Fe-Zn	300	7	3	5000^③	44.2	2.0	26.9	46.1（所有烃）		5.9	11.9	[80]
RhFeLi/TiO₂NRs-500℃^①	250	3	3	6000	15.7	2.2	31.4	53.9	0	12.5	4.93	[81]
CuZnFe_0.5K_0.15	300	6	3	5000	42.3	4.7	32.0	56.4（所有烃）		6.9	13.5	[82]
Cr(1%)-CuFe	320	4	3	6000^②	38.4	—	29.2	—		14.8	11.2	[83]
CZA(1)/K-CMZF(1)	320	5	3	6000^②	42.3	1.3	17.4	67.6（所有烃）		13.8	7.4	[84]
Co@Co₃O₄/C-N	220	2	3	6000^②	18.6	18.3	1.2	79.5	0.7	0	0.22	[85]
Ir/Co(A)-Na₂O/SiO₂	220	2.1	3	2000	7.6	7.8	7.9	35.7	9.6	38.5	0.60	[86]
Na-Co/SiO₂	250	5	3	4000	18.8	~1.2	~8.3	38.7	22.7	29.1	1.45	[87]
Co₃O₄-m^①	200	2	3	6000^②	28.9	10.2	9.0	53.6	27.2	0	2.60	[88]
Cu/Co₃O₄-2h	250	3	3	36000^②	13.9	2.4	15.2	37.9	19.9	6.5	2.11	[89]
Pt/Co₃O₄-m^①	200	2	3	6000^②	10.7	23.6	23.6	14.9	9.6	28.3	2.53	[88]

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Advances in modified Fischer-Tropsch synthesis catalysts for CO/CO₂ hydrogenation to higher alcohols

CO/CO₂ 加氢制低碳醇改性费托合成催化剂研究进展

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