利用SPORL法对玉米秸秆预处理最优条件的筛选
|
摘要
通过SPORL法对玉米秸秆进行预处理并提高其产物有机质含量,探寻固体产物在土壤培肥方面的可利用性及肥料化利用的可行性。在高温高压条件下,以玉米秸秆固体产物的有机质含量作为评价指标,首先筛选出一种最优催化剂,并根据催化剂筛选结果,对催化剂的用量、反应温度进行单因素试验,确定各单因素的条件范围,在此基础上优化反应条件,最后对预处理固体产物的腐殖化程度进行分析。催化剂筛选的结果表明:酸性亚硫酸铵预处理玉米秸秆后的固体产物有机质含量高于其他处理组;以硝酸用量、亚硫酸铵用量和反应温度为三个主要试验因素,进行单因素试验,硝酸用量(V/V)在3%~7%、亚硫酸铵用量(相对于原料干质量,m/m)在10%~20%、反应温度在130~150℃范围内,其固体产物有机质含量较高;以玉米秸秆固体产物有机质含量为响应指标,对试验进行设计并优化反应条件,优化后的反应条件是硝酸用量5.4%、亚硫酸铵用量18%、反应温度150℃,有机质含量预测值为794.40g·kg~(-1);验证试验中有机质含量为788.70 g·kg~(-1),与预测值的相对偏差为5.70 g·kg~(-1)。秸秆固体产物腐殖化分析结果表明,经SPORL法预处理后玉米秸秆固体产物类腐殖物质(HLE)和类胡敏酸(HLA)数量分别增长至20.30 g·kg~(-1)和18.76 g·kg~(-1),类胡敏酸与类富里酸比值(HLA/FLA)增长至12.19。研究表明,玉米秸秆经SPORL法预处理可以产生有机质含量较高的固体产物,并可促进固体产物类腐殖质的形成,提高腐殖化程度。
In this study, we explored the possibility of producing organic fertilizer with the solid product from maize straw treated by the Sul-fite Pretreatment to Overcome Recalcitrance of Lignocelluloses(SPORL)method. The acidic ammonium sulfite was chosen as a catalyst because it could generate a solid product with the highest organic matter content. The catalyst is composed of nitric acid and ammonium sulfite,and the pretreatment process is affected by temperature. Thereafter, a single-factor experiment was carried out to assess the application rate of nitric acid and ammonium sulfite, and reaction temperature. The results showed that the solid product had a higher organic matter content when maize straw was treated with 10%~20% ammonium sulfite(relative to dry weight of the solid, m/m)and 3%~7% of nitric acid(V/V)at 130~150 ℃. Accordingly, the response surface methodology was applied to redesign and optimize the pretreatment conditions using organic matter content of the solid product as a response index. Under the optimized reaction conditions, the maize straw treated with 5.4% nitric acid and 18% ammonium sulfite at 150 ℃ could yield a solid product with an organic matter content as high as 794.40 g·kg~(-1), which was 5.70 g·kg~(-1) more than that obtained in the validation tests. Analysis of humification of the solid product showed that SPORL could promote the formation of humic acid and improve the degree of humification. Therefore, when the maize straw was treated with acidic ammonium sul-fite a catalyst in a reactor at high temperature and high pressure, lignosulfonates could be formed, which could subsequently convert into humic substances that contains a mixture of lingohumic acids and a smaller proportion of low-molecular-weight organic compounds. This method can add to the value of maize straw resource reuse.
In this study, we explored the possibility of producing organic fertilizer with the solid product from maize straw treated by the Sul-fite Pretreatment to Overcome Recalcitrance of Lignocelluloses(SPORL)method. The acidic ammonium sulfite was chosen as a catalyst because it could generate a solid product with the highest organic matter content. The catalyst is composed of nitric acid and ammonium sulfite,and the pretreatment process is affected by temperature. Thereafter, a single-factor experiment was carried out to assess the application rate of nitric acid and ammonium sulfite, and reaction temperature. The results showed that the solid product had a higher organic matter content when maize straw was treated with 10%~20% ammonium sulfite(relative to dry weight of the solid, m/m)and 3%~7% of nitric acid(V/V)at 130~150 ℃. Accordingly, the response surface methodology was applied to redesign and optimize the pretreatment conditions using organic matter content of the solid product as a response index. Under the optimized reaction conditions, the maize straw treated with 5.4% nitric acid and 18% ammonium sulfite at 150 ℃ could yield a solid product with an organic matter content as high as 794.40 g·kg~(-1), which was 5.70 g·kg~(-1) more than that obtained in the validation tests. Analysis of humification of the solid product showed that SPORL could promote the formation of humic acid and improve the degree of humification. Therefore, when the maize straw was treated with acidic ammonium sul-fite a catalyst in a reactor at high temperature and high pressure, lignosulfonates could be formed, which could subsequently convert into humic substances that contains a mixture of lingohumic acids and a smaller proportion of low-molecular-weight organic compounds. This method can add to the value of maize straw resource reuse.
引文
[1]左旭,王红彦,王亚静,等.中国玉米秸秆资源量估算及其自然适宜性评价[J].中国农业资源与区划,2015,36(6):5-10.ZUO Xu,WANG Hong-yan,WANG Ya-jing,et al.Estimation and suitability evaluation of corn straw resources in China[J].Chinese Journal of Agricultural Resources and Regional Planning,2015,36(6):5-10.
[2]崔蜜蜜,蒋琳莉,颜廷武.基于资源密度的作物秸秆资源化利用潜力测算与市场评估[J].中国农业大学学报,2016,21(6):117-131.CUI Mi-mi,JIANG Lin-li,YAN Ting-wu.Potential evaluation and market assessment on crop straw resource utilization based on resource density[J].Journal of China Agricultural University,2016,21(6):117-131.
[3]张培栋,杨艳丽,李光全,等.中国农作物秸秆能源化潜力估算[J].可再生能源,2007,25(6):80-83.ZHANG Pei-dong,YANG Yan-li,LI Guang-quan,et al.Energy potentiality of crop straw resources in China[J].Renewable Energy Resources,2007,25(6):80-83.
[4]袁嫚嫚,邬刚,胡润,等.秸秆还田配施化肥对稻油轮作土壤有机碳组分及产量影响[J].植物营养与肥料学报,2017,23(1):27-35.YUAN Man-man,WU Gang,HU Run,et al.Effects of straw returning plus fertilization on soil organic carbon components and crop yields in rice-rapeseed rotation system[J].Journal of Plant Nutrition and Fertilizer,2017,23(1):27-35.
[5]李新华,郭洪海,朱振林,等.不同秸秆还田模式对土壤有机碳及其活性组分的影响[J].农业工程学报,2016,32(9):130-135.LI Xin-hua,GUO Hong-hai,ZHU Zhen-lin,et al.Effects of different straw return modes on contents of soil organic carbon and fractions of soil active carbon[J].Transactions of the Chinese Society of Agricultural Engineering,2016,32(9):130-135.
[6]李涛,葛晓颖,何春娥,等.豆科秸秆、氮肥配施玉米秸秆还田对秸秆矿化和微生物功能多样性的影响[J].农业环境科学学报,2016,35(12):2377-2384.LI Tao,GE Xiao-ying,HE Chun-e,et al.Effects of straw retention with mixing maize straw by alfalfa straw or N fertilizer on carbon and nitrogen mineralization and microbial functional diversity[J].Journal of AgroEnvironment Science,2016,35(12):2377-2384.
[7]杨丽丽,周米良,邓小华,等.不同腐熟剂对玉米秸秆腐解及养分释放动态的影响[J].中国农学通报,2016,32(30):32-37.YANG Li-li,ZHOU Mi-liang,DENG Xiao-hua,et al.Decomposition rate and nutrient release of corn stalk treated with different decomposition maturing agents[J].Chinese Agricultural Science Bulletin,2016,32(30):32-37.
[8]解恒参,赵晓倩.农作物秸秆综合利用的研究进展综述[J].环境科学与管理,2015,40(1):86-90.XIE Heng-shen,ZHAO Xiao-qian.Research progress of comprehensive utilization of crop straw[J].Environmental Science and Management,2015,40(1):86-90.
[9]Wang G S,Pan X J,Zhu J Y,et al.Sulfite pretreatment to overcome recalcitrance of lignocellulose(SPORL)for robust enzymatic saccharification of hardwoods[J].Biotechnology Progress,2009,25(4):1086-1093.
[10]Zhu J Y,Pan X J,Wang G S,et al.Sulfite pretreatment(SPORL)for robust enzymatic saccharification of spruce and red pine[J].Bioresource Technology,2009,100(8):2411-2418.
[11]Tian S,Zhu W,Gleisner R,et al.Comparisons of SPORL and dilute acid pretreatments for sugar and ethanol productions from aspen[J].Biotechnology Progress,2011,27(2):419-427.
[12]刘云云,王高升,普春刚,等.亚硫酸氢盐预处理对玉米秸秆酶水解的影响[J].林产化学与工业,2010,30(4):73-77.LIU Yun-yun,WANG Gao-sheng,PU Chun-gang,et al.Effect of bisulfite pretreatment on enzymatic hydrolysis of corn stalk[J].Chemistry&Industry of Forest Products,2010,30(4):73-77.
[13]齐临冬,王高升,于孟辉,等.亚硫酸盐预处理对棉秆酶水解的影响[J].农业工程学报,2011,27(9):276-281.QI Lin-dong,WANG Gao-sheng,YU Meng-hui,et al.Effect of sulfite pretreatment on enzymatic hydrolysis of cotton stalk[J].Transactions of the Chinese Society of Agricultural Engineering,2011,27(9):276-281.
[14]刘志佳,董益帆,兰天晴.亚硫酸盐预处理对蔗渣酶解效率的影响[J].林产化学与工业,2016,36(5):89-94.LIU Zhi-jia,DONG Yi-fan,LAN Tian-qing.Effect of sulfite pretreatment on hydrolysis efficiency of sugarcane bagasse[J].Chemistry and Industry of Forest Products,2016,36(5):89-94.
[15]朱文远.SPORL预处理技术在木质生物质转化中应用研究[D].广州:华南理工大学,2010.ZHU Wen-yuan.On application of SPORL pretreatment process in woody biomass conversion[D].Guangzhou:South China University of Technology,2010.
[16]Novák F,譒estauberováM,Hrabal R.Structural features of lignohumic acids[J].Humic Acid,2015,1093:179-185.
[17]王德汉,彭俊杰,林辉东,等.木质素磺酸盐对尿素氮转化与蔬菜硝酸盐积累的影响[J].环境科学,2003,24(5):141-145.WANG De-han,PENG Jun-jie,LIN Hui-dong,et al.Effect of lignosulfonates on controlling of urea nitrogen transformation and nitrate accumulation in vegetable[J].Environmental Science,2003,24(5):141-145.
[18]王琰,朱杨苏,勇强,等.酶水解p H值对酸性亚硫酸氨盐预处理杨木糖化效率的影响[J].纤维素科学与技术,2015,23(3):15-21.WANG Yan,ZHU Yang-su,YONG Qiang,et al.Effects of p H on the enzymatic saccharification of acid sodium bisulfite pretreated poplar[J].Journal of Cellulose Science and Technology,2015,23(3):15-21.
[19]Lan T Q,Lou H,Zhu J Y.Enzymatic saccharification of lignocelluloses should be conducted at elevated p H 5.2~6.2[J].Bioenergy Research,2013,6(2):476-485.
[20]Shuai L,Yang Q,Zhu J Y,et al.Comparative study of SPORL and dilute-acid pretreatments of spruce for cellulosic ethanol production[J].Bioresource Technology,2010,101(9):3106-3114.
[21]Zhou H F,Zhu J Y,Gleisner R,et al.Pilot-scale demonstration of SPORL for bioconversion of lodgepole pine to bioethanol and lignosulfonate[J].Holzforschung,2016,70(1):21-30.
[22]杨甲一,王高升,许杰.亚硫酸盐预处理对麦草组分分离和糖化的影响[J].中华纸业,2010,31(14):15-20.YANG Jia-yi,WANG Gao-sheng,XU Jie.Effects of sulfite pretreatment on the components separation and saccharification of wheat straw[J].China Pulp&Paper Industry,2010,31(14):15-20.
[23]朱文远,姜波,寇佳文,等.酸性亚硫酸盐预处理对棉杆糖化效率的影响[J].纤维素科学与技术,2015,23(4):23-29.ZHU Wen-yuan,JIANG Bo,KOU Jia-wen,et al.Effects of bisulfite pretreatment on enzymatic saccharification of cotton stalk[J].Journal of Cellulose Science and Technology,2015,23(4):23-29.
[24]王德汉,彭俊杰,肖雄师,等.利用麦草造纸碱木素生产螯合锌肥及其对玉米生长的影响[J].植物营养与肥料学报,2004,10(1):78-81.WANG De-han,PENG Jun-jie,XIAO Xiong-shi,et al.Using papermaking alkaline lignin to produce zinc lignosulfonate and its effect on corn growth[J].Plant Nutrition&Fertilizing Science,2004,10(1):78-81.
[25]张泽志,韩春亮,李成未.响应面法在试验设计与优化中的应用[J].河南教育学院学报:自然科学版,2011,20(4):34-37.ZHANG Ze-zhi,HAN Chun-liang,LI Cheng-wei.Application of response surface method in experimental design and optimization[J].Journal of Henan Institute of Education,2011,20(4):34-37.
[26]任天宝,马孝琴,徐桂转,等.响应面法优化玉米秸秆蒸汽爆破预处理条件[J].农业工程学报,2011,27(9):282-286.REN Tian-bao,MA Xiao-qin,XU Gui-zhuan,et al.Optimizing steam explosion pretreatment conditions of corn stalk by response surface methodology[J].Transactions of the Chinese Society of Agricultural Engineering,2011,27(9):282-286.
[27]刘欢,庞博,李海明,等.改善玉米秸秆酶水解糖化得率的碱性亚硫酸盐法预处理工艺的优化[J].中华纸业,2014(2):10-14.LIU Huan,PANG Bo,LI Hai-ming,et al.Optimization of alkaline sulfite pretreatment of corn stover for improving enzymatic hydrolysis saccharification yield[J].China Pulp&Paper Industry,2014(2):10-14.
[28]王菲菲.不同预处理方法对玉米秸秆木质素吸附纤维素酶特征的影响[D].济南:山东大学,2014.WANG Fei-fei.The influence of lignin from corn stover after different pretreament methods to celluanse[D].Jinan:Shandong University,2014.
[29]中华人民共和国农业部.NY 525—2012有机肥料[S].北京:中国农业出版社,2012.Ministry of Agriculture of PRC.NY 525—2012 Organic fertilizer[S].Beijing:China Agriculture Press,2012.
[30]Kumada K,Sato O,Ohsumi Y,et al.Humus composition of mountain soils in central Japan with special reference to the distribution of type humic acid[J].Soil Science&Plant Nutrition,1967,13(5):151-158.
[2]崔蜜蜜,蒋琳莉,颜廷武.基于资源密度的作物秸秆资源化利用潜力测算与市场评估[J].中国农业大学学报,2016,21(6):117-131.CUI Mi-mi,JIANG Lin-li,YAN Ting-wu.Potential evaluation and market assessment on crop straw resource utilization based on resource density[J].Journal of China Agricultural University,2016,21(6):117-131.
[3]张培栋,杨艳丽,李光全,等.中国农作物秸秆能源化潜力估算[J].可再生能源,2007,25(6):80-83.ZHANG Pei-dong,YANG Yan-li,LI Guang-quan,et al.Energy potentiality of crop straw resources in China[J].Renewable Energy Resources,2007,25(6):80-83.
[4]袁嫚嫚,邬刚,胡润,等.秸秆还田配施化肥对稻油轮作土壤有机碳组分及产量影响[J].植物营养与肥料学报,2017,23(1):27-35.YUAN Man-man,WU Gang,HU Run,et al.Effects of straw returning plus fertilization on soil organic carbon components and crop yields in rice-rapeseed rotation system[J].Journal of Plant Nutrition and Fertilizer,2017,23(1):27-35.
[5]李新华,郭洪海,朱振林,等.不同秸秆还田模式对土壤有机碳及其活性组分的影响[J].农业工程学报,2016,32(9):130-135.LI Xin-hua,GUO Hong-hai,ZHU Zhen-lin,et al.Effects of different straw return modes on contents of soil organic carbon and fractions of soil active carbon[J].Transactions of the Chinese Society of Agricultural Engineering,2016,32(9):130-135.
[6]李涛,葛晓颖,何春娥,等.豆科秸秆、氮肥配施玉米秸秆还田对秸秆矿化和微生物功能多样性的影响[J].农业环境科学学报,2016,35(12):2377-2384.LI Tao,GE Xiao-ying,HE Chun-e,et al.Effects of straw retention with mixing maize straw by alfalfa straw or N fertilizer on carbon and nitrogen mineralization and microbial functional diversity[J].Journal of AgroEnvironment Science,2016,35(12):2377-2384.
[7]杨丽丽,周米良,邓小华,等.不同腐熟剂对玉米秸秆腐解及养分释放动态的影响[J].中国农学通报,2016,32(30):32-37.YANG Li-li,ZHOU Mi-liang,DENG Xiao-hua,et al.Decomposition rate and nutrient release of corn stalk treated with different decomposition maturing agents[J].Chinese Agricultural Science Bulletin,2016,32(30):32-37.
[8]解恒参,赵晓倩.农作物秸秆综合利用的研究进展综述[J].环境科学与管理,2015,40(1):86-90.XIE Heng-shen,ZHAO Xiao-qian.Research progress of comprehensive utilization of crop straw[J].Environmental Science and Management,2015,40(1):86-90.
[9]Wang G S,Pan X J,Zhu J Y,et al.Sulfite pretreatment to overcome recalcitrance of lignocellulose(SPORL)for robust enzymatic saccharification of hardwoods[J].Biotechnology Progress,2009,25(4):1086-1093.
[10]Zhu J Y,Pan X J,Wang G S,et al.Sulfite pretreatment(SPORL)for robust enzymatic saccharification of spruce and red pine[J].Bioresource Technology,2009,100(8):2411-2418.
[11]Tian S,Zhu W,Gleisner R,et al.Comparisons of SPORL and dilute acid pretreatments for sugar and ethanol productions from aspen[J].Biotechnology Progress,2011,27(2):419-427.
[12]刘云云,王高升,普春刚,等.亚硫酸氢盐预处理对玉米秸秆酶水解的影响[J].林产化学与工业,2010,30(4):73-77.LIU Yun-yun,WANG Gao-sheng,PU Chun-gang,et al.Effect of bisulfite pretreatment on enzymatic hydrolysis of corn stalk[J].Chemistry&Industry of Forest Products,2010,30(4):73-77.
[13]齐临冬,王高升,于孟辉,等.亚硫酸盐预处理对棉秆酶水解的影响[J].农业工程学报,2011,27(9):276-281.QI Lin-dong,WANG Gao-sheng,YU Meng-hui,et al.Effect of sulfite pretreatment on enzymatic hydrolysis of cotton stalk[J].Transactions of the Chinese Society of Agricultural Engineering,2011,27(9):276-281.
[14]刘志佳,董益帆,兰天晴.亚硫酸盐预处理对蔗渣酶解效率的影响[J].林产化学与工业,2016,36(5):89-94.LIU Zhi-jia,DONG Yi-fan,LAN Tian-qing.Effect of sulfite pretreatment on hydrolysis efficiency of sugarcane bagasse[J].Chemistry and Industry of Forest Products,2016,36(5):89-94.
[15]朱文远.SPORL预处理技术在木质生物质转化中应用研究[D].广州:华南理工大学,2010.ZHU Wen-yuan.On application of SPORL pretreatment process in woody biomass conversion[D].Guangzhou:South China University of Technology,2010.
[16]Novák F,譒estauberováM,Hrabal R.Structural features of lignohumic acids[J].Humic Acid,2015,1093:179-185.
[17]王德汉,彭俊杰,林辉东,等.木质素磺酸盐对尿素氮转化与蔬菜硝酸盐积累的影响[J].环境科学,2003,24(5):141-145.WANG De-han,PENG Jun-jie,LIN Hui-dong,et al.Effect of lignosulfonates on controlling of urea nitrogen transformation and nitrate accumulation in vegetable[J].Environmental Science,2003,24(5):141-145.
[18]王琰,朱杨苏,勇强,等.酶水解p H值对酸性亚硫酸氨盐预处理杨木糖化效率的影响[J].纤维素科学与技术,2015,23(3):15-21.WANG Yan,ZHU Yang-su,YONG Qiang,et al.Effects of p H on the enzymatic saccharification of acid sodium bisulfite pretreated poplar[J].Journal of Cellulose Science and Technology,2015,23(3):15-21.
[19]Lan T Q,Lou H,Zhu J Y.Enzymatic saccharification of lignocelluloses should be conducted at elevated p H 5.2~6.2[J].Bioenergy Research,2013,6(2):476-485.
[20]Shuai L,Yang Q,Zhu J Y,et al.Comparative study of SPORL and dilute-acid pretreatments of spruce for cellulosic ethanol production[J].Bioresource Technology,2010,101(9):3106-3114.
[21]Zhou H F,Zhu J Y,Gleisner R,et al.Pilot-scale demonstration of SPORL for bioconversion of lodgepole pine to bioethanol and lignosulfonate[J].Holzforschung,2016,70(1):21-30.
[22]杨甲一,王高升,许杰.亚硫酸盐预处理对麦草组分分离和糖化的影响[J].中华纸业,2010,31(14):15-20.YANG Jia-yi,WANG Gao-sheng,XU Jie.Effects of sulfite pretreatment on the components separation and saccharification of wheat straw[J].China Pulp&Paper Industry,2010,31(14):15-20.
[23]朱文远,姜波,寇佳文,等.酸性亚硫酸盐预处理对棉杆糖化效率的影响[J].纤维素科学与技术,2015,23(4):23-29.ZHU Wen-yuan,JIANG Bo,KOU Jia-wen,et al.Effects of bisulfite pretreatment on enzymatic saccharification of cotton stalk[J].Journal of Cellulose Science and Technology,2015,23(4):23-29.
[24]王德汉,彭俊杰,肖雄师,等.利用麦草造纸碱木素生产螯合锌肥及其对玉米生长的影响[J].植物营养与肥料学报,2004,10(1):78-81.WANG De-han,PENG Jun-jie,XIAO Xiong-shi,et al.Using papermaking alkaline lignin to produce zinc lignosulfonate and its effect on corn growth[J].Plant Nutrition&Fertilizing Science,2004,10(1):78-81.
[25]张泽志,韩春亮,李成未.响应面法在试验设计与优化中的应用[J].河南教育学院学报:自然科学版,2011,20(4):34-37.ZHANG Ze-zhi,HAN Chun-liang,LI Cheng-wei.Application of response surface method in experimental design and optimization[J].Journal of Henan Institute of Education,2011,20(4):34-37.
[26]任天宝,马孝琴,徐桂转,等.响应面法优化玉米秸秆蒸汽爆破预处理条件[J].农业工程学报,2011,27(9):282-286.REN Tian-bao,MA Xiao-qin,XU Gui-zhuan,et al.Optimizing steam explosion pretreatment conditions of corn stalk by response surface methodology[J].Transactions of the Chinese Society of Agricultural Engineering,2011,27(9):282-286.
[27]刘欢,庞博,李海明,等.改善玉米秸秆酶水解糖化得率的碱性亚硫酸盐法预处理工艺的优化[J].中华纸业,2014(2):10-14.LIU Huan,PANG Bo,LI Hai-ming,et al.Optimization of alkaline sulfite pretreatment of corn stover for improving enzymatic hydrolysis saccharification yield[J].China Pulp&Paper Industry,2014(2):10-14.
[28]王菲菲.不同预处理方法对玉米秸秆木质素吸附纤维素酶特征的影响[D].济南:山东大学,2014.WANG Fei-fei.The influence of lignin from corn stover after different pretreament methods to celluanse[D].Jinan:Shandong University,2014.
[29]中华人民共和国农业部.NY 525—2012有机肥料[S].北京:中国农业出版社,2012.Ministry of Agriculture of PRC.NY 525—2012 Organic fertilizer[S].Beijing:China Agriculture Press,2012.
[30]Kumada K,Sato O,Ohsumi Y,et al.Humus composition of mountain soils in central Japan with special reference to the distribution of type humic acid[J].Soil Science&Plant Nutrition,1967,13(5):151-158.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |