玉米秸秆厌氧消化预处理方法及工艺优化
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摘要
为提高玉米秸秆厌氧消化性能,该文采用碱液、酸液、沼液等方法对玉米秸秆进行预处理,比较不同预处理方式对秸秆成分、含量以及厌氧消化能力的影响。试验结果表明,经超声波辅助碱预处理后,秸秆的木质素和半纤维素总含量显著降低,产气量显著提高。基于Box-Behnken(BBK)试验设计,选择碱液预处理的固固比(Na OH/秸秆,下同)、预处理温度、预处理时间为试验因素,结合响应面分析法对碱液预处理条件进行响应面优化,结果表明,最佳玉米秸秆预处理条件为固固比22.4%,预处理温度37.9℃,预处理时间39.7 h,在此条件下还原糖产量的试验值为738.6 mg/g,沼气累积产量的试验值为661 m L/g,试验值与预测值误差不到0.5%,证明了响应面优化法的准确性和可行性。
Lignocellulose is an abundant renewable energy source in crop straws. Lignocellulose is mainly composed of cellulose, hemicellulose, lignin and ash. The cellulose is not only encapsulated by lignin and hemicellulose, but also has a very stable structure and is not easily degraded in the natural environment. Lignocellulose has a high degree of crystallinity and polymerization, if the crop straw is directly used for biogas production, there are some problems such as slow start, low efficiency, and low conversion and utilization may occur. Therefore, straw raw materials must be pretreated to destroy the crystallinity of cellulose and reduce the degree of polymerization, remove the covering effect of lignin and hemicellulose, increase the hydrolysis rate of cellulose and the gas production of biogas before the biogas fermentation. In order to improve the anaerobic digestion performance of corn straw and reduce the treatment cost, this study used alkaline treatment, acid treatment and biogas slurry treatment to pretreat corn straw, and studied the effects of different pretreatment methods on cellulose content and anaerobic digestion rate. The results showed that the degradation rate of lignin and hemicellulose in alkaline treatment were much higher than that in the acid treatment and the biogas slurry treatment, and the weight loss rate was lower, and the cellulose composition was well preserved. Because of the biogas yield and methane yield were the highest in all treatment groups, the alkali treatment with the best pretreatment effect was selected for the subsequent process optimization experiment. Based on Box-Behnken Design(BBD) test design, the quality percentage of alkali treatment, pretreatment temperature and pretreatment time were selected as the test factors. Combined with the results of single factor test, the response surface analysis method of three factors and three levels was designed, and the response surface methodology was used to establish the process mathematical model with the response value of biogas cumulative yield and reducing sugar yield as the response value. The results showed that the optimum pretreatment conditions of corn straw were: the solid-solid ratio was 22.4%, the pretreatment temperature was 37.9 ℃, and the pretreatment time was 39.7 h. Under this condition, the experimental value of reducing sugar yield was 738.6 mg/g, and the cumulative biogas production value was 661 mL/g. The difference between the test value and the predicted value was less than 0.5%, which proved the accuracy and feasibility of the response surface optimization method. Compared with other pretreatment methods, alkali pretreatment had advantages in improving the conversion rate of straw, increasing the gas production rate and reducing the cost. The pretreatment of straw biogas project should not only consider the increase of gas production rate, but also the subsequent treatment of biogas slurry. The alkaline pretreatment could neutralize various acidic products during the anaerobic fermentation process, and could also prevent the decrease of pH value during subsequent acidification. Alkaline pretreatment was a good additive to prevent acidification of fermentation broth. Alkali pretreatment is an ideal method for biogas fermentation of corn straw in the future.
Lignocellulose is an abundant renewable energy source in crop straws. Lignocellulose is mainly composed of cellulose, hemicellulose, lignin and ash. The cellulose is not only encapsulated by lignin and hemicellulose, but also has a very stable structure and is not easily degraded in the natural environment. Lignocellulose has a high degree of crystallinity and polymerization, if the crop straw is directly used for biogas production, there are some problems such as slow start, low efficiency, and low conversion and utilization may occur. Therefore, straw raw materials must be pretreated to destroy the crystallinity of cellulose and reduce the degree of polymerization, remove the covering effect of lignin and hemicellulose, increase the hydrolysis rate of cellulose and the gas production of biogas before the biogas fermentation. In order to improve the anaerobic digestion performance of corn straw and reduce the treatment cost, this study used alkaline treatment, acid treatment and biogas slurry treatment to pretreat corn straw, and studied the effects of different pretreatment methods on cellulose content and anaerobic digestion rate. The results showed that the degradation rate of lignin and hemicellulose in alkaline treatment were much higher than that in the acid treatment and the biogas slurry treatment, and the weight loss rate was lower, and the cellulose composition was well preserved. Because of the biogas yield and methane yield were the highest in all treatment groups, the alkali treatment with the best pretreatment effect was selected for the subsequent process optimization experiment. Based on Box-Behnken Design(BBD) test design, the quality percentage of alkali treatment, pretreatment temperature and pretreatment time were selected as the test factors. Combined with the results of single factor test, the response surface analysis method of three factors and three levels was designed, and the response surface methodology was used to establish the process mathematical model with the response value of biogas cumulative yield and reducing sugar yield as the response value. The results showed that the optimum pretreatment conditions of corn straw were: the solid-solid ratio was 22.4%, the pretreatment temperature was 37.9 ℃, and the pretreatment time was 39.7 h. Under this condition, the experimental value of reducing sugar yield was 738.6 mg/g, and the cumulative biogas production value was 661 mL/g. The difference between the test value and the predicted value was less than 0.5%, which proved the accuracy and feasibility of the response surface optimization method. Compared with other pretreatment methods, alkali pretreatment had advantages in improving the conversion rate of straw, increasing the gas production rate and reducing the cost. The pretreatment of straw biogas project should not only consider the increase of gas production rate, but also the subsequent treatment of biogas slurry. The alkaline pretreatment could neutralize various acidic products during the anaerobic fermentation process, and could also prevent the decrease of pH value during subsequent acidification. Alkaline pretreatment was a good additive to prevent acidification of fermentation broth. Alkali pretreatment is an ideal method for biogas fermentation of corn straw in the future.
引文
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[2]Georgakakis D,Krintas T.Optimal use of the Hosoya system in composting poultry manure[J].Bioresource Technology,2000,72(1):227-233.
[3]陈子爱,邓小晨.微生物处理利用秸杆的研究进展[J].中国沼气,2006,24(3):31-35.Chen Ziai,Deng Xiaochen.Progress in microbiologic utilization of crop straw[J].China biogas,2006,24(3):31-35.(in Chinese with English abstract)
[4]李平,王焰新,刘琨,等.高效纤维素降解菌系的构建[J].地球科学(中国地质大学学报),2009,34(3):533-538.Li Ping,Wang Yanxin,Liu Kun,et al.Construction of a microbial system or efficient degradation of cellulose[J].Earth Science(Journel of China University of Geoscience),2009,34(3):533-538.(in Chinese with English abstract)
[5]覃国栋,刘荣厚,孙辰.NaOH预处理对水稻秸秆沼气发酵的影响[J].农业工程学报,2011,27(增刊1):59-63.Qin Guodong,Liu Ronghou,Sun Chen.Effects of different concentrations of NaOH pretreatment on anaerobic digestion of rice straw for biogas production[J].Transactions of the Chinese Society of Agricultural Engineering(Transactions of the CSAE),2011,27(Supp.l):59-63.(in Chinese with English abstract)
[6]李淑兰,梅自力,张国治,等.秸秆厌氧消化预处理技术综述[J].中国沼气,2011,29(5):29-33.Li Shulan,Mei Zili,Zhang Guozhi,et al.Review of pretreatment technology for crop straw anaerobic digestion[J].China Biogas,2011,29(5):29-33.(in Chinese with English abstract)
[7]李刚,李东亮,王许涛,等.玉米秸秆蒸汽爆破用于厌氧发酵的技术评价[J].农业工程学报,2011,27(1):286-290.Li Gang,Li Dongliang,Wang Xutao,et al.Technology evaluation of steam exploded corn stalk anaerobic fermentation[J].Transactions of the Chinese Society of Agricultural Engineering(Transactions of the CSAE),2011,27(1):286-290.(in Chinese with English abstract)
[8]冯磊,李润东,Bernhard Raninger,等.微波预处理对秸秆厌氧消化影响的研究[J].环境工程学报,2009,3(8):1503-1508.Feng Lei,Li Rundong,Bernhard Raninger,et al.Efficiency of anaerobic digestion of straw pretreated with microwave energy[J].Chinese Journal of Environmental Engineering,2009,3(8):1503-1508.(in Chinese with English abstract)
[9]寇巍,赵勇,闫昌国,等.膨化预处理玉米秸秆提高还原糖酶解产量的效果[J].农业工程学报,2010,26(11):265-269.Kou Wei,Zhao Yong,Yan Changguo,et al.Corn straw expansion pretreatment to improve enzymolysis reducing sugar yield[J].Transactions of the Chinese Society of Agricultural Engineering(Transactions of the CSAE),2010,26(11):265-269.(in Chinese with English abstract)
[10]胡斌,张亮亮,胡青平.超声波预处理玉米秸秆的条件优化[J].西北农业学报,2012,21(2):153-156.Hu Bin,Zhang Liangliang,Hu Qingping.Optimization of ultrasonic pretreatment for corn straw[J].Acta Agriculturae Boreali-occidentalis Sinica.2012,21(2):153-156.(in Chinese with English abstract)
[11]Lukas,Tomas.The effect of process parameters during the thermal-expansionary pretreatment of wheat straw on hydrolysate quality and on biogas yield[J].Renewable Energy.2015,77:250-258.
[12]黄仁亮,刘锐,苏荣欣,等.玉米芯氨水预处理及酶解工艺研究[J].化学工程,2009,37(9):40-43.Huang Renliang,Liu Rui,Su Rongxin,et al.Aqueous ammonia pretreatment and enzymatic hydrolysis of corn cobs[J].Chemical Engineering(China),2009,37(9):40-43.(in Chinese with English abstract)
[13]Viola E,Zimbardi F,Cardinale M,et al.Processing cereal straws by steam explosion in a pilot plant to enhance digestibility in ruminants[J].Bioresource Technology,2008,99(4):681-689.
[14]Carrasco J E,Ma C S,Navarro A,et al.Effects of dilute acid and steam explosion pretreatments on the cellulose structure and kinetics of cellulosic fraction hydrolysis by dilute acids in lignocellulosic materials[J].Applied Biochemistry and Biotechnology,1994,45/46(1):23-34.
[15]Tucker M P,Kim K H,Newman M M,et al.Effects of temperature and moisture on dilute-acid steam explosion pretreatment of corn stover and cellulase enzyme digestibility[J].Applied Biochemistry and Biotechnology,2003,105(1/2/3):165-177.
[16]靳胜英,张福琴,张礼安.木质纤维原料制乙醇原料预处理技术[J].中国工程科学,2008,10(11):82-88.Jin Shengying,Zhang Fuqin,Zhang Li’an.Pretreatment method of lignocellulosic materials for bioethanol production[J].Engineering Sciences,2008,10(11):82-88.(in Chinese with English abstract)
[17]马兴元,刘琪,马君.氨化预处理对生物质秸秆厌氧发酵的影响[J].生态环境学报,2011,20(10):1503-1506.Ma Xingyuan,Liu Qi,Ma Jun.The effects of ammoniation pretreatment on anaerobic fermentation of the Biomass straw[J].Ecology and Environmental Sciences,2011,20(10):1503-1506.(in Chinese with English abstract)
[18]马淑勍,袁海荣,朱保宁,等.氨化预处理对稻草厌氧消化产气性能影响[J].农业工程学报,2011,27(6):294-299.Ma Shuqing,Yuan Hairong,Zhu Baoning,et al.Effects of ammoniation pretreatment on anaerobic digestion performance of rice straw[J].Transactions of the Chinese Society of Agricultural Engineering(Transactions of the CSAE),2011,27(6):294-299.(in Chinese with English abstract)
[19]刘研萍,方刚,党锋,等.Na OH和H2O2预处理对玉米秸秆厌氧消化的影响[J].农业工程学报,2011,27(12):260-263.Liu Yanping,Fang Gang,Dang Feng,et al.Effect of NaOHand H2O2 pretreatment on corn straw anaerobic digestion[J].Transactions of the Chinese Society of Agricultural Engineering(Transactions of the CSAE),2011,27(12):260-263.(in Chinese with English abstract)
[20]覃国栋,刘荣厚,孙辰.酸预处理对水稻秸秆沼气发酵的影响[J].上海交通大学学报:农业科学版,2011,29(1):58-61.Qin Guodong,Liu Ronghou,Sun Chen.Effects of acid pretreatment on biogas fermentation of rice straw[J].Journal of Shanhai Jiaotong University:Agricultural Science,2011,29(1):58-61.(in Chinese with English abstract)
[21]徐龙君,安丽娜,农丽薇,等.稀盐酸预处理对稻草厌氧消化的影响[J].环境工程学报,2011,5(3):671-674.Xu Longjun,An Lina,Nong Liwei,et al.Effect of pretreatment of dilute hydrochloric acid on anaerobic digestion of rice straw[J].Chinese Journal of Environmental Engineering,2011,5(3):671-674.(in Chinese with English abstract)
[22]Deepa J S,Pranav K,Sneha T M,et al.Alkali pretreatment at ambient temperature:A promising method to enhance biomethanation of rice straw[J].Bioresource Technology.2017,226(2):80-88.
[23]Song Zilin,Zhang Chao.Anaerobic codigestion of pretreated wheat straw with cattle manure and analysis of the microbial community[J].Bioresource Technology.2015,186(6):128-135.
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