玉米秸秆酶解上清液厌氧发酵产氢工艺优化
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摘要
该文主要以粒度小于0.088 mm秸秆粉的酶解上清液为底物与热预处理后的活性污泥进行厌氧发酵产氢试验,以累积产氢量为考察指标,基于响应面Box-Behnken模型研究不同影响因素对玉米秸秆酶解上清液厌氧发酵产氢的影响,对玉米秸秆酶解上清液厌氧发酵产氢工艺进行优化。结果表明:温度、初始p H值和还原糖浓度三因素中,温度和还原糖浓度对玉米秸秆酶解上清液厌氧发酵产氢的影响最大。采用Box-Behnken模型获得的最佳产氢条件为:温度38.32℃,初始p H值4.93,还原糖浓度20.70 mg/m L,最大产氢量685.59 m L,此时最大产氢率为57.13 m L/g(玉米秸秆)。通过试验验证,实际最大产氢量为659.24 m L,产氢率为54.94 m L/g(玉米秸秆),与模型预测值相比,相对误差为3.84%,说明该模型具有较好的拟合性。该优化工艺可为后期连续流状态下的生物制氢系统提供参考。
In recent years, hydrogen as eco-friendly clean energy has received the widespread attention. In numerous hydrogen production methods, anaerobic fermentation bio-hydrogen production has become a research hotspot in the field of renewable energy because it can utilize biomass raw materials effectively, reduce the agricultural waste pollution to the environment. The straw biomass is the main agricultural waste of crop production in China, which can be used to take direct or prepare molding fuel combustion and convert into biogas for comprehensive utilization generally. Cellulose content in maize straw(about 36%) is higher than that in wheat、soybean and sorghum straws, the research of cellulose energy efficient transformation in maize straw has important scientific significance and practical value. In this study, anaerobic fermentation experiments were performed for bio-hydrogen production from enzymatic hydrolyzate of corn stalk powder(<0.088 mm) using heat pretreated activated sludge as fermentation microorganism, choosing cumulative amount of hydrogen production as main experiment parameter,the influences of different factors on anaerobic fermentation bio-hydrogen production of corn stalk's enzymolysis were studied based on Box-Behnken model of response surface method. The significance of interactions between different factors during the anaerobic bio-hydrogen production process was examined and the anaerobic fermentation bio-hydrogen production process of corn stalk's enzymolysis was optimized. The results showed that temperature and enzymatic hydrolysate concentration were the factors that mostly impacted on the corn stalk anaerobic fermentation bio-hydrogen production process comparing with initial p H value. The interaction of two factors on the effect of hydrogen yield were all significant(P<0.05). Box-Behnken model was used to obtain the optimal conditions of hydrogen production. The optimal conditions were temperature of 38.32℃, the initial p H value of 4.93, and the enzymatic hydrolysate concentration of 20.70 mg/mL. Under such condition, the maximum hydrogen yield was 685.59 mL and the maximum hydrogen production rate was 57.13 mL /g straw. The model was validated through experiment, the actual maximum hydrogen yield can reach 659.24 mL and the hydrogen production rate was 54.94 mL /g straw, with the prediction error of 3.84%, which proved that this model had a good fitness.
In recent years, hydrogen as eco-friendly clean energy has received the widespread attention. In numerous hydrogen production methods, anaerobic fermentation bio-hydrogen production has become a research hotspot in the field of renewable energy because it can utilize biomass raw materials effectively, reduce the agricultural waste pollution to the environment. The straw biomass is the main agricultural waste of crop production in China, which can be used to take direct or prepare molding fuel combustion and convert into biogas for comprehensive utilization generally. Cellulose content in maize straw(about 36%) is higher than that in wheat、soybean and sorghum straws, the research of cellulose energy efficient transformation in maize straw has important scientific significance and practical value. In this study, anaerobic fermentation experiments were performed for bio-hydrogen production from enzymatic hydrolyzate of corn stalk powder(<0.088 mm) using heat pretreated activated sludge as fermentation microorganism, choosing cumulative amount of hydrogen production as main experiment parameter,the influences of different factors on anaerobic fermentation bio-hydrogen production of corn stalk's enzymolysis were studied based on Box-Behnken model of response surface method. The significance of interactions between different factors during the anaerobic bio-hydrogen production process was examined and the anaerobic fermentation bio-hydrogen production process of corn stalk's enzymolysis was optimized. The results showed that temperature and enzymatic hydrolysate concentration were the factors that mostly impacted on the corn stalk anaerobic fermentation bio-hydrogen production process comparing with initial p H value. The interaction of two factors on the effect of hydrogen yield were all significant(P<0.05). Box-Behnken model was used to obtain the optimal conditions of hydrogen production. The optimal conditions were temperature of 38.32℃, the initial p H value of 4.93, and the enzymatic hydrolysate concentration of 20.70 mg/mL. Under such condition, the maximum hydrogen yield was 685.59 mL and the maximum hydrogen production rate was 57.13 mL /g straw. The model was validated through experiment, the actual maximum hydrogen yield can reach 659.24 mL and the hydrogen production rate was 54.94 mL /g straw, with the prediction error of 3.84%, which proved that this model had a good fitness.
引文
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[5]Saha Badal C.Hemicellulose bioconversion[J].Ind Microbiol Biotechnol,2003,30(5):279-291.
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[9]胡庆丽.玉米秸秆厌氧发酵生物制氢放大实验研究[D].郑州:郑州大学,2007.Hu Qingli.Study on Scale-up Experiment of Bio-hydrogen Production from Cornstalk by Fermentation[D].Zhengzhou:Zhengzhou University,2007.(in Chinese with English abstract)
[10]荆艳艳.超微秸秆光合生物产氢体系多相流数值模拟与流变特性实验研究[D].郑州:河南农业大学,2011.Jing Yanyan.Mathematical Simulation and Rheological Properties of Photosynthetic Bacteria Hydrogen Production System with Supemicro Straw[D].Zhengzhou:Henan Agricultural University,2011.(in Chinese with English abstract)
[11]Zhang Zhiping,Yue Jianzhi,Zhou Xuehua,et al.Photo-fermentative bio-hydrogen production from agricultural residue enzymatic hydrolyzate and the enzyme reuse[J].Bio Resources,2014,9(2):2299-2310.
[12]Sudhanshu S P,Valentine N N,Ahmad A Z,et al.Biohydrogen production from wheat straw hydrolysate using Caldicellulosiruptor saccharolyticus followed by biogas production in a two-step uncoupled process[J].International Journal of Hydrogen Energy,2013,38:9121-9130.
[13]任晓.厌氧与光合微生物联合制氢工艺实验研究[D].郑州:河南农业大学,2012.Ren Xiao.Experimental Study of Hydrogen Production by Anaerobic and Photosynthetic Microorganisms Combined with Fecalsewage[D].Zhengzhou:Henan Agricultural University,2012.(in Chinese with English abstract)
[14]金浩,李柏林,欧杰,等.污水处理活性污泥微生物群落多样性研究[J].微生物学杂志,2012,32(4):1-5.Jin Hao,Li Bolin,Ou Jie,et al.Microbial population diversity of activated sludge for wastewater treatment[J].Journal of Microbiology,2012,32(4):1-5.(in Chinese with English abstract)
[15]刘佳.表面活性剂在废木质纤维素制酒精中的应用基础研究[D].长沙:湖南大学,2008.Liu Jia.The Fundmental Research on the Application of Surfactants in the Production of Ethanol from Lignocellulose[D].Changsha:Hunan University,2008.(in Chinese with English abstract)
[16]张志萍.秸秆类生物质超微预处理技术及其产氢可行性研究[D].郑州:河南农业大学,2012.Zhang Zhiping.Study on the Technology of Ultramicro Pretreatment by Straw Biomass and Feasibility Study of Hydrogen Production[D].Zhengzhou:Henan Agricultural University,2012.(in Chinese with English abstract)
[17]国家环境保护总局.水和废水监测分析方法[M].北京:中国环境科学出版社,2002.
[18]王玉万,徐文玉.木质纤维素固体基质发酵物中半纤维素、纤维素和木质素的定量测定分析程序[J].微生物学报,1987(2):82-84.Wang Yuwan,Xu Wenyu.The quantitative analysis program of hemicelluloses,cellulose and lignin in the lignocellulose solid substrate yeast[J].Acta Microbiologica Sinica,1987(2):82-84.(in Chinese with English abstract)
[19]Liu Wei,Yu Yanying,Yang Ruzhen,et al.Optimization of total flavonoid compound extraction from Gynura medica leaf using response surface methodology and chemical composition analysis[J].Int J Mol Sci,2010,11(11):4750-4763.
[20]Mao Weihua,Han Lujia,Shi Bo.Optimization of microwave-assisted extraction of flavonoid from Radix Astragali using response surface methodology[J].Sep Sci Technol,2008,43(3):671-681.
[21]Ashan S E,Miganad T,Ariffa A,et al.Optimization of enzymatic synthesis of palm-based kojic acid ester using response surface methodology[J].J Oleo Sci,2009,58(10):503-510.
[22]汤桂兰,孙振钧.厌氧污泥发酵制氢工艺试验研究[J].农业工程学报,2007,23(9):201-204.Tang Guilan,Sun Zhenjun.Experimental study of anaerobic sludge fermentation hydrogen production process[J]Transactions of the Chinese Society of Agricultural Engineering(Transactions of the CSAE),2007,23(9):201-204.(in Chinese with English abstract)
[23]沈其君.SAS统计分析[M].南京:东南大学出版社,2009:9-56.
[24]Auja S K,Ferreira G M,Moreira A R.Application of Plaekett-Burman design and response surface methodology to achieve exponential growth for aggregated shipworm bacterium[J].Biotechnol Bioeng,2004,85(6):666-675.
[25]Silva E M,Rogez H,Larondelle Y.Optimization of extraction of phenolics from Inga edulis leaves using response surface methodology[J].Sep Purif Technol,2007,55(3):381-387.
[26]路朝阳,王毅,荆艳艳,等.基于BBD模型的玉米秸秆光合生物制氢优化实验研究[J].太阳能学报,2014,35(8):1511-1516.Lu Chaoyang,Wang Yi,Jing Yanyan,et al.Experiment optimization of bio-hydrogen production from corn stalks based on BBD model[J].Acta Energiae Solaris Sinica,2014,35(8):1511-1516.(in Chinese with English abstract)
[27]Zhang Zhiping,Wang Yi,Hu Jianjun,et al.Influence of mixing method and hydraulic retention time on hydrogen production through photo-fermentation with mixed strains[J].International Journal of Hydrogen Energy,2015,40:6521-6529.
[28]才金玲,王广策.发酵生物制氢反应器研究进展[J].环境科学与技术,2013,36(6):78-84.Cai Jinling,Wang Guangce.Bioreactor for fermentative hydrogen production:A review[J].Environmental Science&Technology,2013,36(6):78-84.(in Chinese with Englishabstract)
[29]刘晓烨,张洪,李永峰.水力停留时间对复合式厌氧折流板反应器乙醇型发酵制氢系统的影响[J].环境科学,2014,35(6):2433-2438.Liu Xiaoye,Zhang Hong,Li Yongfeng.Influences of hydraulic retention time on the ethanol type fermentation hydrogen production system in a hybrid anaerobic baffled reactor[J].Environmental Science,2014,35(6):2433-2438.(in Chinese with English abstract)
[30]荆艳艳,李丁丁,罗晓,等.超微玉米秸秆的沉降稳定性及产氢能力研究[J].太阳能学报,2014,35(6):960-964.Jing Yanyan,Li Dingding,Luo Xiao,et al.Sedimentationstability and capacity of photosynthetic hydrogen production with superfine corn straw[J].Acta Energiae Solaris Sinica,2014,35(6):960-964.(in Chinese with English abstract)
[31]荆艳艳,周雪花,赵民善,等.高粱秸秆光合产氢体系流变特性的影响因素[J].农业工程学报,2011,27(增刊2),139-143.Jing Yanyan,Zhou Xuehua,Zhao Minshan,et al.Influencing factors of rheological properties of photosynthetic bacteria hydrogen production system with sorghum straw[J].Transactions of the Chinese Society of Agricultural Engineering(Transactions of the CSAE),2011,27(Supp.2):139-143.(in Chinese with English abstract)
[32]罗娟,田宜水,宋成军,等.玉米秸秆厌氧产氢工艺参数优化[J].农业工程学报,2015,31(2):235-240.Luo Juan,Tian Yishui,Song Chengjun,et al.Parameter optimization of hydrogen production by anaerobic fermentation with corn straw[J].Transactions of the Chinese Society of Agricultural Engineering(Transactions of the CSAE),2015,31(2):235-240.(in Chinese with English abstract)
[2]田松峰,罗伟光,荆有印,等.玉米秸秆燃烧过程及燃烧动力学分析[J].太阳能学报,2008,29(12):1570-1572.Tian Songfeng,Luo Weigua,Jing Youyin,et al.Combustion process and kinetic sanalysis of cornstalk[J].Acta Energiae Solaris Sinica,2008,29(12):1570-1572.(in Chinese with English abstract)
[3]田潇瑜,侯振东,徐杨.玉米秸秆成型块微观结构研究[J].农业机械学报,2011,42(3):105-108.Tian Xiaoyu,Hou Zhendong,Xu Yang.Microstructure of corn stover briquette[J].Transactions of the Chinese Society for Agricultural Machinery,2011,42(3):105-108.(in Chinese with English abstract)
[4]王飞,蔡亚庆,仇焕广.中国沼气发展的现状、驱动及制约因素分析[J].农业工程学报,2012,28(1):184-189.Wang Fei,Cai Yaqing,Qiu Huanguang.Current status,incentives and constraints for future development of biogas industry in China[J].Transaction of the Chinese Society of Agricultural Engineering(Transaction of the CSAE),2012,28(1):184-189.(in Chinese with English abstract)
[5]Saha Badal C.Hemicellulose bioconversion[J].Ind Microbiol Biotechnol,2003,30(5):279-291.
[6]Sun Ye,Cheng Jiayang.Hydrolysis of lignocellulosic materials for ethanol production:A review[J].Bioresource Technology,2002,3(6):22-23.
[7]包红旭,王爱杰,任南琪.预处理方法对细菌降解玉米秸秆产氢能力的影响[J].大连海事大学学报,2008,34(4):41-52.Bao Hongxu,Wang Aijie,Ren Nanqi.Effects of pretreatment methods on bio-hydrogen production from corn stalk by Clostridium sp.X9[J].Journal of Dalian Maritime University,2008,34(4):41-52.(in Chinese with English abstract)
[8]孙学习,李涛,计新静,等.玉米秸秆发酵制氢影响因素及变化规律研究[J].现代化工,2010,30(6):60-62.Sun Xuexi,Li Tao,Ji Xinjing,et al.Parameter effects and mechanism of fermentative bio-hydrogen production from cornstalks[J].Modern Chemical Industry,2010,30(6):60-62.(in Chinese with English abstract)
[9]胡庆丽.玉米秸秆厌氧发酵生物制氢放大实验研究[D].郑州:郑州大学,2007.Hu Qingli.Study on Scale-up Experiment of Bio-hydrogen Production from Cornstalk by Fermentation[D].Zhengzhou:Zhengzhou University,2007.(in Chinese with English abstract)
[10]荆艳艳.超微秸秆光合生物产氢体系多相流数值模拟与流变特性实验研究[D].郑州:河南农业大学,2011.Jing Yanyan.Mathematical Simulation and Rheological Properties of Photosynthetic Bacteria Hydrogen Production System with Supemicro Straw[D].Zhengzhou:Henan Agricultural University,2011.(in Chinese with English abstract)
[11]Zhang Zhiping,Yue Jianzhi,Zhou Xuehua,et al.Photo-fermentative bio-hydrogen production from agricultural residue enzymatic hydrolyzate and the enzyme reuse[J].Bio Resources,2014,9(2):2299-2310.
[12]Sudhanshu S P,Valentine N N,Ahmad A Z,et al.Biohydrogen production from wheat straw hydrolysate using Caldicellulosiruptor saccharolyticus followed by biogas production in a two-step uncoupled process[J].International Journal of Hydrogen Energy,2013,38:9121-9130.
[13]任晓.厌氧与光合微生物联合制氢工艺实验研究[D].郑州:河南农业大学,2012.Ren Xiao.Experimental Study of Hydrogen Production by Anaerobic and Photosynthetic Microorganisms Combined with Fecalsewage[D].Zhengzhou:Henan Agricultural University,2012.(in Chinese with English abstract)
[14]金浩,李柏林,欧杰,等.污水处理活性污泥微生物群落多样性研究[J].微生物学杂志,2012,32(4):1-5.Jin Hao,Li Bolin,Ou Jie,et al.Microbial population diversity of activated sludge for wastewater treatment[J].Journal of Microbiology,2012,32(4):1-5.(in Chinese with English abstract)
[15]刘佳.表面活性剂在废木质纤维素制酒精中的应用基础研究[D].长沙:湖南大学,2008.Liu Jia.The Fundmental Research on the Application of Surfactants in the Production of Ethanol from Lignocellulose[D].Changsha:Hunan University,2008.(in Chinese with English abstract)
[16]张志萍.秸秆类生物质超微预处理技术及其产氢可行性研究[D].郑州:河南农业大学,2012.Zhang Zhiping.Study on the Technology of Ultramicro Pretreatment by Straw Biomass and Feasibility Study of Hydrogen Production[D].Zhengzhou:Henan Agricultural University,2012.(in Chinese with English abstract)
[17]国家环境保护总局.水和废水监测分析方法[M].北京:中国环境科学出版社,2002.
[18]王玉万,徐文玉.木质纤维素固体基质发酵物中半纤维素、纤维素和木质素的定量测定分析程序[J].微生物学报,1987(2):82-84.Wang Yuwan,Xu Wenyu.The quantitative analysis program of hemicelluloses,cellulose and lignin in the lignocellulose solid substrate yeast[J].Acta Microbiologica Sinica,1987(2):82-84.(in Chinese with English abstract)
[19]Liu Wei,Yu Yanying,Yang Ruzhen,et al.Optimization of total flavonoid compound extraction from Gynura medica leaf using response surface methodology and chemical composition analysis[J].Int J Mol Sci,2010,11(11):4750-4763.
[20]Mao Weihua,Han Lujia,Shi Bo.Optimization of microwave-assisted extraction of flavonoid from Radix Astragali using response surface methodology[J].Sep Sci Technol,2008,43(3):671-681.
[21]Ashan S E,Miganad T,Ariffa A,et al.Optimization of enzymatic synthesis of palm-based kojic acid ester using response surface methodology[J].J Oleo Sci,2009,58(10):503-510.
[22]汤桂兰,孙振钧.厌氧污泥发酵制氢工艺试验研究[J].农业工程学报,2007,23(9):201-204.Tang Guilan,Sun Zhenjun.Experimental study of anaerobic sludge fermentation hydrogen production process[J]Transactions of the Chinese Society of Agricultural Engineering(Transactions of the CSAE),2007,23(9):201-204.(in Chinese with English abstract)
[23]沈其君.SAS统计分析[M].南京:东南大学出版社,2009:9-56.
[24]Auja S K,Ferreira G M,Moreira A R.Application of Plaekett-Burman design and response surface methodology to achieve exponential growth for aggregated shipworm bacterium[J].Biotechnol Bioeng,2004,85(6):666-675.
[25]Silva E M,Rogez H,Larondelle Y.Optimization of extraction of phenolics from Inga edulis leaves using response surface methodology[J].Sep Purif Technol,2007,55(3):381-387.
[26]路朝阳,王毅,荆艳艳,等.基于BBD模型的玉米秸秆光合生物制氢优化实验研究[J].太阳能学报,2014,35(8):1511-1516.Lu Chaoyang,Wang Yi,Jing Yanyan,et al.Experiment optimization of bio-hydrogen production from corn stalks based on BBD model[J].Acta Energiae Solaris Sinica,2014,35(8):1511-1516.(in Chinese with English abstract)
[27]Zhang Zhiping,Wang Yi,Hu Jianjun,et al.Influence of mixing method and hydraulic retention time on hydrogen production through photo-fermentation with mixed strains[J].International Journal of Hydrogen Energy,2015,40:6521-6529.
[28]才金玲,王广策.发酵生物制氢反应器研究进展[J].环境科学与技术,2013,36(6):78-84.Cai Jinling,Wang Guangce.Bioreactor for fermentative hydrogen production:A review[J].Environmental Science&Technology,2013,36(6):78-84.(in Chinese with Englishabstract)
[29]刘晓烨,张洪,李永峰.水力停留时间对复合式厌氧折流板反应器乙醇型发酵制氢系统的影响[J].环境科学,2014,35(6):2433-2438.Liu Xiaoye,Zhang Hong,Li Yongfeng.Influences of hydraulic retention time on the ethanol type fermentation hydrogen production system in a hybrid anaerobic baffled reactor[J].Environmental Science,2014,35(6):2433-2438.(in Chinese with English abstract)
[30]荆艳艳,李丁丁,罗晓,等.超微玉米秸秆的沉降稳定性及产氢能力研究[J].太阳能学报,2014,35(6):960-964.Jing Yanyan,Li Dingding,Luo Xiao,et al.Sedimentationstability and capacity of photosynthetic hydrogen production with superfine corn straw[J].Acta Energiae Solaris Sinica,2014,35(6):960-964.(in Chinese with English abstract)
[31]荆艳艳,周雪花,赵民善,等.高粱秸秆光合产氢体系流变特性的影响因素[J].农业工程学报,2011,27(增刊2),139-143.Jing Yanyan,Zhou Xuehua,Zhao Minshan,et al.Influencing factors of rheological properties of photosynthetic bacteria hydrogen production system with sorghum straw[J].Transactions of the Chinese Society of Agricultural Engineering(Transactions of the CSAE),2011,27(Supp.2):139-143.(in Chinese with English abstract)
[32]罗娟,田宜水,宋成军,等.玉米秸秆厌氧产氢工艺参数优化[J].农业工程学报,2015,31(2):235-240.Luo Juan,Tian Yishui,Song Chengjun,et al.Parameter optimization of hydrogen production by anaerobic fermentation with corn straw[J].Transactions of the Chinese Society of Agricultural Engineering(Transactions of the CSAE),2015,31(2):235-240.(in Chinese with English abstract)