木质纤维类废弃物定向生物转化乳酸、乙酸研究进展

doi:10.16085/j.issn.1000-6613.2023-0055

化工进展 ›› 2023, Vol. 42 ›› Issue (5): 2691-2701.DOI: 10.16085/j.issn.1000-6613.2023-0055

木质纤维类废弃物定向生物转化乳酸、乙酸研究进展

黄越¹^,²(), 赵立欣², 姚宗路², 于佳动²(), 李再兴³, 申瑞霞², 安柯萌¹^,², 黄亚丽¹

^1.河北科技大学环境科学与工程学院，河北石家庄 050018
^2.中国农业科学院农业环境与可持续发展研究所，农业农村部华北平原农业绿色低碳重点实验室，北京 100081
^3.北京石油化工学院环境工程系，北京 102617

收稿日期:2023-01-12 修回日期:2023-02-07 出版日期:2023-05-10 发布日期:2023-06-02
通讯作者: 于佳动
作者简介:黄越（2000—），女，硕士研究生，研究方向为农业废弃物厌氧发酵工艺。E-mail：haungyue20000504@163.com。
基金资助:
国家重点研发计划(2022YFD2002102);中国农业科学院科技创新工程项目;中央级公益性科研院所基本科研业务费专项(BSRF202204)

Research progress in directed bioconversion of lactic acid and acetic acid from wood lignocellulosic wastes

HUANG Yue¹^,²(), ZHAO Lixin², YAO Zonglu², YU Jiadong²(), LI Zaixing³, SHEN Ruixia², AN Kemeng¹^,², HUANG Yali¹

^1.School of Environmental Science and Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, Hebei, China
^2.Institute of Environment and Sustainable Development in Agriculture, Chinese Academy of Agricultural Sciences, Key Laboratory of Low-carbon Green Agriculture in North China, Ministry of Agriculture and Rural Affairs, PRC，Beijing 100081, China
^3.Department of Environmental Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China

Received:2023-01-12 Revised:2023-02-07 Online:2023-05-10 Published:2023-06-02
Contact: YU Jiadong

摘要/Abstract

摘要：

依托厌氧发酵技术处理秸秆和牛粪等木质纤维类废弃物，是资源循环利用的重要方式之一。乳酸和乙酸是厌氧发酵的重要中间产物，是生产沼气、中链脂肪酸等能源化工产品的重要前体物质，但定向生物转化协同生产效率不高、对木质纤维类废弃物协同产乳酸、乙酸机制等问题有待深入探索。本文基于对产酸代谢途径机理的分析，梳理了同步发酵和分步发酵协同产乳酸、乙酸特性，归纳了影响生物转化产酸效率的关键因素，发现在较高含固率15%~20%、接种20%~40%的活性物质和适宜的过程参数[pH为5.0左右、中温和有机负荷5~10kgVS/(m³·d)]下，木质纤维类废弃物具有良好的协同产酸效果。进一步探明物化和生物强化耦合手段对木质纤维素降解和目标产物的促进效应，为开发生物转化乳酸、乙酸协同生产关键技术以及促进秸秆等木质纤维类废弃物高值转化利用提供理论依据。

关键词: 乳酸, 乙酸, 厌氧发酵, 协同产酸, 中链脂肪酸, 木质纤维类废弃物

Abstract:

Anaerobic fermentation technology is one of the critical ways of resource recycling to treat wood lignocellulosic wastes such as straw and cow manure. Lactic acid and acetic acid are essential intermediate products of anaerobic fermentation, and significant precursor substances for the production of biogas, medium chain fatty acids and additional energy chemical products. However, the collaborative production efficiency of directed biotransformation is not elevated, and the mechanism of collaborative production of lactic acid and acetic acid from wood lignocellulosic waste still needs to be further explored. Based on the analysis of the metabolic pathway mechanism of acid production, this paper sorted out the characteristics of simultaneous fermentation and stepwise fermentation in collaborative production of lactic acid and acetic acid and summarized the key factors affecting the efficiency of biological transformation in acid production. It was found that the wood lignocellulosic waste had a favorable synergic acid production effect under high solid content of 15%—20%, inoculation of 20%—40% active substances and appropriate process parameters [pH=5.0, moderate temperature and moderate organic load 5—10kgVS/(m³·d)]. In addition,we explored the promoting effect of physicochemical and bio strengthening coupling means on lignocellulosic degradation and target products, which provided a theoretical basis for the development of key technologies for the collaborative production of lactic acid and acetic acid by bioconversion, and the promotion of high-value conversion and utilization of wood lignocellulosic waste such as straw.

Key words: lactic acid, acetic acid, anaerobic fermentation, co-production of acid, medium chain fatty acid, wood lignocellulosic waste

中图分类号:

TQ921

黄越, 赵立欣, 姚宗路, 于佳动, 李再兴, 申瑞霞, 安柯萌, 黄亚丽. 木质纤维类废弃物定向生物转化乳酸、乙酸研究进展[J]. 化工进展, 2023, 42(5): 2691-2701.

HUANG Yue, ZHAO Lixin, YAO Zonglu, YU Jiadong, LI Zaixing, SHEN Ruixia, AN Kemeng, HUANG Yali. Research progress in directed bioconversion of lactic acid and acetic acid from wood lignocellulosic wastes[J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2691-2701.

图/表 6

表1 7种产酸途径

产酸阶段	反应方程	反应条件	目标酸产量	关键菌	参考文献
乙酸/乙醇型代谢途径	1. C₆H₁₂O₆ + 2H₂O $→$ 2CH₃COOH+ 2CO₂ + 4H₂ 2. CH₃CH₂COOH + 2H₂O $→$ CH₃COOH+ CO₂ + 3H₂ 3. CH₃CH₂CH₂COOH + 2H₂O $→$ 2CH₃COOH + 2H₂ 4. CH₃CH₂OH + 2H₂O $→$ CH₃COOH+ 2H₂ 5. C₆H₁₂O₆ + H₂O $→$ CH₃CH₂OH+ CH₃COOH + 2H₂ + 2CO₂	HRT 5h、pH=4.3~4.4	乙醇3.82gCOD/L 乙酸0.66gCOD/L		[17]
丙酮-丁醇-乙醇发酵	1. C₆H₁₂O₆ + H₂O $→$ CH₃COCH₃ + 4H₂+ 3CO₂ 2. C₆H₁₂O₆ $→$ 2CH₃CH₂OH + 2CO₂ 3.C₆H₁₂O₆ $→$ CH₃CH₂CH₂ CH₂OH+ H₂O + 2CO₂	326h饲喂、葡萄糖474.9g/L、间歇性气体汽提、补料分批发酵	丙酮-丁醇-乙醇172g/L	hyper-butanol producing Clostridium acetobutylicum JB200	[18]
丙酸型代谢途径	1. C₆H₁₂O₆ + 2H₂ $→$ 2CH₃CH₂COOH+ 2H₂ 2. 3C₆H₁₂O₆ $→$ 4CH₃CH₂COOH + 2CH₃COOH + 2CO₂ + 2H₂O	两相发酵	丙酸7.13gCOD/L	Propionibacteriumacidipropionici	[19]
丁酸型代谢途径	1. C₆H₁₂O₆ $→$ CH₃CH₂CH₂COOH + 2CO₂ + 2H₂ 2. 4C₆H₁₂O₆ $→$ 8H₂ + 8CO₂ + 2CH₃COOH + 3CH₃CH₂CH₂COOH	50%含菌培养基	丁酸8.06g/L	Clostridium tyrobutyricum strain RPT-4213	[20]
混合酸代谢途径	1. 3C₆H₁₂O₆ $→$ 4CH₃CH₂COOH + 2CH₃COOH + 2CO₂ + 2H₂O 2. C₆H₁₂O₆ + H₂O $→$ CH₃CH₂OH + CH₃COOH + 2H₂ + 2CO₂ 3. 4C₆H₁₂O₆ $→$ 8H₂ +8CO₂ + 2CH₃COOH + 3CH₃CH₂CH₂COOH	pH=6.5、缓冲液15~20mmol/gVS	挥发酸及乙醇70mol/L		[21]
乳酸型代谢途径	1. C₆H₁₂O₆ $→$ 2CH₃CH(OH)COOH 2. C₆H₁₂O₆ $→$ CH₃CH(OH)COOH+ CO₂ + CH₃CH₂OH 3. C₆H₁₂O₆ $→$ CH₃CH(OH)COOH+ CO₂ + CH₃COOH	固体负荷为60g/L、35℃	乳酸14.7g/L、乙酸4.0g/L、乙醇3.2g/L	Lactobacillus brevis、Lactobacillus fermentum	[22]
同型产乙酸发酵	1. 4H₂ + 2CO₂ $→$ CH₃COOH + 2H₂O 2. C₆H₁₂O₆ $→$ 3CH₃COOH	氢分压1700mbar、pH=7.0	乙酸44g/L	Acetobacterium woodii	[15]

表1 7种产酸途径

产酸阶段	反应方程	反应条件	目标酸产量	关键菌	参考文献
乙酸/乙醇型代谢途径	1. C₆H₁₂O₆ + 2H₂O $→$ 2CH₃COOH+ 2CO₂ + 4H₂ 2. CH₃CH₂COOH + 2H₂O $→$ CH₃COOH+ CO₂ + 3H₂ 3. CH₃CH₂CH₂COOH + 2H₂O $→$ 2CH₃COOH + 2H₂ 4. CH₃CH₂OH + 2H₂O $→$ CH₃COOH+ 2H₂ 5. C₆H₁₂O₆ + H₂O $→$ CH₃CH₂OH+ CH₃COOH + 2H₂ + 2CO₂	HRT 5h、pH=4.3~4.4	乙醇3.82gCOD/L 乙酸0.66gCOD/L		[17]
丙酮-丁醇-乙醇发酵	1. C₆H₁₂O₆ + H₂O $→$ CH₃COCH₃ + 4H₂+ 3CO₂ 2. C₆H₁₂O₆ $→$ 2CH₃CH₂OH + 2CO₂ 3.C₆H₁₂O₆ $→$ CH₃CH₂CH₂ CH₂OH+ H₂O + 2CO₂	326h饲喂、葡萄糖474.9g/L、间歇性气体汽提、补料分批发酵	丙酮-丁醇-乙醇172g/L	hyper-butanol producing Clostridium acetobutylicum JB200	[18]
丙酸型代谢途径	1. C₆H₁₂O₆ + 2H₂ $→$ 2CH₃CH₂COOH+ 2H₂ 2. 3C₆H₁₂O₆ $→$ 4CH₃CH₂COOH + 2CH₃COOH + 2CO₂ + 2H₂O	两相发酵	丙酸7.13gCOD/L	Propionibacteriumacidipropionici	[19]
丁酸型代谢途径	1. C₆H₁₂O₆ $→$ CH₃CH₂CH₂COOH + 2CO₂ + 2H₂ 2. 4C₆H₁₂O₆ $→$ 8H₂ + 8CO₂ + 2CH₃COOH + 3CH₃CH₂CH₂COOH	50%含菌培养基	丁酸8.06g/L	Clostridium tyrobutyricum strain RPT-4213	[20]
混合酸代谢途径	1. 3C₆H₁₂O₆ $→$ 4CH₃CH₂COOH + 2CH₃COOH + 2CO₂ + 2H₂O 2. C₆H₁₂O₆ + H₂O $→$ CH₃CH₂OH + CH₃COOH + 2H₂ + 2CO₂ 3. 4C₆H₁₂O₆ $→$ 8H₂ +8CO₂ + 2CH₃COOH + 3CH₃CH₂CH₂COOH	pH=6.5、缓冲液15~20mmol/gVS	挥发酸及乙醇70mol/L		[21]
乳酸型代谢途径	1. C₆H₁₂O₆ $→$ 2CH₃CH(OH)COOH 2. C₆H₁₂O₆ $→$ CH₃CH(OH)COOH+ CO₂ + CH₃CH₂OH 3. C₆H₁₂O₆ $→$ CH₃CH(OH)COOH+ CO₂ + CH₃COOH	固体负荷为60g/L、35℃	乳酸14.7g/L、乙酸4.0g/L、乙醇3.2g/L	Lactobacillus brevis、Lactobacillus fermentum	[22]
同型产乙酸发酵	1. 4H₂ + 2CO₂ $→$ CH₃COOH + 2H₂O 2. C₆H₁₂O₆ $→$ 3CH₃COOH	氢分压1700mbar、pH=7.0	乙酸44g/L	Acetobacterium woodii	[15]

图1 木质纤维类废弃物协同生产乳酸、乙酸途径

图2 木质纤维类废弃物协同产乳酸、乙酸示意图

图3 木质纤维类废弃物协同产乳酸、乙酸工艺

表2 不同影响因素对木质纤维类废弃物协同产酸的影响

影响因素	底物	接种物	调控因素	主要微生物	目标产物	参考文献
底物含固率	帝王草		萎蔫处理、30℃枯萎12h至帝王草含水量63%	Lactococcus、Enterococcus	乳酸4.07g/kgDM 乙酸16.73g/kgDM	[43]
接种物	稻草	青贮废水	黑麦草青贮出水180mL，加入100g稻草鲜料（FM）中，液固比9∶5	Lactobacillus、Weissella、Enterococcus	乳酸4.6%DM 乙酸2.1%DM	[44]
接种物	玉米秸秆	黑麦草、Lactobacillus plantarum (L694)	黑麦草70%、玉米秸秆30%	Lactobacillus plantarum、 Lactobacillus hammesii、 Lactobacillus brevis、 Lactobacillus coryniformi	乳酸14.98%DM 乙酸2.30%DM	[45]
	燕麦秸秆	Pediococcus acidilactici DSM 20284	pH=3.7 发酵35天		乳酸94.19g/kgDM 乙酸5.18g/kgDM	[46]
过程参数	纤维素生物污泥	Lactobacillus rhamnosus CECT-288	初始液固比12g/g、同步糖化产酸工艺、pH=4.85、分批补料		乳酸42g/L 乙酸4.3g/L	[47]
	玉米泡粉	30FPU（滤纸单位）/g 纤维素酶、P.acidilactici PA204	12% 秸秆、同步糖化产酸工艺、37℃、pH=6.0		乳酸0.77g/g 秸秆乙酸0.08g/g 秸秆	[48]
	小麦秸秆	Bacillus coagulans DSM 2314、酶制剂GC 220	20.0%（质量体积浓度）氢氧化钙悬浮液将pH控制在6.0、分批补料、同步糖化发酵		乳酸40.7g/L 乙酸1.5g/L	[49]
	青贮秸秆	Lactobacillus plantarum	pH=3.95±0.22	Lactobacillus plantarum、 Lactobacillus brevis、 Weissella cibaria、 Pediococcus acidilactici	乳酸5.14 % DM 乙酸1.06 % DM	[50]
	玉米秸秆	20FPU/g纤维素酶	50℃、NaOH每12h调整pH至6.0、分批补料、NHB15 预处理		乳酸51.4g/L 乙酸42g/L	[51]

表3 不同强化手段及强化效果

强化手段	底物	强化条件	强化效果	参考文献
物理和化学强化	玉米秸秆	蒸汽爆破-氯化胆碱、1∶2.2（质量比）、1.0MPa、184℃、15min	有效脱除84.7%的木质素和78.9%的木聚糖	[59]
	玉米秸秆	碳酸铵作为氨化剂浓度20%、11d、固含量50%	还原糖产量为312.67mg/g，比对照增加了51.80%	[60]
	芦苇秸秆	深共熔溶剂（氯化苄三乙胺/甲酸）	葡萄糖得率达76.64%，比生芦苇秸秆高5.24倍左右	[61]
生物强化	青贮玉米秸秆	白腐菌固态发酵、15d	纤维素、半纤维素和木质素降解率分别为9.9%、23.2%、15.2%	[62]
	玉米秸秆	接种从青贮中分离菌株Lb. farciminis 1101、Lb. brevis 0991	乳酸含量分别为>150mmol/L、0.203mol/L，乙酸含量均为38mmol/L	[63]
	玉米秸秆	添加凝结芽孢杆菌、粪链球菌和乳酸杆菌，发酵60h	乳酸含量6.88g/L，乙酸含量14.53g/L	[64]
联合强化	玉米秸秆	超声波-好氧水解	初始还原糖含量12.62mg/mL，以乙酸为主的挥发性脂肪酸含量16.24g/L	[65]
联合强化	水稻秸秆	细菌（Cupriavidus basilensis B-8）与稀酸预处理	酶消化率提高了70%	[66]

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木质纤维类废弃物定向生物转化乳酸、乙酸研究进展

Research progress in directed bioconversion of lactic acid and acetic acid from wood lignocellulosic wastes

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