基于微生物发酵构建生物基材料及单体模块

doi:10.16085/j.issn.1000-6613.2025-0090

摘要/Abstract

摘要：

生物基材料是推动化工新材料领域产业升级转型的重要支撑，本文以发酵法为核心，系统总结了生物基材料及单体模块原料端、过程端、产品端的相关进展；概括了生物制造产业背景下第二代、第三代碳源迭代更新的技术壁垒和挑战，提出构建多维生物质碳源供给体系和保障机制，以突破第一代碳源供给的局限性；围绕生物基塑料、生物基橡胶、生物基尼龙、生物基多糖材料四个模块，阐述了乙二醇、1,3-丙二醇、1,4-丁二醇、丁二酸、己二酸、对苯二甲酸等聚合物单体以及聚乳酸、聚羟基烷酸酯、透明质酸、细菌纤维素等聚合物材料的发酵工艺技术。本文还提出了完善发酵法生物基材料的产品体系，以实现石化材料的逐步替代，进而推动化工新材料领域的可持续发展。

关键词: 生物基材料, 发酵, 单体, 碳源, 塑料

Abstract:

Bio-based materials are recognized as a critical enabler for advancing chemical engineering advanced materials toward industrial upgrading and transformation. This article focused on the fermentation methodologies employed in the production of bio-based materials and systematically summarized their progress across raw material, process, and product domains. The study also examined the technological barriers and challenges associated with the iterative updates of second-generation and third-generation carbon sources within the biomanufacturing industry. It proposed the construction of a multidimensional biomass carbon source supply system and guarantee mechanism. The article delved into the fermentation process technology for key polymer monomers such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, succinic acid, adipic acid, and terephthalic acid, as well as polymer materials including polylactic acid, polyhydroxyalkanoates, hyaluronic acid, and bacterial cellulose. The study outlined four critical modules: bio-based plastics, bio-based rubbers, bio-based nylon, and bio-based polysaccharide materials. It advocated for enhancing the product system of bio-based materials through fermentation methods to gradually replace petrochemical-based materials, paving the way for future advancements in the field.

Key words: bio-based materials, ferment, monomers, carbon source, plastic

中图分类号:

TQ31

王良玉, 曹辉, 谭天伟. 基于微生物发酵构建生物基材料及单体模块[J]. 化工进展, 2025, 44(5): 2394-2406.

WANG Liangyu, CAO Hui, TAN Tianwei. Constructing bio-based materials and monomer modules based on microbial fermentation[J]. Chemical Industry and Engineering Progress, 2025, 44(5): 2394-2406.

图/表 8

图1 生物质多维碳源供给体系下的代表性生物基单体和聚合物材料

图2 以缩合反应驱动的双酚合成策略[17]

表1 发酵法合成单体模块的重要指标

单体模块	底物	菌种	滴度/g·L^-1	得率/g·g^-1	生产速率/g·L^-1·h^-1	参考文献
乙二醇	木糖	E. coli W3110	108.2	0.3600	2.250	[37]
1,3-丙二醇	甘油	K. pneumoniae LDH526	102.1	0.5200	2.130	[38]
	葡萄糖	E. coli	135.0	1.200	3.500	[38]
	葡萄糖	C. glutamicum MBP14	110.4	0.4200	2.300	[39]
1,4-丁二醇	葡萄糖	E. coli	125.0	0.4000	0.3500	[4]
对苯二甲酸	对二甲苯	E. coli DH5α	6.700	0.6200	0.2800	[44]
对苯二甲酸	对二甲苯	P. putida KT2440	38.25	0.6400	—	[45]
丁二酸	甘蔗汁	I. orientalis SD108	63.10	0.5000	0.6600	[42]
丁二酸	葡萄糖	Y. lipolytica Hi-SA2	111.9	0.7900	1.790	[5]
己二酸	葡萄糖和甘油	E. coli Mad123146	68.00	0.3800	0.8100	[70]
黏康酸	葡萄糖	C. glutamicum MA8	88.20	0.3000	—	[76]
黏康酸	木质纤维素水解液	C. glutamicum EMA1	19.90	0.3300	—	[76]
苯乙烯	葡萄糖	E. coli YHP05	5.300	—	0.09000	[34]
丁二烯	葡萄糖	E. coli CFB22	2.130	—	—	[55]

图3 以葡萄糖为原料从头生产1,3-丙二醇的生物合成路线[40]ppc—磷酸烯醇式丙酮酸羧化酶；gltA—柠檬酸合酶；aspDH—天冬氨酸脱氢酶；aspA—天冬氨酸氨裂合酶；panD—天冬氨酸脱羧酶；bauA—β-丙氨酸丙酮酸氨基转移酶；ydfG—3-羟基酸脱氢酶；M_1456(Msed_1456)—3-羟基丙酰辅酶A合成酶；pduP—醛脱氢酶；yqhD—乙醇脱氢酶；thrA—天冬氨酸激酶/高丝氨酸脱氢酶1；metL—天冬氨酸激酶/高丝氨酸脱氢酶2；lysC—赖氨酸敏感天冬氨酸激酶3；panC—泛酸合成酶

图4 两步法合成对二甲苯[46]

图5 聚羟基脂肪酸酯的代表性种类及其结构PHB—聚羟基丁酸酯；PHBV—聚(3-羟基丁酸酯-co-3-羟基戊酸酯)的共聚物；PHBHHX—聚(3-羟基丁酸酯-co-3-羟基己酸酯)；P34HB—聚-3-羟基丁酸酯-4-羟基丁酸酯

图6 顺式、反式混合聚异戊二烯和天然橡胶骨架结构的生物合成途径[61]

图7 谷氨酸棒杆菌中酸生产黏康酸的代谢途径[76]G6P—6-磷酸葡萄糖；F6P—6-磷酸果糖；FBP—果糖-1,6-二磷酸；GAP—甘油醛-3-磷酸；PEP—磷酸烯醇丙酮酸；PYR—丙酮酸；Ru5P—核酮-5-磷酸；X5P—木酮糖-5-磷酸；GAP—甘油醛-3-磷酸；E4P—D-赤藓糖4-磷酸；DAHP—3-脱氧-D-阿拉伯庚烯酸-7-磷酸酯；DHQ—3-脱氢奎尼酸酯；DHS—3-脱氢莽草酸；PCA—原儿茶酸酯；CA—儿茶酚；MA—顺式,顺式黏康酸；tktA—转酮醇酶Ⅰ；pyk—丙酮酸激酶；aroG—磷酸-2-脱氢-3-脱氧庚酸醛缩酶；aroB—DHQ合成酶；aroD—DHQ脱水酶；aroE—莽草酸5-脱氢酶；qsuB—磷酸异构酶；pcaG/H—PCA脱氧原酶α/β亚基；aroY, kpdB/D—PCA脱羧酶及其亚基；catA—CA 1,2-双加氧酶；catB—氯甲酸环异构酶

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