合成气乙醇发酵技术研究进展
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摘要
采用合成气发酵生产燃料乙醇具有反应条件温和、产物耐受性好、原料来源丰富等优点,是燃料乙醇生产的一种新型工艺。文章综述了国内外合成气厌氧发酵的微生物种类,常见合成气乙醇发酵微生物的生长、代谢特点以及底物利用范围;分析了合成气乙醇发酵的Wood-Ljungdahl代谢途径,以及Wood-Ljungdahl代谢途径中涉及的关键酶类甲酸脱氢酶和CO脱氢酶/乙酰辅酶A合成酶;探讨了过程工艺参数如培养介质、还原剂、pH、气体组成、终产物、培养基和培养方法对合成气发酵的影响;比较了不同反应器在体积传质系数等方面的差异,并重点分析了搅拌罐式反应器和柱式反应器等的反应特点。同时,对合成气发酵的未来发展方向进行了展望。
Bioethanol production through syngas fermentation has many advantages, such as mild reaction conditions, higher end-product tolerance, rich source of raw carbon materials and so on, which is a novel method for fuel ethanol productions. In this paper, the types of microorganisms for syngas fermentation, the characteristics of growth, metabolism and substrate utilization of the mainmicroorganisms, Wood-Ljungdahl pathways, the key enzymes of formate dehydrogenase and carbonmonoxide dehydrogenase/acetyl-CoA synthase, the influence factors of culture medium, reducing agent,pH, gas composition, products, medium composition and culture methods on syngas fermentation, and the types of syngas fermentation reactor were reviewed. The prospect of future development direction of syngas fermentation was proposed.
Bioethanol production through syngas fermentation has many advantages, such as mild reaction conditions, higher end-product tolerance, rich source of raw carbon materials and so on, which is a novel method for fuel ethanol productions. In this paper, the types of microorganisms for syngas fermentation, the characteristics of growth, metabolism and substrate utilization of the mainmicroorganisms, Wood-Ljungdahl pathways, the key enzymes of formate dehydrogenase and carbonmonoxide dehydrogenase/acetyl-CoA synthase, the influence factors of culture medium, reducing agent,pH, gas composition, products, medium composition and culture methods on syngas fermentation, and the types of syngas fermentation reactor were reviewed. The prospect of future development direction of syngas fermentation was proposed.
引文
[1]刘朝全. 2017年国内外油气行业发展报告[M].北京:石油工业出版社, 2018.LIU Chaoquan. Report on development of domestic and foreign oiland gas industry in 2017[M]. Beijing:Petroleum Industry Press,2018.
[2]袁振宏.能源微生物学[M].北京:化学工业出版社,2012.YUAN Zhenhong. Energy microbiology[M]. Beijing:ChemicalIndustry Press, 2012.
[3]袁振宏.生物质能高效利用技术[M].北京:化学工业出版社,2014.YUAN Zhenhong. Technologies on bioenergy high efficiencyutilization[M]. Beijing:Chemical Industry Press, 2014.
[4]徐惠娟.合成气梭菌发酵乙醇及其代谢途径分析[D].北京:中国科学院大学,2016.XU Huijuan. Syngas fermentation to ethanol with Clostridium andits metabolic pathway[D]. Beijing:University of Chinese Academyof Sciences,2016.
[5] MUNASINGHE P C, KHANAL S K. Biomass-derived syngasfermentation into biofuels:opportunities and challenges[J].Bioresource Technology, 2010, 101:5013-5022.
[6] WU C, TU X. Biological and fermentative conversion of syngas[M]//RAFAEL L, CAROL S K L, KAREN W, et al. Handbook ofbiofuels production. Duxford:Woodhead Publishing, 2011:335-357.
[7] BRADLEY E S, RYAN A B, DILA R B, et al. Syngas fermentationto biofuels:effects of hydrogen partial pressure on hydrogenase efficiency[J]. Biomass and Bioenergy,2013,55:156-162.
[8] DEBABOV V G. Bioethanol from synthesis gas[J]. AppliedBiochemistry and Microbiology, 2013, 49(7):619-628.
[9] PHILLIPS J R CLAUSEN E C, GADDY J L, et a1. Biologicalproduction of ethanol from coal synthesis gas[J]. AppliedBiochemistry and Biotechnology, 1993, 39/40(1):559-571.
[10] HENSTRA A M, SIPMA J, RINZEMA A, et a1. Microbiology ofsynthesis gas fermentation for biofuel production[J]. CurrentOpinion in Biotechnology, 2007, 18:200-206.
[11] ABUBACKAR H N, VEIGA M C, KENNES C. Biologicalconversion of carbon monoxide:rich syngas or waste gases tobioethanol[J]. Biofuels, Bioproducts and Biorefining, 2011, 5(1):93-114.
[12] MOHAMMADI M, NAJAFPOUR G D, YOUNESI H, et al.Bioconversion of synthesis gas to second generation biofuels:areview[J]. Renewable and Sustainable Energy Reviews, 2011, 15(9), 4255-4273.
[13] LIEW F M, K?PKE M, SIMPSON S D. Gas fermentation forcommercial biofuels production[M]//FANG Z, editor. Biofuel ProdDev Prospect. Rijeka:InTech, 2013:125-74.
[14] GADDY J L, CLAUSEN E C. Clostridiumm ljungdahlii, ananaerobic ethanol and acetate producing microorganism:US5173429[P]. 1992-12-22.
[15] KLASSON K T, ACKERSON C M D, CLAUSEN E C, et al.Biological conversion of synthesis gas into fuels[J]. InternationalJournal of Hydrogen Energy, 1992, 17(4):281-288.
[16] TANNER R S, MILLER L M, YANG D. Clostridium ljungdahlii sp. nov., an acetogenic species in clostridial r RNA homologygroup I[J]. International Journal of Systematic Bacteriology, 1993,43:232-236.
[17] RAJAGOPALAN S, DATAR R P, LEWIS R S. Formation ofethanol from carbon monoxide via a new microbial catalyst[J].Biomass and Bioenergy, 2002, 23:487-493.
[18] DATAR R P, SHENKMAN R M, CATENI B G, et al.Fermentation of biomass-generated producer gas to ethanol[J].Biotechnology and Bioengineering, 2004, 86:587-594.
[19] ABRINI J, NAVEAU H, NYNS E J. Clostridium autoethanogenum, sp. nov., an anerobic bacterium that producesethanol from carbon monoxide[J]. Archives of Microbiology, 1994,161:345-351.
[20]郭颖.合成气乙醇发酵培养基及工艺优化研究[D].北京:中国科学院大学,2010.GUO Ying. Medium and process optimization for the biologicalproduction of ethanol from syngas[D]. Beijing:University ofChinese Academy of Sciences,2010.
[21] XU H, LIANG C, YUAN Z, et al. A study of CO/syngasbioconversion by Clostridium autoethanogenum with a flexible gas-cultivation system[J]. Enzyme and Microbial Technology, 2017,101:24-29.
[22]徐惠娟,梁翠谊,许敬亮,等. CO一步法C. autoethanogenum发酵产乙醇的工艺研究[J].农业工程学报,2017,33(23):246-251.XU Huijuan, LIANG Cuiyi, XU Jingliang, et al. Study on one-stepethanol production from CO by C. autoethanogenum[J].Transactions of the Chinese Society of Agricultural Engineering,2017, 33(23):246-251.
[23] HURST K M, LEWIS R S. Carbon monoxide partial pressureeffects on the metabolic process of syngas fermentation[J].Biochemical Engineering Journal, 2010, 48:159-165.
[24]朱小飞,谭相石.金属组学:Wood-Ljungdahl通路中的金属蛋白/金属酶[J].中国科学B辑(化学), 2009, 39(7):607-619.ZHU Xiaofei, TAN Xiangshi. Metalloproteins/metalloenzymes forthe synthesis of acetyl-CoA in the Wood-Ljungdahl pathway[J].Science in China Series B(Chemistry), 2009, 39(7):607-619.
[25] RAGSDALE S W. Life with carbon monoxide[J]. Critical Reviewsin Biochemistry and Molecular Biology, 2004, 39:165-195.
[26] KIM Y K, PARK S E, LEE H, et al. Enhancement of bioethanolproduction in syngas fermentation with Clostridium ljungdahlii using nanoparticles[J]. Bioresource Technology, 2014, 159:446-450.
[27] SUN X, ATIYEH H K, KUMAR A, et al. Enhanced ethanolproduction by Clostridium ragsdalei from syngas by incorporatingbiochar in the fermentation medium[J]. Bioresource Technology,2018, 247:291-301.
[28] ABUBACKAR N H, VEIGA M C, KENNES C. Biologicalconversion of carbon monoxide to ethanol:effect of pH, gaspressure, reducing agent and yeast extract[J]. BioresourceTechnology, 2012, 114:518-522.
[29] SIM J H, KAMARUDDIN A H. Optimization of acetic acidproduction from synthesis gas by chemolithotrophic bacterium—Clostridium aceticum using statistical approach[J]. BioresourceTechnology, 2008, 99:2724-2735.
[30] KIMURA Z I, KITA A, IWASAKI Y, et al. Glycerol acts asalternative electron sink during syngas fermentation bythermophilic anaerobe Moorella thermoacetica[J]. Journal ofBioscience and Bioengineering, 2016, 121(3):268-273.
[31] TISSERA S D, K?PKE M, SIMPSON S D, et al. Syngasbiorefinery and syngas utilization[J]. Advances in BiochemicalEngineering/Biotechnology, 2017, 5:1-34.
[32] AHMED A, CATENI B G, HUHNKE R L, et al. Effects ofbiomass-generated producer gas constituents on cell growth,product distribution and hydrogenase activity of Clostridium carboxidivorans P7T[J]. Biomass Bioenergy, 2006, 30:665-672.
[33] AHMED A, LEWIS R L. Fermentation of biomass generatedsynthesis gas:effects of nitric oxide[J]. Biotechnology andBioengineering, 2007, 97(5):1080-1086.
[34] ESQUIVEL-ELIZONDO S, DELGADO A G, RITTMANN B E, etal. The effects of CO2and H2on CO metabolism by pure andmixed microbial cultures[J]. Biotechnology for Biofuels, 2017,10:220.
[35] ZHANG J, TAYLOR S, WANG Y. Effects of end products onfermentation profiles in Clostridium carboxidivorans P7 for syngasfermentation[J]. Bioresource Technology, 2016, 218:1055-1063.
[36] MADDIPATI P, ATIYEH H K, BELLMER D D, et al. Ethanolproduction from syngas by Clostridium strain P11 using corn steepliquor as a nutrient replacement to yeast extract[J]. BioresourceTechnology, 2011, 102:6494-6501.
[37] GUO Y, XU J L, ZHANG Y, et al. Medium optimization forethanol production with Clostridium autoethanogenum with carbonmonoxide as sole carbon source[J]. Bioresource Technology, 2010,101:8784-8789.
[38] KUNDIYANA D K, HUHNKE R L, WILKINS M R. Effect ofnutrient limitation and two-stage continuous fermentor design onproductivities during"Clostridium ragsdalei"syngas fermentation[J]. Bioresource Technology, 2011, 102:6058-6064.
[39] DIENDER M, STAMS A J M, SOUSA D Z. Production of medium-chain fatty acids and higher alcohols by a synthetic co-culturegrown on carbon monoxide or syngas[J]. Biotechnology forBiofuels, 2016, 9, 82:1-11.
[40] MUNASINGHE P C, KHANAL S K. Syngas fermentation tobiofuel:evaluation of carbon monoxide mass transfer coefficient(kLa)in different reactor configurations[J]. Biotechnology Progress,2010, 26(6):1616-1621.
[41] LANE J. Coskata’s technology re-emerges as Synata Bio:biofuels digest[EB/OL].[2016-01-24]. http://www.biofuelsdigest.com/bdigest/2016/01/24/coskatas-technology-re-emerges-as-synata-bio/.
[42] HEIJSTRA B D, LEANG C, JUMINAGA A. Gas fermentation:cellular engineering possibilities and scale up[J]. Microbial CellFactories, 2017, 16:60.
[43] FUNGMIN L, ANNE M H, MICHAEL K, et al. Metabolicengineering of Clostridium autoethanogenum for selective alcoholproduction[J]. Metabolic Engineering, 2017, 40:104-114.
[44] MUELLER A, KOEPKE M, NAGARAJU S. Recombinantmicroorganisms and uses therefor:US9890384[P]. 2018-02-13.
[45] FENG X, ZHUANG W Q, COLLETTI P, et al. Metabolic pathwaydetermination and flux analysis in nonmodel microorganismsthrough 13C-isotope labeling[J]. Microbial Systems Biology, 2012,96(4):309-330.
[2]袁振宏.能源微生物学[M].北京:化学工业出版社,2012.YUAN Zhenhong. Energy microbiology[M]. Beijing:ChemicalIndustry Press, 2012.
[3]袁振宏.生物质能高效利用技术[M].北京:化学工业出版社,2014.YUAN Zhenhong. Technologies on bioenergy high efficiencyutilization[M]. Beijing:Chemical Industry Press, 2014.
[4]徐惠娟.合成气梭菌发酵乙醇及其代谢途径分析[D].北京:中国科学院大学,2016.XU Huijuan. Syngas fermentation to ethanol with Clostridium andits metabolic pathway[D]. Beijing:University of Chinese Academyof Sciences,2016.
[5] MUNASINGHE P C, KHANAL S K. Biomass-derived syngasfermentation into biofuels:opportunities and challenges[J].Bioresource Technology, 2010, 101:5013-5022.
[6] WU C, TU X. Biological and fermentative conversion of syngas[M]//RAFAEL L, CAROL S K L, KAREN W, et al. Handbook ofbiofuels production. Duxford:Woodhead Publishing, 2011:335-357.
[7] BRADLEY E S, RYAN A B, DILA R B, et al. Syngas fermentationto biofuels:effects of hydrogen partial pressure on hydrogenase efficiency[J]. Biomass and Bioenergy,2013,55:156-162.
[8] DEBABOV V G. Bioethanol from synthesis gas[J]. AppliedBiochemistry and Microbiology, 2013, 49(7):619-628.
[9] PHILLIPS J R CLAUSEN E C, GADDY J L, et a1. Biologicalproduction of ethanol from coal synthesis gas[J]. AppliedBiochemistry and Biotechnology, 1993, 39/40(1):559-571.
[10] HENSTRA A M, SIPMA J, RINZEMA A, et a1. Microbiology ofsynthesis gas fermentation for biofuel production[J]. CurrentOpinion in Biotechnology, 2007, 18:200-206.
[11] ABUBACKAR H N, VEIGA M C, KENNES C. Biologicalconversion of carbon monoxide:rich syngas or waste gases tobioethanol[J]. Biofuels, Bioproducts and Biorefining, 2011, 5(1):93-114.
[12] MOHAMMADI M, NAJAFPOUR G D, YOUNESI H, et al.Bioconversion of synthesis gas to second generation biofuels:areview[J]. Renewable and Sustainable Energy Reviews, 2011, 15(9), 4255-4273.
[13] LIEW F M, K?PKE M, SIMPSON S D. Gas fermentation forcommercial biofuels production[M]//FANG Z, editor. Biofuel ProdDev Prospect. Rijeka:InTech, 2013:125-74.
[14] GADDY J L, CLAUSEN E C. Clostridiumm ljungdahlii, ananaerobic ethanol and acetate producing microorganism:US5173429[P]. 1992-12-22.
[15] KLASSON K T, ACKERSON C M D, CLAUSEN E C, et al.Biological conversion of synthesis gas into fuels[J]. InternationalJournal of Hydrogen Energy, 1992, 17(4):281-288.
[16] TANNER R S, MILLER L M, YANG D. Clostridium ljungdahlii sp. nov., an acetogenic species in clostridial r RNA homologygroup I[J]. International Journal of Systematic Bacteriology, 1993,43:232-236.
[17] RAJAGOPALAN S, DATAR R P, LEWIS R S. Formation ofethanol from carbon monoxide via a new microbial catalyst[J].Biomass and Bioenergy, 2002, 23:487-493.
[18] DATAR R P, SHENKMAN R M, CATENI B G, et al.Fermentation of biomass-generated producer gas to ethanol[J].Biotechnology and Bioengineering, 2004, 86:587-594.
[19] ABRINI J, NAVEAU H, NYNS E J. Clostridium autoethanogenum, sp. nov., an anerobic bacterium that producesethanol from carbon monoxide[J]. Archives of Microbiology, 1994,161:345-351.
[20]郭颖.合成气乙醇发酵培养基及工艺优化研究[D].北京:中国科学院大学,2010.GUO Ying. Medium and process optimization for the biologicalproduction of ethanol from syngas[D]. Beijing:University ofChinese Academy of Sciences,2010.
[21] XU H, LIANG C, YUAN Z, et al. A study of CO/syngasbioconversion by Clostridium autoethanogenum with a flexible gas-cultivation system[J]. Enzyme and Microbial Technology, 2017,101:24-29.
[22]徐惠娟,梁翠谊,许敬亮,等. CO一步法C. autoethanogenum发酵产乙醇的工艺研究[J].农业工程学报,2017,33(23):246-251.XU Huijuan, LIANG Cuiyi, XU Jingliang, et al. Study on one-stepethanol production from CO by C. autoethanogenum[J].Transactions of the Chinese Society of Agricultural Engineering,2017, 33(23):246-251.
[23] HURST K M, LEWIS R S. Carbon monoxide partial pressureeffects on the metabolic process of syngas fermentation[J].Biochemical Engineering Journal, 2010, 48:159-165.
[24]朱小飞,谭相石.金属组学:Wood-Ljungdahl通路中的金属蛋白/金属酶[J].中国科学B辑(化学), 2009, 39(7):607-619.ZHU Xiaofei, TAN Xiangshi. Metalloproteins/metalloenzymes forthe synthesis of acetyl-CoA in the Wood-Ljungdahl pathway[J].Science in China Series B(Chemistry), 2009, 39(7):607-619.
[25] RAGSDALE S W. Life with carbon monoxide[J]. Critical Reviewsin Biochemistry and Molecular Biology, 2004, 39:165-195.
[26] KIM Y K, PARK S E, LEE H, et al. Enhancement of bioethanolproduction in syngas fermentation with Clostridium ljungdahlii using nanoparticles[J]. Bioresource Technology, 2014, 159:446-450.
[27] SUN X, ATIYEH H K, KUMAR A, et al. Enhanced ethanolproduction by Clostridium ragsdalei from syngas by incorporatingbiochar in the fermentation medium[J]. Bioresource Technology,2018, 247:291-301.
[28] ABUBACKAR N H, VEIGA M C, KENNES C. Biologicalconversion of carbon monoxide to ethanol:effect of pH, gaspressure, reducing agent and yeast extract[J]. BioresourceTechnology, 2012, 114:518-522.
[29] SIM J H, KAMARUDDIN A H. Optimization of acetic acidproduction from synthesis gas by chemolithotrophic bacterium—Clostridium aceticum using statistical approach[J]. BioresourceTechnology, 2008, 99:2724-2735.
[30] KIMURA Z I, KITA A, IWASAKI Y, et al. Glycerol acts asalternative electron sink during syngas fermentation bythermophilic anaerobe Moorella thermoacetica[J]. Journal ofBioscience and Bioengineering, 2016, 121(3):268-273.
[31] TISSERA S D, K?PKE M, SIMPSON S D, et al. Syngasbiorefinery and syngas utilization[J]. Advances in BiochemicalEngineering/Biotechnology, 2017, 5:1-34.
[32] AHMED A, CATENI B G, HUHNKE R L, et al. Effects ofbiomass-generated producer gas constituents on cell growth,product distribution and hydrogenase activity of Clostridium carboxidivorans P7T[J]. Biomass Bioenergy, 2006, 30:665-672.
[33] AHMED A, LEWIS R L. Fermentation of biomass generatedsynthesis gas:effects of nitric oxide[J]. Biotechnology andBioengineering, 2007, 97(5):1080-1086.
[34] ESQUIVEL-ELIZONDO S, DELGADO A G, RITTMANN B E, etal. The effects of CO2and H2on CO metabolism by pure andmixed microbial cultures[J]. Biotechnology for Biofuels, 2017,10:220.
[35] ZHANG J, TAYLOR S, WANG Y. Effects of end products onfermentation profiles in Clostridium carboxidivorans P7 for syngasfermentation[J]. Bioresource Technology, 2016, 218:1055-1063.
[36] MADDIPATI P, ATIYEH H K, BELLMER D D, et al. Ethanolproduction from syngas by Clostridium strain P11 using corn steepliquor as a nutrient replacement to yeast extract[J]. BioresourceTechnology, 2011, 102:6494-6501.
[37] GUO Y, XU J L, ZHANG Y, et al. Medium optimization forethanol production with Clostridium autoethanogenum with carbonmonoxide as sole carbon source[J]. Bioresource Technology, 2010,101:8784-8789.
[38] KUNDIYANA D K, HUHNKE R L, WILKINS M R. Effect ofnutrient limitation and two-stage continuous fermentor design onproductivities during"Clostridium ragsdalei"syngas fermentation[J]. Bioresource Technology, 2011, 102:6058-6064.
[39] DIENDER M, STAMS A J M, SOUSA D Z. Production of medium-chain fatty acids and higher alcohols by a synthetic co-culturegrown on carbon monoxide or syngas[J]. Biotechnology forBiofuels, 2016, 9, 82:1-11.
[40] MUNASINGHE P C, KHANAL S K. Syngas fermentation tobiofuel:evaluation of carbon monoxide mass transfer coefficient(kLa)in different reactor configurations[J]. Biotechnology Progress,2010, 26(6):1616-1621.
[41] LANE J. Coskata’s technology re-emerges as Synata Bio:biofuels digest[EB/OL].[2016-01-24]. http://www.biofuelsdigest.com/bdigest/2016/01/24/coskatas-technology-re-emerges-as-synata-bio/.
[42] HEIJSTRA B D, LEANG C, JUMINAGA A. Gas fermentation:cellular engineering possibilities and scale up[J]. Microbial CellFactories, 2017, 16:60.
[43] FUNGMIN L, ANNE M H, MICHAEL K, et al. Metabolicengineering of Clostridium autoethanogenum for selective alcoholproduction[J]. Metabolic Engineering, 2017, 40:104-114.
[44] MUELLER A, KOEPKE M, NAGARAJU S. Recombinantmicroorganisms and uses therefor:US9890384[P]. 2018-02-13.
[45] FENG X, ZHUANG W Q, COLLETTI P, et al. Metabolic pathwaydetermination and flux analysis in nonmodel microorganismsthrough 13C-isotope labeling[J]. Microbial Systems Biology, 2012,96(4):309-330.