厌氧发酵生物制氢影响因素的研究
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摘要
在开发新能源的领域中,氢气以环保无污染的特性被认为是理想的新能源。制取氢气的方法多种多样,在众多的物理、化学、生物制氢法中,以混合菌种(厌氧活性污泥)为接种微生物的发酵法生物制氢最受科学界的关注。此种方法发展前景广阔,很有潜力达到工业化大规模生产。目前微生物厌氧发酵法生物制氢存在的主要问题是产氢率不高,产氢不连续。污泥预处理可以改善其产氢性能,污泥预处理的方法,对于快速启动生物制氢反应器、缩短发酵时间,提高反应设备的产氢能力和增强产氢过程稳定性,均具有重要的影响。
本实验以污水处理厂的厌氧污泥为接种微生物进行厌氧发酵生物制氢,采用批式试验,为了提高产氢性能从两方面研究,一方面通过对污泥进行5种预处理实验选出其中效果较好的三种预处理方法,确定其最佳控制参数。另一方面对生态因子进行考察,在pH值、COD浓度、碳氮质量比、温度方面研究对产氢性能的影响。
研究结果表明:
(1)本实验比较5种污泥预处理方法其中酸处理、碱处理、热处理方法造价低,效果理想适合大规模工业化生产。
(2)预处理实验所用的酸采用乙酸,碱采用氨水。酸处理最佳控制参数为:最佳酸处理时间3.0h,pH值为4.0,碱处理最佳控制参数为:最佳碱处理时间3.0h,pH值为10.0。热处理最佳控制参数为:最佳热处理时间为10 min,温度为90℃。
(3)由本实验得出污泥预处理方法中,酸处理效果最佳。
(4)在生态因子方面考察了pH值、COD浓度、碳氮质量比、温度等生态因子对产氢能力的影响。实验结果表明:在温度35℃,pH值为5.0,产氢性能最好。产气速率随进水COD浓度的增加而升高,但COD浓度超过7000 mg/L时致使反应停止。
厌氧发酵生物制氢试验中通过预处理污泥不仅提高产氢率,而且产氢的同时也降解了有机物,废水得到净化。
In the field of developing new energy sources, environmental pollution to the characteristics of hydrogen is considered to be the ideal new energy. Many ways to produce hydrogen, in many physical, chemical, biological hydrogen production methods. The mixed bacteria (anaerobic activated sludge) is inoculated with microbial fermentation hydrogen production much attention to the scientific community, Broad prospects for development of this method, a lot of potential to achieve industrial scale production of biological hydrogen production technology. Anaerobic fermentation of biological hydrogen production is currently the main question is the hydrogen production rate is not high, hydrogen production is not continuous. The sludge pretreatment can improve hydrogen production performance. Sludge pretreatment methods , for the Quick Start hydrogen production reactor, shorten the fermentation time and improve response capabilities and equipment, hydrogen production process of enhancing the stability of hydrogen production, all have an important impact.
In this experiment, the anaerobic wastewater treatment plant sludge for anaerobic microbial fermentation of inoculated biological hydrogen production by batch tests, in order to improve the performance of hydrogen production from two studies, one by sludge pre-experimental selection of 5 out the better of the three pretreatment methods to determine the optimal control parameters. Study of ecological factors on the other hand, in the pH, COD concentration, carbon and nitrogen ratio, temperature aspects of research on hydrogen production performance.
The results show that:
(1) In this study, which compared the five pretreatment sludge: acid treatment, alkali treatment, heat treatment. these methods are low cost, the result is ideal for large-scale industrial production.
(2) Pretreatment with acetic acid used in the experiments, alkaline using ammonia. Optimal control parameters for the acid treatment:The best time of acid treatment 3.0h, pH value of 4.0, the best control parameters for the alkali treatment: The best alkali treatment time 3.0h, pH value of 10. Optimal control parameters for the best heat treatment time was 10 min, the temperature is 90℃.
(3) Pretreatment of sludge obtained by the experimental method, the acid treatment was the best results.
(4) Investigated in terms of ecological factors pH, COD concentration, carbon and nitrogen ratio, temperature and other ecological factors on hydrogen production ability. The results show that:the temperature of 35℃, pH=5.0, hydrogen production performance of the best. Gas production rate increased with increasing concentration of the influent COD increased, but the COD concentration in excess of 7000 mg/L resulted in reaction time to stop.
Anaerobic bio-hydrogen test increased by pretreatment of the sludge is not only the hydrogen yield and hydrogen production as well as degradation of the organic compounds, waste water purification.
本实验以污水处理厂的厌氧污泥为接种微生物进行厌氧发酵生物制氢,采用批式试验,为了提高产氢性能从两方面研究,一方面通过对污泥进行5种预处理实验选出其中效果较好的三种预处理方法,确定其最佳控制参数。另一方面对生态因子进行考察,在pH值、COD浓度、碳氮质量比、温度方面研究对产氢性能的影响。
研究结果表明:
(1)本实验比较5种污泥预处理方法其中酸处理、碱处理、热处理方法造价低,效果理想适合大规模工业化生产。
(2)预处理实验所用的酸采用乙酸,碱采用氨水。酸处理最佳控制参数为:最佳酸处理时间3.0h,pH值为4.0,碱处理最佳控制参数为:最佳碱处理时间3.0h,pH值为10.0。热处理最佳控制参数为:最佳热处理时间为10 min,温度为90℃。
(3)由本实验得出污泥预处理方法中,酸处理效果最佳。
(4)在生态因子方面考察了pH值、COD浓度、碳氮质量比、温度等生态因子对产氢能力的影响。实验结果表明:在温度35℃,pH值为5.0,产氢性能最好。产气速率随进水COD浓度的增加而升高,但COD浓度超过7000 mg/L时致使反应停止。
厌氧发酵生物制氢试验中通过预处理污泥不仅提高产氢率,而且产氢的同时也降解了有机物,废水得到净化。
In the field of developing new energy sources, environmental pollution to the characteristics of hydrogen is considered to be the ideal new energy. Many ways to produce hydrogen, in many physical, chemical, biological hydrogen production methods. The mixed bacteria (anaerobic activated sludge) is inoculated with microbial fermentation hydrogen production much attention to the scientific community, Broad prospects for development of this method, a lot of potential to achieve industrial scale production of biological hydrogen production technology. Anaerobic fermentation of biological hydrogen production is currently the main question is the hydrogen production rate is not high, hydrogen production is not continuous. The sludge pretreatment can improve hydrogen production performance. Sludge pretreatment methods , for the Quick Start hydrogen production reactor, shorten the fermentation time and improve response capabilities and equipment, hydrogen production process of enhancing the stability of hydrogen production, all have an important impact.
In this experiment, the anaerobic wastewater treatment plant sludge for anaerobic microbial fermentation of inoculated biological hydrogen production by batch tests, in order to improve the performance of hydrogen production from two studies, one by sludge pre-experimental selection of 5 out the better of the three pretreatment methods to determine the optimal control parameters. Study of ecological factors on the other hand, in the pH, COD concentration, carbon and nitrogen ratio, temperature aspects of research on hydrogen production performance.
The results show that:
(1) In this study, which compared the five pretreatment sludge: acid treatment, alkali treatment, heat treatment. these methods are low cost, the result is ideal for large-scale industrial production.
(2) Pretreatment with acetic acid used in the experiments, alkaline using ammonia. Optimal control parameters for the acid treatment:The best time of acid treatment 3.0h, pH value of 4.0, the best control parameters for the alkali treatment: The best alkali treatment time 3.0h, pH value of 10. Optimal control parameters for the best heat treatment time was 10 min, the temperature is 90℃.
(3) Pretreatment of sludge obtained by the experimental method, the acid treatment was the best results.
(4) Investigated in terms of ecological factors pH, COD concentration, carbon and nitrogen ratio, temperature and other ecological factors on hydrogen production ability. The results show that:the temperature of 35℃, pH=5.0, hydrogen production performance of the best. Gas production rate increased with increasing concentration of the influent COD increased, but the COD concentration in excess of 7000 mg/L resulted in reaction time to stop.
Anaerobic bio-hydrogen test increased by pretreatment of the sludge is not only the hydrogen yield and hydrogen production as well as degradation of the organic compounds, waste water purification.
引文
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[14] R.E.Hungate,The Rumen and Its Microbes,New york.Academic Press Inc.1966:8-90
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[27]肖本益,刘俊新.pH值对碱处理污泥厌氧发酵产氢的影响.科学通报,2005,50(24):2734-2738
[28]李兴杰.沼气发酵[J/OL].生物学通报,1999,34(3):16-17.
[29]Hu Bo,Chen Shulin.Pretreatment of methanogenic granules for immobilizedhydrogen fermentation[J].International Journal of Hydrogen Energy.2007
[30]王凯军,秦人伟.发酵工业废水处理[M]化学工业出版社. 2000.10-36。
[31]杨洁,季民等.污泥超声预处理促进厌氧消化反应试验[J]天津大学学报2006,39(10)1205-1208
[32]Schlafe O,Sievers M,K lotzucherH,et al Improvement of biological activity by low energy ultrasound assisted ioreactors[J].Ultasounics 2000,38(1/8):711-716
[33]王翠玲,谷晋川.微波技术在废水处理中的应用[J]环境监测管理与技术.2007,19(4):35-38
[34] Neher E.,Sakmann B..Single-channel currents recorded from membrane of denervated frog muscle fibers[J].Nature,1976,(260):779-802
[35]田禹,方琳,黄君礼等.微波辐射预处理对污泥结构及脱水性能的影响[J].中国环境科学,2006,26(4):459~463
[36]史苏佳,曹栋.微波原理及其在食品上的应用[J].山西食品工业.2002,3:8-9
[37]J.L.Garcia,B.K.C.Patel,B.Ollivier.Taxonomic,phylogenetic and ecological diversity of methanogenic archaea[J].Anaerobe,2000,6:205-226.
[38]Herbert H.P.Fang,Hong Liu.Effect of pH on hydrogen production from glucose by a mixed culture[J].Bioresource technology,2002,82:87-93.
[39]Chin-Chao Chen,Chiu-Yue Lin,Min-Cheng Lin.Acid-base enrichment enhances anaerobic hydrogen production process[J].Applied Microbiology and Biotechnology,2002,58:224-228.
[40]Wang CC,Chang CW,Chu CP,Lee DJ,Chang BV,Liao CS.Producing hydrogen fromwastewater sludge by Clostridium bifermentans[J].Journal of Biotechnology,2003,102:83-92.
[41]杜连祥.工业微生物学实验技术[M].天津:天津科学技术出版社, 1992. 32-42.
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[2]李文华.杨修.环境与发展.科学技术文献出版社.1994:12-13
[3]鲍德佑.太阳能-氢能系统的发展前景.太阳能学报.1995,16(1):114-122
[4]P.Hoffmann.Liquid Hydrogen Powers Third EQHHPP Demonstrain Bus.Hydogen and Fuel Cell Letter.1996.11(5):4-8
[5]李晨林.厌氧发酵生物制氢技术的研究[D]郑州:郑州大学.2002:1-4
[6]王艳辉.吴迪墉.迟建.氢能及制氢的应用技术现状及发展趋势.化工进展.2001(l):6-8
[7]任南琪.王爱杰.厌氧生物技术原理与应用[M]北京:化学工业出版社.2004:212-213
[8] King-Thom chung,Inhibitory Effects of H2 on Growth of Closrrium cettobioparuni,Applied and Evironmental Microiology,1976,31(3):342-348
[9]MichaelG..Doremus,James C.lindent,and Antonio R.Moreirat,Agitation and Pressure Efects on Acetone-butanol Fermentation,Biotechnology and Bioengineering,1985:27,852-860
[10]Linda K. owless,William L. Ellefson,Efects of Butanol on Clostrium ocetobutylicum,Applied and Eviromental Microiology,1985,50(5):1165-1170
[11]H.Bahl,M.Gottwald,A.Kuhn,et al.Nutritional Factors Affecting the Ratio of Solvents Produced by Clostrium acetoutylicum,Appied and Evironmental Microbiology,1988,52(1):169-172
[12]Run-Tao Yan,Chang-Xi Zhu,Christine Go oski et al.Expression of solvent-forming Enzymes and Onset of Production in Batch Cultures of Clostrium beyerinckii(Clostrium butylicum),Appied and Evironmental Microbiology,1488,54(3):642-648
[13]Birgit Darock,Huert Bahl,Gerhard Gottschalk,Parameters Affecting Solvent Production by Clostrium Pasteurianum,Appied and Evironmental Microbiology,1992,58(4):1233-1239
[14] R.E.Hungate,The Rumen and Its Microbes,New york.Academic Press Inc.1966:8-90
[15]刘克鑫,徐洁泉,廖多群等,沼气池中产氢细菌的研究,微生物学报,1980,20(4):385~389
[16]Pinder,Acidogenic Fermentation of Lactose,Biotechology and Bioengineering,1987,15:88-95
[17]任南琪.王爱杰.厌氧生物技术原理与应用[M].北京:化学工业出版社.2004:212-275
[18]李杨,玉米秸秆厌氧发酵制氢实验研究[D]郑州:郑州大学2006:1-8
[19]M.A.Rachman,Y.Furutani,Y.Nakashimada,T.Kakizono,N.Nishio.EnhancedHydrogen Production in Altered Mixed Acid Fermentation of Glucose by Enteroacter aerogengs.J.Ferment. Technol.1997,83(4):358-363
[20]G.Y.Jung,J.R.Kim,J,Y.Park.Hydrogen Production by a New Chemoheterotrophic Bacterium Citrobacter sp.Y19.int.J.Hydrogen Energy 2002,27:601-610
[21]N.Kumar.D.Das.Enhancement of Hydrogen Production by Enterobacter cloacae T-BT08.Process Biocemistry.2000,35:589-593
[22]李建政.汪群慧.废物资源化与生物能源[M]化学工业出版社。2004.12-26
[23]刘敏,任南琪等,糖蜜、淀粉与乳品废水厌氧发酵法生物制氢[J]环境科学2004,(25)5:65-69
[24]张无敌,尹芳等.农村秸秆与粪便发酵产氢的研究[J]可再生能源2008,(26)2:69-72
[25]任保增,唐大惠等.厌氧发酵生物制氢试验研究[J]郑州大学学报(工学版)2004,(25)4:65-66
[26]Xiao B Y,Liu J X.Effects of thermally pretreated temperature on bio-hydrogen production from sewage.J Environ Sci,2006,18(1):6-12
[27]肖本益,刘俊新.pH值对碱处理污泥厌氧发酵产氢的影响.科学通报,2005,50(24):2734-2738
[28]李兴杰.沼气发酵[J/OL].生物学通报,1999,34(3):16-17.
[29]Hu Bo,Chen Shulin.Pretreatment of methanogenic granules for immobilizedhydrogen fermentation[J].International Journal of Hydrogen Energy.2007
[30]王凯军,秦人伟.发酵工业废水处理[M]化学工业出版社. 2000.10-36。
[31]杨洁,季民等.污泥超声预处理促进厌氧消化反应试验[J]天津大学学报2006,39(10)1205-1208
[32]Schlafe O,Sievers M,K lotzucherH,et al Improvement of biological activity by low energy ultrasound assisted ioreactors[J].Ultasounics 2000,38(1/8):711-716
[33]王翠玲,谷晋川.微波技术在废水处理中的应用[J]环境监测管理与技术.2007,19(4):35-38
[34] Neher E.,Sakmann B..Single-channel currents recorded from membrane of denervated frog muscle fibers[J].Nature,1976,(260):779-802
[35]田禹,方琳,黄君礼等.微波辐射预处理对污泥结构及脱水性能的影响[J].中国环境科学,2006,26(4):459~463
[36]史苏佳,曹栋.微波原理及其在食品上的应用[J].山西食品工业.2002,3:8-9
[37]J.L.Garcia,B.K.C.Patel,B.Ollivier.Taxonomic,phylogenetic and ecological diversity of methanogenic archaea[J].Anaerobe,2000,6:205-226.
[38]Herbert H.P.Fang,Hong Liu.Effect of pH on hydrogen production from glucose by a mixed culture[J].Bioresource technology,2002,82:87-93.
[39]Chin-Chao Chen,Chiu-Yue Lin,Min-Cheng Lin.Acid-base enrichment enhances anaerobic hydrogen production process[J].Applied Microbiology and Biotechnology,2002,58:224-228.
[40]Wang CC,Chang CW,Chu CP,Lee DJ,Chang BV,Liao CS.Producing hydrogen fromwastewater sludge by Clostridium bifermentans[J].Journal of Biotechnology,2003,102:83-92.
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