低碳合成气生物转化及产乙醇发酵工艺探索

doi:10.16085/j.issn.1000-6613.2023-1815

化工进展 ›› 2024, Vol. 43 ›› Issue (11): 6111-6118.DOI: 10.16085/j.issn.1000-6613.2023-1815

• 能源加工与技术 • 上一篇

低碳合成气生物转化及产乙醇发酵工艺探索

方崇¹^,²(), 刘云云¹, 徐惠娟²(), 周雨²^,³, 邱雨心¹, 巨苗苗¹

^1.陕西科技大学机电工程学院，陕西西安 710016
^2.中国科学院广州能源研究所，中国科学院可再生能源重点实验室，广东广州 510640
^3.汕头大学海洋生物研究所，广东汕头 510632

收稿日期:2023-10-16 修回日期:2023-11-22 出版日期:2024-11-15 发布日期:2024-12-07
通讯作者: 徐惠娟
作者简介:方崇（1998—），男，硕士，研究方向为生物质资源高效转化与利用技术开发。E-mail：2816135041@qq.com。
基金资助:
国家重点研发计划(2019YFB1503904);陕西省自然科学基础研究计划面上项目(2021JM-382)

Bioconversion of low-carbon syngas to ethanol and the process development

FANG Chong¹^,²(), LIU Yunyun¹, XU Huijuan²(), ZHOU Yu²^,³, QIU Yuxin¹, JU Miaomiao¹

^1.School of Mechanical & Electrical Engineering, Shaanxi University of Science & Technology, Xi’an 710016, Shaanxi, China
^2.CAS Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^3.Institute of Marine Biology, Shantou University, Shantou 510632, Guangdong, China

Received:2023-10-16 Revised:2023-11-22 Online:2024-11-15 Published:2024-12-07
Contact: XU Huijuan

摘要/Abstract

摘要：

在碳中和大目标下，生物质气化合成气（主要成分为CO、CO₂和H₂）的资源化利用受到广泛关注，将合成气转化为燃料乙醇具有碳减排和能源生产的双重功效。针对化学催化转化过程存在合成气不能被完全利用的问题，采用生物法对其尾气（低碳合成气）进行进一步利用, 以提高合成气的利用率。本文从气体底物、发酵工艺等方面对乙醇梭菌（Clostridium autoethanogenum）发酵产乙醇过程进行了研究。结果表明：在合成气发酵中，菌株会优先利用CO，之后再利用CO₂和H₂，CO和H₂消耗的比值为0.99±0.12，产物中乙醇与乙酸的摩尔比为0.78±0.10；以100% CO为底物时，CO消耗与CO₂生成的比值为1.72±0.21，乙醇与乙酸的摩尔比为1.00±0.11。木糖-合成气共发酵时菌株对木糖的利用比较缓慢，与合成气发酵相比，菌体浓度较高，但乙醇浓度较低。培养基中添加乙酸钠浓度为4g/L时对菌株活性没有影响，高浓度（≥12g/L）则对菌株生长产生明显的抑制作用。3L搅拌罐式反应器的发酵实验显示，当发酵过程出现“酸崩溃”时，菌株的产乙醇代谢受到抑制，导致乙醇产量低；在菌株对数生长后期降低发酵温度可有效避免“酸崩溃”，发酵得到的最高乙醇浓度为3.46g/L，最高乙醇与乙酸的摩尔比达到2.01，最大乙醇产率达到0.35g/(L∙d)。上述研究结果可为Clostridium autoethanogenum发酵产乙醇过程工艺优化提供参考。

关键词: 合成气, 燃料乙醇, 气体发酵, 乙酸, 乙醇梭菌

Abstract:

As an effort to achieve carbon neutrality, utilization of biomass gasification-based syngas (mainly consisting of CO, CO₂, and H₂) has been extensively studied. Conversion of syngas to fuel ethanol has the dual effects of carbon emission reduction and energy production. Since syngas can not be completely converted in chemical catalytic process, the tail gas produced, known as low-carbon syngas, is considered to be further utilized by biological process. In this study, fermentation of Clostridium autoethanogenum for ethanol production was investigated from the aspects of gaseous substrate and fermentation technology. Results showed that Clostridium autoethanogenum preferentially consumed CO other than CO₂ and H₂in syngas fermentation, the ratio of CO consumption to H₂ consumption was 0.99±0.12, and the molar ratio of ethanol and acetic acid achieved was 0.78±0.10; when 100% CO was used as substrate, the ratio of CO consumption to CO₂ production was 1.72±0.21, and the molar ratio of ethanol and acetic acid was 1.00±0.11. During the process of xylose-syngas co-fermentation, xylose was consumed slowly, and compared to syngas fermentation, the cell density increased, but ethanol concentration was lower. Cell activities were not affected when 4g/L of sodium acetate was added in the medium, while significant inhibition on cell growth was observed under higher concentrations (≥12g/L). Fermentation results in the 3L stirred-tank reactor showed that the ethanol yield was low once "acid crash" happened, while lowering temperature at the late logarithmic phase of cell growth could prevent "acid crash". Consequently, the maximum ethanol concentration obtained was 3.46g/L, maximum ethanol and acetic acid molar ratio was 2.01, and the highest ethanol yield was 0.35g/(L∙d). This study provided references for the process optimization of ethanol production from low-carbon syngas via Clostridium autoethanogenum fermentation.

Key words: syngas, fuel ethanol, gaseous fermentation, acetate, Clostridium autoethanogenum

中图分类号:

方崇, 刘云云, 徐惠娟, 周雨, 邱雨心, 巨苗苗. 低碳合成气生物转化及产乙醇发酵工艺探索[J]. 化工进展, 2024, 43(11): 6111-6118.

FANG Chong, LIU Yunyun, XU Huijuan, ZHOU Yu, QIU Yuxin, JU Miaomiao. Bioconversion of low-carbon syngas to ethanol and the process development[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6111-6118.

图/表 5

参考文献 41

1	ABUBACKAR Haris Nalakath, VEIGA María C, KENNES Christian. Syngas fermentation for bioethanol and bioproducts[M]//Sustainable resource recovery and zero waste approaches. Amsterdam: Elsevier, 2019: 207-221.
2	ROBAK Katarzyna, BALCEREK Maria. Review of second-generation bioethanol production from residual biomass[J]. Food Technology and Biotechnology, 2018, 56(2): 174-187.
3	OWOADE Ademola, ALSHAMI Ali S, LEVIN David, et al. Progress and development of syngas fermentation processes toward commercial bioethanol production[J]. Biofuels, Bioproducts and Biorefining, 2023, 17(5): 1328-1342.
4	曹运齐, 解先利, 郭振强, 等. 木质纤维素预处理技术研究进展[J]. 化工进展, 2020, 39(2): 489-495.
	CAO Yunqi, XIE Xianli, GUO Zhenqiang, et al. Research progress on lignocellulose pretreatment technology[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 489-495.
5	FRAZÃO Cláudio J R, WALTHER Thomas. Syngas and methanol-based biorefinery concepts[J]. Chemie Ingenieur Technik, 2020, 92(11): 1680-1699.
6	GRIFFIN Derek W, SCHULTZ Michael A. Fuel and chemical products from biomass syngas: A comparison of gas fermentation to thermochemical conversion routes[J]. Environmental Progress & Sustainable Energy, 2012, 31(2): 219-224.
7	PHILLIPS John, HUHNKE Raymond, ATIYEH Hasan. Syngas fermentation: A microbial conversion process of gaseous substrates to various products[J]. Fermentation, 2017, 3(2): 28.
8	PEREZ-CARBAJO J, GÓMEZ-ÁLVAREZ P, BUENO-PEREZ R, et al. Optimisation of the Fischer Tropsch process using zeolites for tail gas separation[J]. Physical Chemistry Chemical Physics, 2014, 16(12): 5678-5688.
9	WAINAINA Steven, HORVÁTH Ilona Sárvári, TAHERZADEH Mohammad J. Biochemicals from food waste and recalcitrant biomass via syngas fermentation: A review[J]. Bioresource Technology, 2018, 248: 113-121.
10	KIM Ji-Yeon, LEE Mungyu, Soyoung OH, et al. Acetogen and acetogenesis for biological syngas valorization[J]. Bioresource Technology, 2023, 384: 129368.
11	DANIELL James, Michael KÖPKE, SIMPSON Séan. Commercial biomass syngas fermentation[J]. Energies, 2012, 5(12): 5372-5417.
12	ABRINI Jamal, NAVEAU Henry, NYNS Edmond-Jacques. Clostridium autoethanogenum, sp. nov., an anaerobic bacterium that produces ethanol from carbon monoxide[J]. Archives of Microbiology, 1994, 161(4): 345-351.
13	ACHARYA Bimal, ROY Poritosh, DUTTA Animesh. Review of syngas fermentation processes for bioethanol[J]. Biofuels, 2014, 5(5): 551-564.
14	SUN Xiao, ATIYEH Hasan K, HUHNKE Raymond L, et al. Syngas fermentation process development for production of biofuels and chemicals: A review[J]. Bioresource Technology Reports, 2019, 7: 100279.
15	ABUBACKAR Haris Nalakath, VEIGA María C, KENNES Christian. Carbon monoxide fermentation to ethanol by Clostridium autoethanogenum in a bioreactor with no accumulation of acetic acid[J]. Bioresource Technology, 2015, 186: 122-127.
16	徐惠娟, 梁翠谊, 许敬亮, 等. 合成气发酵梭菌C.autoethanogenum的生长特性与CO发酵性能[J]. 华南理工大学学报(自然科学版), 2014, 42(11): 136-142.
	XU Huijuan, LIANG Cuiyi, XU Jingliang, et al. Growth characteristics and carbon monoxide fermentation performance of Clostridium autoethanogenum [J]. Journal of South China University of Technology (Natural Science Edition), 2014, 42(11): 136-142.
17	XIE Bintao, LIU Ziyong, TIAN Lei, et al. Physiological response of Clostridium ljungdahlii DSM 13528 of ethanol production under different fermentation conditions[J]. Bioresource Technology, 2015, 177: 302-307.
18	SCHULZ Sarah, MOLITOR Bastian, ANGENENT Largus T. Acetate augmentation boosts the ethanol production rate and specificity by Clostridium ljungdahlii during gas fermentation with pure carbon monoxide[J]. Bioresource Technology, 2023, 369: 128387.
19	COTTER Jacqueline L, CHINN Mari S, GRUNDEN Amy M. Influence of process parameters on growth of Clostridium ljungdahlii and Clostridium autoethanogenum on synthesis gas[J]. Enzyme and Microbial Technology, 2009, 44(5): 281-288.
20	RAJAGOPALAN Srini, DATAR Rohit P, LEWIS Randy S. Formation of ethanol from carbon monoxide via a new microbial catalyst[J]. Biomass and Bioenergy, 2002, 23(6): 487-493.
21	XU Huijuan, LIANG Cuiyi, YUAN Zhenhong, et al. A study of CO/syngas bioconversion by Clostridium autoethanogenum with a flexible gas-cultivation system[J]. Enzyme and Microbial Technology, 2017, 101: 24-29.
22	徐惠娟, 吴逸豪, 张敏, 等. 一种用于检测气体采样袋体积的装置及方法: CN113532577A[P]. 2021-10-22.
	XU Huijuan, WU Yihao, ZHANG Min, et al. The invention relates to a device and a method for detecting the volume of a gas sampling bag: CN113532577A[P]. 2021-10-22.
23	SINHAROY Arindam, PAKSHIRAJAN Kannan, LENS Piet N L. Syngas fermentation for bioenergy production: Advances in bioreactor systems[M]//SINHAROY Arindam, LENS Piet N L, eds. Applied environmental science and engineering for a sustainable future. Cham: Springer, 2022: 325-358.
24	RAGSDALE Steve W, LJUNGDAHL Lars G. Hydrogenase from acetobacterium woodii[J]. Archives of Microbiology, 1984, 139(4): 361-365.
25	HURST Kendall M, LEWIS Randy S. Carbon monoxide partial pressure effects on the metabolic process of syngas fermentation[J]. Biochemical Engineering Journal, 2010, 48(2): 159-165.
26	NORMAN Rupert O J, MILLAT Thomas, SCHATSCHNEIDER Sarah, et al. Genome-scale model of C. autoethanogenum reveals optimal bioprocess conditions for high-value chemical production from carbon monoxide[J]. Engineering Biology, 2019, 3(2): 32-40.
27	ALLAART Maximilienne T, DIENDER Martijn, SOUSA Diana Z, et al. Overflow metabolism at the thermodynamic limit of life: How carboxydotrophic acetogens mitigate carbon monoxide toxicity[J]. Microbial Biotechnology, 2023, 16(4): 697-705.
28	HERMANN Maria, TELEKI Attila, WEITZ Sandra, et al. Electron availability in CO₂, CO and H₂ mixtures constrains flux distribution, energy management and product formation in Clostridium ljungdahlii [J]. Microbial Biotechnology, 2020, 13(6): 1831-1846.
29	RICHTER H, MOLITOR B, WEI H, et al. Ethanol production in syngas-fermenting Clostridium ljungdahlii is controlled by thermodynamics rather than by enzyme expression[J]. Energy & Environmental Science, 2016, 9(7): 2392-2399.
30	MOLITOR Bastian, MARCELLIN Esteban, ANGENENT Largus T. Overcoming the energetic limitations of syngas fermentation[J]. Current Opinion in Chemical Biology, 2017, 41: 84-92.
31	MANN Marcel, MUNCH Garret, REGESTEIN Lars, et al. Cultivation strategies of Clostridium autoethanogenum on xylose and carbon monoxide combination[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(7): 2632-2639.
32	ABUBACKAR Haris Nalakath, Ánxela FERNÁNDEZ-NAVEIRA, VEIGA María C, et al. Impact of cyclic pH shifts on carbon monoxide fermentation to ethanol by Clostridium autoethanogenum [J]. Fuel, 2016, 178: 56-62.
33	XU Huijuan, LIANG Cuiyi, CHEN Xiaoyan, et al. Impact of exogenous acetate on ethanol formation and gene transcription for key enzymes in Clostridium autoethanogenum grown on CO[J]. Biochemical Engineering Journal, 2020, 155: 107470.
34	KWON Soo Jae, LEE Joungmin, LEE Hyun Sook. Acetate-assisted carbon monoxide fermentation of Clostridium sp. AWRP[J]. Process Biochemistry, 2022, 113: 47-54.
35	ZHANG Jie, TAYLOR Steven, WANG Yi. Effects of end products on fermentation profiles in Clostridium carboxidivorans P7 for syngas fermentation[J]. Bioresource Technology, 2016, 218: 1055-1063.
36	Hongrae IM, AN Taegwang, KWON Rokgyu, et al. Effect of organic nitrogen supplements on syngas fermentation using Clostridium autoethanogenum [J]. Biotechnology and Bioprocess Engineering, 2021, 26(3): 476-482.
37	MADDOX I S, STEINER E, HIRSCH S, et al. The cause of “acid-crash” and “acidogenic fermentations” during the batch acetone-butanol-ethanol (ABE-) fermentation process[J]. Journal of Molecular Microbiology and Biotechnology, 2000, 2(1): 95-100.
38	YANG Xuepeng, TU Maobing, XIE Rui, et al. A comparison of three pH control methods for revealing effects of undissociated butyric acid on specific butanol production rate in batch fermentation of Clostridium acetobutylicum[J]. AMB Express, 2013, 3(1): 1-8.
39	Sara RAMIÓ-PUJOL, Ramon GANIGUÉ, Lluís BAÑERAS, et al. Incubation at 25℃ prevents acid crash and enhances alcohol production in Clostridium carboxidivorans P7[J]. Bioresource Technology, 2015, 192: 296-303.
40	ANGGRAINI Irika Devi, KERYANTI Keryanti, KRESNOWATI Made Tri Ari Penia, et al. Bioethanol production via syngas fermentation of clostridium ljungdahlii in a hollow fiber membrane supported bioreactor[J]. International Journal of Technology, 2019, 10(3): 481-490.
41	BENEVENUTI Carolina, BRANCO Marcelle, NASCIMENTO-CORREA Mariana DO, et al. Residual gas for ethanol production by Clostridium carboxidivorans in a dual impeller stirred tank bioreactor (STBR)[J]. Fermentation, 2021, 7(3): 199.

[1]	郑云香, 高艺伦, 李宴汝, 刘青霖, 张浩腾, 王向鹏. 氨基三乙酸酐改性多孔双网络水凝胶的制备及吸附性能[J]. 化工进展, 2024, 43(8): 4542-4549.
[2]	张真, 张凡, 云祉婷. 绿氢在石化和化工行业的减碳经济性分析[J]. 化工进展, 2024, 43(6): 3021-3028.
[3]	曾壮, 李柯志, 苑志伟, 杜金涛, 李卓师, 王悦. CO/CO₂ 加氢制低碳醇改性费托合成催化剂研究进展[J]. 化工进展, 2024, 43(6): 3061-3079.
[4]	黄澎, 邹颖, 王宝焕, 王逍妍, 赵勇, 梁鑫, 胡迪. 二氧化碳电催化还原反应制合成气催化剂研究进展[J]. 化工进展, 2024, 43(5): 2760-2775.
[5]	王嘉锐, 刘大伟, 邓耀, 徐瑾, 马晓迅, 徐龙. 载氧体在甲烷化学链重整反应中的研究进展[J]. 化工进展, 2024, 43(5): 2235-2253.
[6]	王欣宇, 王超, 张梦娟, 刘方正, 李晗旸, 王正林, 贾鑫, 宋兴飞, 许光文, 韩振南. 松木颗粒流态化两段气化制备清洁燃气的工艺稳定性验证[J]. 化工进展, 2024, 43(5): 2576-2586.
[7]	李娜, 赵婉彤, 凌丽霞, 王宝俊, 章日光. RhCu催化剂中限域环境调控合成气转化生成CH _x 反应性能[J]. 化工进展, 2024, 43(5): 2684-2695.
[8]	成昊霖, 年瑶, 韩优. CH₄和CO₂共转化反应机理研究进展[J]. 化工进展, 2024, 43(1): 60-75.
[9]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[10]	陆洋, 周劲松, 周启昕, 王瑭, 刘壮, 李博昊, 周灵涛. CeO₂/TiO₂吸附剂煤气脱汞产物的浸出规律[J]. 化工进展, 2023, 42(7): 3875-3883.
[11]	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.
[12]	阮鹏, 杨润农, 林梓荣, 孙永明. 甲烷催化部分氧化制合成气催化剂的研究进展[J]. 化工进展, 2023, 42(4): 1832-1846.
[13]	田园, 娄舒洁, 孟闪茹, 闫敬如, 肖海成. 合成气制高碳醇钴基催化剂研究进展[J]. 化工进展, 2023, 42(4): 1869-1876.
[14]	胡鹏, 赵丹, 纪红兵. 温控构筑仿生契合辨识机制强化合成气提纯[J]. 化工进展, 2023, 42(12): 6133-6135.
[15]	唐裕芳, 刘磊, 杨雨欣, 曾彦霖, 李玉芹, 周蓉, 张妙玲. 胺鲜酯和2,4-二氯苯氧乙酸协同诱导裂殖壶菌积累DHA[J]. 化工进展, 2023, 42(11): 5900-5907.

低碳合成气生物转化及产乙醇发酵工艺探索

Bioconversion of low-carbon syngas to ethanol and the process development

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 5

参考文献 41

相关文章 15

编辑推荐

Metrics

本文评价