合成气制高碳醇钴基催化剂研究进展

doi:10.16085/j.issn.1000-6613.2022-1022

摘要/Abstract

摘要：

6个碳原子以上的高碳醇，在工业领域有着广泛的应用。合成气制备高碳醇原料来源广泛、技术路线短。钴基催化剂利用Co⁰相解离CO、促进碳链增长的能力，引入Cu和Co₂C相促进CO的非解离活化以调控醇类的选择性。本文综述了近年来钴基合成气制备高碳醇催化剂的研究进展，指出活性相在反应条件下的均匀分散是高选择性生成C₆₊OH的关键，可以通过对催化剂表面预处理或利用水滑石、钙钛矿等结构促进分散。载体和助剂通过影响表面金属的偏析或者CoC_x相的生成来影响反应性能。文中指出：需要开发表面态的精确表征与可控合成技术，研究催化剂结构、反应网络在反应气氛下的动态变化，提升高碳醇的选择性与催化剂寿命。

关键词: 合成气, 高碳醇, 改性费托, Co基催化剂

Abstract:

Linear alcohols with six carbon atoms or more are used extensively in industry. Syngas to higher alcohols is a short route suitable for a wide variety of carbon resources. Cobalt-based catalysts have the Co⁰ active phase to dissociate CO and promote the carbon-chain growth, and Cu and Co₂C active phase are introduced to promote the CO no-dissociative activation and enhance the selectivity towards alcohols. This article summarized the recent progress on Co-catalyzed syngas to higher alcohols, and found the highly dispersed active phases under reaction conditions was the key of high C₆₊OH selectivity. Dispersion of active phase could be improved by pretreatment on the catalyst surface, or via the structure of hydrotalcite or perovskite. Supports and promoters would influence the surface metal segregation and the formation of CoC _x, thus affected the catalytic performance. To improve the selectivity towards higher alcohols and prolong catalyst life, further studies were needed on accurate characterization of catalyst surface state, controllable synthesis technology, dynamic evolution of the catalyst structure and reaction network under the reaction atmosphere.

Key words: syngas, higher alcohols, modified Fischer-Tropsch synthesis, Co-based catalyst

中图分类号:

田园, 娄舒洁, 孟闪茹, 闫敬如, 肖海成. 合成气制高碳醇钴基催化剂研究进展[J]. 化工进展, 2023, 42(4): 1869-1876.

TIAN Yuan, LOU Shujie, MENG Shanru, YAN Jingru, XIAO Haicheng. Recent progress of Co-based catalysts for higher alcohols synthesis form syngas[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1869-1876.

图/表 3

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催化剂	反应条件	CO转化率 /%	选择性/%			醇类选择性/%			文献
催化剂	反应条件	CO转化率 /%	HC	ROH	CO₂	C₁OH	C_2~5OH	C₆₊OH	文献
Cu@(CuCo-alloy)/Al₂O₃(Cu∶Co=2∶1)	220℃, 2MPa, H₂/CO=2, GHSV=2000mL/(g_cat·t)	21.5	42.2	50.6	7.2	19.2	31.9	48.9	[59]
15Co4Cu4Mn	220℃, 3MPa, GHSV=500/h	52.2	72.7	23.5	3.8	6.6	54.2	39.2	[61]
Co/3GO-OMS	225℃, 3MPa, H₂/CO=2, GHSV=10800mL/(g_cat·h)	35.4	56.2	43.3	0.5	44.3	52.6	3.1	[32]
15Co-5Fe/AC	220℃, 3MPa, GHSV=4L_syngas/(g_cat·t)	30.9	80.4	18.1	1.5	11.4	57.5	31.0	[54]
0.5La-Co/AC	220℃, 3MPa, GHSV=1500/h	21.4	56.0	38.9	5.1	7.7	58.1	34.2	[49]
0.01Li-Co/AC	220℃, 3MPa, GHSV=500/h	29.4	67.7	31.2	1.1	4.9	48.2	56.9	[40]
15Co-2.1SiO₂/AC	220℃, 3MPa, GHSV=500/h	52.7	73.2	25.9	0.9	4.2	37.7	58.5	[34]

催化剂	反应条件	CO转化率 /%	选择性/%			醇类选择性/%			文献
催化剂	反应条件	CO转化率 /%	HC	ROH	CO₂	C₁OH	C_2~5OH	C₆₊OH	文献
Cu@(CuCo-alloy)/Al₂O₃(Cu∶Co=2∶1)	220℃, 2MPa, H₂/CO=2, GHSV=2000mL/(g_cat·t)	21.5	42.2	50.6	7.2	19.2	31.9	48.9	[59]
15Co4Cu4Mn	220℃, 3MPa, GHSV=500/h	52.2	72.7	23.5	3.8	6.6	54.2	39.2	[61]
Co/3GO-OMS	225℃, 3MPa, H₂/CO=2, GHSV=10800mL/(g_cat·h)	35.4	56.2	43.3	0.5	44.3	52.6	3.1	[32]
15Co-5Fe/AC	220℃, 3MPa, GHSV=4L_syngas/(g_cat·t)	30.9	80.4	18.1	1.5	11.4	57.5	31.0	[54]
0.5La-Co/AC	220℃, 3MPa, GHSV=1500/h	21.4	56.0	38.9	5.1	7.7	58.1	34.2	[49]
0.01Li-Co/AC	220℃, 3MPa, GHSV=500/h	29.4	67.7	31.2	1.1	4.9	48.2	56.9	[40]
15Co-2.1SiO₂/AC	220℃, 3MPa, GHSV=500/h	52.7	73.2	25.9	0.9	4.2	37.7	58.5	[34]

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