液-液萃取技术在中链羧酸原位提取中的研究进展

doi:10.13560/j.cnki.biotech.bull.1985.2025-1171

摘要/Abstract

摘要：

中链羧酸（medium chain carboxylic acids, MCCAs）作为高附加值化学品，凭借其独特的理化性质，在食品、化工、医药及生物材料等领域都展现出广阔的应用前景。传统化学合成法生产MCCAs，存在高度依赖石化资源且产品产率与纯度低、能耗高以及植物性油脂原料供应链稳定性差等诸多技术瓶颈，现有产能已无法满足快速增长的市场需求。鉴于此，利用微生物碳链延长技术将废弃生物质转化为高附加值的MCCAs，不仅推动了有机碳源的循环利用，而且降低了对化石资源的依赖，兼具环保效益、经济可行性与应用潜力，在绿色生物制造领域备受关注。然而，微生物碳链延长合成MCCAs的高效分离技术，仍是制约其规模化生产的关键瓶颈之一。在众多分离技术中，液-液萃取凭借其显著优势脱颖而出，已被证实在MCCAs原位提取与纯化方面展现出巨大的应用潜力。本文以微生物碳链延长合成MCCAs的代谢途径为切入点，在对比分析几种现有MCCAs原位提取技术的基础上，系统综述了原位液-液萃取MCCAs的技术原理、工艺参数、关键影响因素以及规模化应用瓶颈。未来，可通过萃取剂剂型创新与在线提取数字化升级等手段，推动MCCAs生产技术的规模化应用，助力“双碳”目标实现。

关键词: 中链羧酸, 微生物碳链延长, 废弃生物质, 液-液萃取, 原位提取

Abstract:

Medium chain carboxylic acids (MCCAs), as high-value platform chemicals, show extensive applications in food, chemical, pharmaceutical, and biomaterial industries due to their unique physicochemical properties. There are numerous technical bottlenecks, including high dependence on petrochemical resources, low product yield and purity, high energy consumption, and poor stability of the vegetable oil raw material supply chain in traditional chemical synthesis methods for producing MCCAs. Existing production capacity can no longer meet the rapidly growing market demand. Therefore, the application of microbial carbon chain elongation technology to convert waste biomass into high-value MCCAs not only facilitates the recycling of organic carbon sources, but also mitigates reliance on fossil resources. This synergistically integrates environmental sustainability, economic viability, and industrial scalability, positioning it as a highly promising strategy in green biomanufacturing. However, the efficient separation technology for microbial carbon chain elongation-derived MCCAs is still a critical bottleneck. Among various separation technologies, liquid-liquid extraction stands out with its significant advantages, demonstrating considerable potential for in situ extraction and purification of MCCAs. This review begins with the metabolic pathway of microbial carbon chain elongation for MCCAs synthesis. Through a comparative analysis of several in-situ separation technologies for MCCAs, it systematically reviews the technical principles, process parameters, key influencing factors, and bottlenecks in scale-up application of liquid-liquid in-situ extraction of MCCAs. In the future, the large-scale application of MCCAs production technology can be facilitated through innovations in extractant formulations and digital upgrades to online extraction processes, thereby contributing to the achievement of the “dual carbon” goal.

Key words: medium chain carboxylic acids, microbial carbon chain elongation, waste biomass, liquid-liquid extraction, in situ extraction

王婷, 徐少钦, 明庭红, 徐嘉杰. 液-液萃取技术在中链羧酸原位提取中的研究进展[J]. 生物技术通报, 2026, 42(7): 81-96.

WANG Ting, XU Shao-qin, MING Ting-hong, XU Jia-jie. Research Progress in Liquid-liquid Extraction Technology for In Situ Extraction of Medium Chain Carboxylic Acids[J]. Biotechnology Bulletin, 2026, 42(7): 81-96.

图/表 8

图1 可再生生物质资源（A）通过微生物碳链延长途径（B）合成中链羧酸（C）及其潜在的应用价值（D）

Fig. 1 Renewable biomass resources (A) via microbial carbon chain elongation pathway (B) to synthesize medium chain carboxylic acids (C) and their potential applications (D)

表1 短链和中链羧酸的理化性质

Table 1 Physicochemical characteristics of short and medium chain carboxylic acids

类别 Category	化合物 Compound	碳原子数 Number of carbon atoms	溶解度 Solubility （mg/L） ^a	电子密度 Electron density （g COD/g） ^b	酸度系数 Acidity coefficient （pKa）
短链羧酸	乙酸	2	互溶	1.07	4.76
	丙酸	3	互溶	1.51	4.88
	丁酸	4	60 000	1.82	4.82
	戊酸	5	24 000	2.04	4.84
中链羧酸	己酸	6	10 300	2.20	4.80
	庚酸	7	2 820	2.34	4.80
	辛酸	8	735 ^c	2.44	4.89
	壬酸	9	284 ^d	2.53	4.95
	癸酸	10	62	2.60	4.90
	十一烷酸	11	52	2.66	4.95
	月桂酸	12	4.8	2.72	5.30

图2 以乙醇和乳酸作为碳链延长电子供体通过逆β氧化（RBO）途径生产MCCAs示意图

Fig. 2 Schematic diagram of MCCAs production through reverse β-oxidation (RBO) pathway using ethanol and lactate as carbon chain elongation electron donors

图3 几种原位提取MCCAs技术的示意图

Fig. 3 Schematic diagram of several in-situ extraction technologies used for MCCAs

表2 非极性萃取剂、磷基萃取剂及胺基萃取剂分类汇总

Table 2 Summary and classification of non-polar extractants, phosphorus-based extractants, and amine-based extractants

类别 Category	萃取机理 Extraction mechanism	代表性萃取剂 Representative extractant	萃取的羧酸 Extracted carboxylic acids	参考文献 Reference
非极性萃取剂	主要通过范德华力与MCCAs分子发生疏水性缔合	正己烷	己酸	［45］
磷基萃取剂	通过磷氧基（P=O）上的孤对电子与MCCAs的羧基形成配位键或氢键	磷酸三丁酯（TBP）	己酸	［46］
		三辛基氧膦（TOPO）	乙酸、丁酸、丙酸、己酸、辛酸	［47-49］
		Cyanex 923	己酸、辛酸	［47， 49］
胺基萃取剂	与MCCAs形成氢键或离子对（酸碱反应）	三辛胺（TOA）	己酸、辛酸	［47］
		Aliquat 336	己酸	［50］
		三月桂胺（TDA）、三己胺（THA）、三丙胺（TPA）、三辛胺（TOA）	己酸	［51］

图4 MCCAs原位液-液萃取技术的示意图

Fig. 4 Schematic diagram of in-situ liquid-liquid extraction technology for MCCAs

图5 MCCAs原位液-液萃取后端回收示意图，包括酸/碱或盐添加法（A）［60, 63］、蒸馏法（B）［47, 63］和膜电解法（C）［28, 65］

Fig. 5 Schematic diagram of in-situ liquid-liquid extraction for MCCAs backward recovery, including addition of acid/base, or salt (A)[60, 63], distillation (B)[47, 63], and membrane electrolysis (C)[28, 65]

图6 萃取剂对发酵液中碳链延长微生物的细胞毒性效应

Fig. 6 Cytotoxicity of extractants on carbon chain elongation microorganisms in fermentation broth

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