化学-生物级联转化CO2合成单细胞蛋白研究进展

doi:10.16085/j.issn.1000-6613.2024-2057

化工进展 ›› 2025, Vol. 44 ›› Issue (5): 2429-2440.DOI: 10.16085/j.issn.1000-6613.2024-2057

• 合成生物制造 • 上一篇

化学-生物级联转化CO₂合成单细胞蛋白研究进展

吴孟勤¹^,²^,³(), 王佳瑶²^,³^,⁴, 徐友强¹(), 王钰²^,³()

^1.北京工商大学食品与健康学院，北京 100048
^2.中国科学院天津工业生物技术研究所低碳合成工程生物学重点实验室，天津 300308
^3.国家合成生物技术创新中心，天津 300308
^4.天津科技大学生物工程学院，天津 300222

收稿日期:2024-12-18 修回日期:2025-01-25 出版日期:2025-05-25 发布日期:2025-05-20
通讯作者: 徐友强,王钰
作者简介:吴孟勤（1998—），女，博士研究生，研究方向为微生物进化技术与单细胞蛋白合成。E-mail：znwmqin@163.com.cn。
基金资助:
国家重点研发计划(2024YFA0918100);天津市自然科学基金(24JCJQJC00010)

Progress in cascade conversion of CO₂ to single cell protein through chemical and biological catalysis

WU Mengqin¹^,²^,³(), WANG Jiayao²^,³^,⁴, XU Youqiang¹(), WANG Yu²^,³()

^1.School of Food and Health, Beijing Technology and Business University, Beijing 100048, China
^2.Key Laboratory of Engineering Biology for Low-Carbon Manufacturing, Tianjin Institute of Industrial Biotechnology, Chinese Academy of Sciences, Tianjin 300308, China
^3.National Center of Technology Innovation for Synthetic Biology, Tianjin 300308, China
^4.College of Biotechnology, Tianjin University of Science and Technology, Tianjin 300222, China

Received:2024-12-18 Revised:2025-01-25 Online:2025-05-25 Published:2025-05-20
Contact: XU Youqiang, WANG Yu

摘要/Abstract

摘要：

工业发展导致CO₂大量排放，加剧了全球温室效应和环境污染。此外，全球人口的不断增长将会导致蛋白质供应不足。通过化学催化CO₂还原合成甲醇等有机一碳化合物，进一步通过微生物将甲醇转化为多碳产物，是一条高效的CO₂固定和转化利用路线。因此，从原料和产品层面考虑，本文提出了利用化学-生物级联转化CO₂生产单细胞蛋白（single cell protein, SCP）的策略，即将CO₂通过化学转化生产甲醇，再进一步利用微生物细胞工厂代谢甲醇和无机铵生产SCP，SCP产品有望应用于饲料和食品工业。本文首先介绍了CO₂加氢可持续生产甲醇的反应过程及反应机制，总结了相关催化剂的研究进展。其次，介绍了自然界中发现的可利用甲醇的微生物及甲醇代谢途径，以及利用甲醇生产SCP的研究进展。最后，对CO₂化学-生物级联转化工业化制造SCP的瓶颈和解决方案进行了展望。

关键词: 一碳化工, 甲醇, 级联转化, 单细胞蛋白, 微生物细胞工厂

Abstract:

As the development of industry, a large amount of CO₂ emissions has aggravated greenhouse effect of the world and environmental pollution. In addition, the growing global population will face the problem of insufficient supply of protein resources. A more efficient route for CO₂ fixation and conversion involves chemical reduction of CO₂ to synthesize methanol, followed by microbial conversion of methanol into multi-carbon products. Therefore, from both a feedstock and product perspective, this review suggests the use of a chemical-biological cascade process for CO₂ conversion to produce single-cell protein (SCP), which involves the chemical reduction of CO₂ to methanol, followed by the microbial production of SCP from methanol and ammonium using microbial cell factories. The SCP from CO₂ can be used in the feed and food industries. Firstly, the reaction processes, mechanisms, and catalyst design for the sustainable hydrogenation of CO₂ to methanol are introduced. Secondly, methanol-utilizing microorganisms found in the nature, their methanol metabolic pathways, and their application in converting methanol into SCP are summarized. Finally, the bottlenecks and potential solutions for the industrial-scale production of SCP via chemical-biological cascade conversion of CO₂ are prospected.

Key words: one-carbon chemical engineering, methanol, cascade conversion, single cell protein, microbial cell factory

中图分类号:

TQ93

吴孟勤, 王佳瑶, 徐友强, 王钰. 化学-生物级联转化CO₂合成单细胞蛋白研究进展[J]. 化工进展, 2025, 44(5): 2429-2440.

WU Mengqin, WANG Jiayao, XU Youqiang, WANG Yu. Progress in cascade conversion of CO₂ to single cell protein through chemical and biological catalysis[J]. Chemical Industry and Engineering Progress, 2025, 44(5): 2429-2440.

图/表 3

图1 化学催化CO2加氢产生甲醇的反应机制（*表示吸附物质）

表1 CO2加氢生产甲醇催化剂的反应条件、催化性能及反应机理

	催化剂	温度 /K	压力 /MPa	H₂∶CO₂	气体时空速度 /mL∙h^-1∙g^-1	CO₂转化率 /%	甲醇选择性 /%	时空产率 /g_MeOH∙g_cat^-1∙h^-1	催化剂稳定性/h	反应途径	参考文献
Cu基催化剂
	CuZnAl	533	1.5	3	—	2	约54	0.73	—	甲酸盐	[19]
	Cu-20%MgO/ZnO	473	3	H₂∶CO₂∶N₂= 3∶1∶1	7200	8.7	99	0.202	>120	—	[20]
	Cu-ZrO₂	493	3	H₂∶CO₂∶Ar= 72∶24∶4	15000	7.2	约77.8	2.617	约16	CO加氢	[21]
	30%CuO/49.65%ZnO/20.35%Al₂O₃	575	8.5	4	19000	13	50	0.22	—	—	[22]
	60%CuO-30%ZnO10%Al₂O₃	575	8.5	4	19000	21	49.5	0.425	—	—
	60%CuO-27%ZnO/3%La₂O₃/10%Al₂O₃	575	8.5	4	55000	10	65	0.79	—	—
贵金属基催化剂
	Pt(3)/MoO _x (30)/TiO₂	423	—	5	—	—	约85	—	—	甲酸盐	[23]
	PdZn/CeO₂	473	2	3	3600	14.1	97.2	0.17	>100	甲酸盐	[24]
	PdZn/ZnO/SiO₂	533	5	3	60000	3.3	65.3	0.443	—	—	[25]
金属氧化物催化剂
	In₂O₃/ZrO₂	573	5	4∶1	16000	5.2	99.8	0.295	1000	—	[16]
	hexagonalIn₂O₃	543	5	4∶1	20000	6.7	99.5	0.365	136	甲酸盐	[26]
固溶体催化剂
	ZnO-ZrO₂	588-593	5	（3∶1）~（4∶1）	24000	>10%（单程）	86~91	—	>500	甲酸盐	[18]
	有序介孔结构ZnO-ZrO₂	593	5.5	H₂∶CO₂∶Ar= 72∶24∶4	24000	约10	约81	0.708	40	—	[27]
金属有机框架催化剂
	Cu@FAU	513	3	3	12000	11.5	89.5	0.41	200	甲酸盐	[28]
	20%-Cu@ZrO₂-U	533	3	3	2400	12.1	70.5	0.073	100	甲酸盐	[29]
	In₂O₃@ZrO₂-MIL-68@UiO-66	563	3	—	—	10.4	84.6	0.29	—	甲酸盐	[30]
	CuO/s-UiO-66 (4.29%)	513	3	—	18000	2.43	76.8	2.649	130	甲酸盐	[31]
混合催化剂
	PdCu/Ce_0.3Zr_0.7O₂ (PdCu/CZ-3)	523	5	3	3600	25.5	30~40	0.07	>100	甲酸盐	[32]
	Ag/In₂O₃	573	5	H₂∶CO₂∶N₂= 76∶19∶5	21000	13.6	58.2	0.453	10	CO加氢	[33]
	0.8%Pd-ZnZrO _x	593	4	H₂∶CO₂∶N₂= 76∶19∶5	24000	约18	约60	约0.6	100	甲酸盐	[34]

图2 天然甲基营养菌的甲醇代谢途径MDH—甲醇脱氢酶(methanol dehydrogenase)；AOX—甲醇氧化酶(alcohol oxidase)；FADH—甲醛脱氢酶；HPS—己糖-6-磷酸合酶(3-hexulose-6-phosphate synthase)；PHI—6-磷酸-3-己酮糖异构酶(6-phospho-3-hexuloisomerase)；PFK—6-磷酸果糖激酶(6-phosphofructokinase)；FBA—果糖二磷酸醛缩酶/景天庚酮糖-1,7-二磷酸醛缩酶(fructose-bisphosphate aldolase/sedoheptulose-bisphosphate aldolase)；TKT—转酮醇酶(transketolase)；RPE—磷酸核酮糖差向异构酶(ribulose-phosphate 3-epimerase)；RPI—核糖5-磷酸异构酶(ribose-5-phosphate isomerase)；GLPX—双功能果糖二磷酸酶/景天庚酮糖双磷酸酯酶(bifunctional fructose bisphosphatase/sedoheptulose bisphosphatase)；DAS—二羟基丙酮合酶(dihydroxyacetone synthase)；DHAK—二羟基丙酮激酶(dihydroxyacetone kinase)；FBP—果糖二磷酸酶(fructose bisphosphatase)；SBP—景天庚酮糖双磷酸酯酶(sedoheptulose bisphosphatase)；SHMT—丝氨酸羟甲基转移酶(serine hydroxymethyltransferase)；SGA—丝氨酸乙醛酸氨基转移酶(serine glyoxylate aminotransferase)；HPR—羟基丙酮酸还原酶(hydroxypyruvate reductase)；GCK—甘油酸激酶(glycerate kinase)；ENO—烯醇化酶(enolase)；PPC—磷酸烯醇丙酮酸羧化酶(phosphoenolpyruvate carboxylase)；MADH—苹果酸脱氢酶(malate dehydrogenase)；MTK—苹果酸硫激酶 (malate thiokinase)；MCL—苹果酰辅酶A裂解酶(malyl-CoA lyase)；Ru5P—核酮糖-5-磷酸(ribulose-5-phosphate)；Ru15dP—核酮糖-1,5-二磷酸(ribulose-1,5-bisphosphate)；R5P—核糖-5磷酸(ribose-5-phosphate)；Xu5P—木酮糖-5-磷酸(xylulose-5-phosphate)；H6P—3-己酮糖-6-磷酸(hexulose-6-phosphate)；F6P—果糖-6磷酸(fructose-6-phosphate)；F16dP—果糖-1,6-二磷酸(fructose-1,6-bisphosphate)；DHAP—磷酸二羟基丙酮(dihydroxyacetone phosphate)；DHA—二羟基丙酮(dihydroxyacetone)；G3P—甘油醛-3-磷酸(glyceraldehyde-3-phosphate)；E4P—赤藓糖-4-磷酸(erythrose-4-phosphate)；S7P—景天庚酮糖-7-磷酸(sedoheptulose-7-phosphate)；S17dP—1, 7-二磷酸景天庚酮糖(sedoheptulose-1,7-bisphosphate)；PGA—磷酸甘油酸酯(2-phosphate-glycerate)；PEP—磷酸烯醇式丙酮酸(phosphoenolpyruvate)；OAA—草酰乙酸(oxaloacetate)

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化学-生物级联转化CO₂合成单细胞蛋白研究进展

Progress in cascade conversion of CO₂ to single cell protein through chemical and biological catalysis

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