以CO2为原料的第三代生物炼制现状

doi:10.16085/j.issn.1000-6613.2024-1982

化工进展 ›› 2025, Vol. 44 ›› Issue (5): 2811-2824.DOI: 10.16085/j.issn.1000-6613.2024-1982

• CO2减排利用 • 上一篇

以CO₂为原料的第三代生物炼制现状

李煜真¹^,²(), 贺铭敬¹^,², 王皓明³, 马小清¹, 刘立成³, 李福利¹^,⁴()

^1.太阳能光电转化与利用全国重点实验室，青岛新能源山东省实验室，一碳炼制山东省工程研究中心，中国科学院青岛生物能源与过程研究所，山东青岛 266101
^2.中国科学院大学，北京 100049
^3.中国海洋大学，山东青岛 266100
^4.山东能源研究院，山东青岛 266101

收稿日期:2024-12-04 修回日期:2025-03-27 出版日期:2025-05-25 发布日期:2025-05-20
通讯作者: 李福利
作者简介:李煜真（1999—），男，硕士研究生，研究方向为一碳气体生物转化与利用。E-mail：liyz@qibebt.ac.cn。
基金资助:
国家自然科学基金联合基金重点项目(U22A20425)

Current status of the third-generation carbon-one biorefinery using CO₂ as raw material

LI Yuzhen¹^,²(), HE Mingjing¹^,², WANG Haoming³, MA Xiaoqing¹, LIU Licheng³, LI Fuli¹^,⁴()

^1.Key Laboratory of Photoelectric Conversion and Utilization of Solar Energy (CAS), Qingdao New Energy Shandong Laboratory, Shandong C1 Refinery Engineering Research Center, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, Shandong, China
^2.University of Chinese Academy of Sciences, Beijing 100049, China
^3.Ocean University of China, Qingdao 266100, Shandong, China
^4.Shandong Energy Institute, Qingdao 266101, Shandong, China

Received:2024-12-04 Revised:2025-03-27 Online:2025-05-25 Published:2025-05-20
Contact: LI Fuli

摘要/Abstract

摘要：

利用微生物发酵一碳气体生产生物燃料及化学品，是当今实现碳资源捕捉利用和绿色生物制造的重要途径之一。CO₂和CO、甲烷、甲醇以及甲酸等含有一个碳原子的物质被称为一碳（one carbon，C₁）资源，其来源广泛且价格低廉，有望成为生物制造的替代原料。C₁原料生物转化有助于缓解温室效应、助力“碳中和”目标。本文总结了近年来以CO₂为原料通过微生物炼制生产重要能源和化学品的研究进展，论述CO₂的生物代谢途径以及产物合成途径，讨论以CO₂为原料的C₁生物炼制中微生物的工程化改造，并展望未来绿色生物制造的新路线。

关键词: 一碳气体, 生物炼制, 固碳途径, 代谢工程

Abstract:

The microbial fermentation of one-carbon (C₁) gases to produce biofuels and chemicals represents a key pathway for carbon resource capture, utilization, and green biomanufacturing. One-carbon feedstocks, such as CO, CO₂, methane, methanol, and formic acid, are characterized by their single-carbon atom composition. These resources are abundant, low-cost, and hold potential as alternative feedstocks for biomanufacturing. Additionally, their bioconversion contributes to mitigating the greenhouse effect and supports the achievement of carbon neutrality goals. This article reviews recent progress in microbial refining of CO₂ to produce essential organic acids and alcohols, elaborates on the biological metabolic pathways of CO₂ and product synthesis, discusses the genetic engineering of microorganisms in C₁ biorefining, and envisions future pathways for green biomanufacturing.

Key words: one carbon, bio-refinery, carbon fixation, metabolic engineering

中图分类号:

Q819

李煜真, 贺铭敬, 王皓明, 马小清, 刘立成, 李福利. 以CO₂为原料的第三代生物炼制现状[J]. 化工进展, 2025, 44(5): 2811-2824.

LI Yuzhen, HE Mingjing, WANG Haoming, MA Xiaoqing, LIU Licheng, LI Fuli. Current status of the third-generation carbon-one biorefinery using CO₂ as raw material[J]. Chemical Industry and Engineering Progress, 2025, 44(5): 2811-2824.

图/表 9

图1 第三代生物炼制技术发展里程碑[6]

表1 不同代谢途径特点

代谢途径	关键酶	代谢特点	是否厌氧	能量需求（以 ATP数量计算）	还原力需求（以 NAD(P)H数量计算）	能量来源
卡尔文循环	RuBisCO	与磷酸戊糖途径密切相关	否	9	4	光能
伍德-永达尔途径	CO dehydrogenase, formate dehydrogenase, hydrogenase	直接还原CO₂	是	<1	4	氢气
还原性甘氨酸途径	reductive glycine cleavage complex	直接还原CO₂	否	2	4	光能、硫
二羧酸/4-羟基丁酸循环	4-hydroxy butyryl-CoA dehydratase	通过pyruvate synthase固定1分子CO₂，通过PEP羧化酶固定1分子碳酸氢盐	是	5	4	氢气、硫
3-羟基丙酸/4-羟基丁酸循环	4-hydroxy butyryl-CoA dehydratase	通过acetyl-CoA/propionyl-CoA羧化酶固定2分子碳酸氢盐	否	6	4	氢气、氧气
3-羟基丙酸双循环	malonyl-CoA reductase, propionyl-CoA synthase	通过acetyl-CoA/propionyl-CoA羧化酶固定2分子碳酸氢盐	否	7	4	光能、硫
还原性三羧酸循环	ATP-citrate lyase, 2-ketoglutarate synthase	通过逆转TCA循环来固定2分子CO₂	否	2	4	光能、硫

图2 卡尔文循环代谢示意图Ribulose-5-P—5-磷酸核酮糖；Ribulose-1,5-BP—1,5-二磷酸核酮糖；3-P-glycerate—3-磷酸甘油酸；1,3-BP-glycerate—1,3-二磷酸甘油酸；3-P-glyceraldehyde—3-磷酸甘油醛

图3 伍德-永达尔途径Formate—甲酸；10-formyl-THF—10-甲酰四氢叶酸；5,10-methenyl-THF—5,10-次甲基四氢叶酸；5,10-methylene-THF—5,10-亚甲基四氢叶酸；5-methyl-THF—5-甲基四氢叶酸；CoFeS—钴铁硫蛋白；Acetyl-CoA—乙酰辅酶A

图4 还原性甘氨酸途径Formate—甲酸；THF—四氢叶酸；10-formyl-THF—10-甲酰四氢叶酸；5,10-methenyl-THF—5,10-次甲基四氢叶酸；5,10-methylene-THF—5,10-亚甲基四氢叶酸；Glycine—甘氨酸；SHMT—丝氨酸羟甲基转移酶；Serine—丝氨酸；Pyruvate—丙酮酸

图5 DC/4HB 循环Acetyl-CoA—乙酰辅酶A；Pyruvate—丙酮酸；Phosphoenolpyruvate—磷酸烯醇式丙酮酸；Oxaloacetate—草酰乙酸；Malate—苹果酸；Fumarate—延胡索酸；Succinate—琥珀酸；Succinate semialdehyde—琥珀酸半醛；4-hydroxybutyrate—4-羟基丁酸；Crotonyl-CoA—巴豆酰辅酶A；3-hydroxybutyryl-CoA—3-羟基丙酰辅酶A；Acetoacetyl-CoA—乙酰乙酰辅酶A

图6 3HP/4HB循环Acetyl-CoA—乙酰辅酶A；Malonyl-CoA—丙二酰辅酶A；Malonate semialdehyde—丙二酰半醛；3-hydroxypropionate—3-羟基丙酸；3-hydroxypropionyl-CoA—3-羟基丁酰辅酶A；Acrylyl-CoA—丙烯酰辅酶A；Propionyl-CoA—丙酰辅酶A；Methylmalonyl-CoA—甲基丙二酰辅酶A；Succinyl-CoA—琥珀酰辅酶A；Succinate semialdehyde—琥珀酸半醛；4-hydroxybutyrate—4-羟基丁酸；Crotonyl-CoA—巴豆酰辅酶A；3-hydroxybutyryl-CoA—3-羟基丙酰辅酶A；Acetoacetyl-CoA—乙酰乙酰辅酶A

图7 3-HP双循环Acetyl-CoA—乙酰辅酶A；Malonyl-CoA—丙二酰辅酶A；Malonate semialdehyde—丙二酸半醛；3-hydroxypropionyl-CoA—3-羟基丙酰辅酶A；Acrylyl-CoA—丙烯酰辅酶A；Propionyal-CoA—丙酰辅酶A；第一循环—Methylmalonyl-CoA—甲基丙二酰辅酶A；Succinyl-CoA—琥珀酰辅酶A；Succinate—琥珀酸；UOred/UOox—某还原态蛋白/某氧化态蛋白；Fumarate—延胡索酸；Malate—苹果酸；Malyl-CoA—苹果酰辅酶A；Glyoxylate—乙醛酸；第二循环—Metylmalyl-CoA—甲基苹果酰辅酶A；Mesaconyl-CoA—中康酰辅酶A；Citramalyl-CoA—柠苹酸辅酶A；Pyruvate—丙酮酸

图8 还原TCA循环Succinate—琥珀酸；Succinyl-CoA—琥珀酰辅酶A；Fdred/Fdox—还原/氧化态铁氧还蛋白；2-Ketoglutarate—2-酮戊二酸；Isocitrate—异柠檬酸；Aconitate—乌头酸；Citrate—柠檬酸；Acetyl-CoA—乙酰辅酶A；Oxaloacetate—草酰乙酸；Matale—苹果酸；Fumarate—延胡索酸

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以CO₂为原料的第三代生物炼制现状

Current status of the third-generation carbon-one biorefinery using CO₂ as raw material

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