CO/CO2 加氢制低碳醇改性费托合成催化剂研究进展

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

摘要/Abstract

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

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

中图分类号:

TQ426

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.

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.

图/表 20

图1 乙醇和低碳醇主要合成路线

图2 CO/CO2加氢制低碳醇催化剂中低碳醇选择性与CO/CO2转化率的关系

表1 CO/CO2加氢反应过程中重要反应的热力学数据[17-18]

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

表1 CO/CO2加氢反应过程中重要反应的热力学数据[17-18]

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

图3 CO/CO2加氢生成乙醇和甲烷时平衡组成随温度变化趋势[18-19]

图4 CO/CO2加氢生成低碳醇、甲醇、烃类的反应路径[7,19]

表2 CO加氢制低碳醇Fe基催化剂的性能汇总

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]

图5 Ca-Fe催化上低碳醇的生成路径[32]

图6 CuFe双金属催化剂在反应过程中的产物选择性变化和相分离[39]

图7 CuFeMg-LDHs衍生Cu4Fe1催化剂中Fe5C2纳米簇在Cu纳米颗粒上的分布[11]

图8 酸性MFI沸石负载的CuFe催化剂上CO加氢制低碳醇反应网络

图9 Au-Fe-10双面型催化剂长周期反应过程中的稳定性[23]

图10 CoFe合金碳化物的结构及Co/Fe摩尔比对其稳定性的影响[24-25]

表3 CO加氢制低碳醇Co基催化剂的性能汇总

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]

图11 Co2C(111)和面心立方堆积Co(100)表面CO吸附能、吸附构型和CO解离活化能[62]

图12 CoGa-ZnAl-LDO/γ-Al2O3催化剂的结构演化过程和元素分布[65]

图13 通过DFT计算和微动力学模型预测的甲烷、甲醇、乙醇的选择性随催化剂中单金属Cu位点、单金属Co位点、CuCo合金位点的相对比例的变化趋势[68]

图14 核壳型Cu@(CuCo-alloy)/Al2O3催化剂在原位生长、焙烧和还原过程中物相演变过程[71]

表4 CO2加氢制低碳醇改性FTS催化剂的性能汇总

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]

图15 Cs-Cu0.8Fe1.0Zn1.0催化剂上CO2加氢的反应路径[79]

图16 辅助光照处理对Na-Co@C催化剂表面中间体和反应路径的影响[93]

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CO/CO₂ 加氢制低碳醇改性费托合成催化剂研究进展

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

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