摘要
以一级脱水沼渣为原料,通过热重-红外联用分析其失重行为及热解气相产物的组成,采用单因素试验方法,考察炭化温度、升温速率、保温时间对沼渣炭的得率、理化性质的影响。结果表明:360~480℃区域为热解的主要阶段。随着温度的升高,炭得率、挥发分含量降低,灰分含量增加,固定碳含量在700℃最高(18.37%);随着升温速率提高,灰分、固定碳含量提高,炭得率及挥发分含量降低;随着保温时间的延长,炭得率逐渐降低,对灰分、挥发分、固定碳影响不显著;原料及炭热值较低;重金属Cd和Pb含量低于"有机-无机复混肥料"标准限值(GB 18877—2009);Hg和Cr含量较低,符合肥料用有害重金属元素限值标准,而有益于植物生长的元素Mn和Zn含量较高,本研究为减量化处理复杂沼渣提供了理论依据。
The digestate after the first-stage dehydration was used as the raw material in this study. Its weight loss behavior and the compositions of the pyrolysis gas products were analyzed by thermogravimetry-Fourier Transform infrared spectroscopy( TG-FTIR). The single-factor test method was used to investigate the effects of carbonization temperature, heating rate and holding time on the yields and physiochemical properties of biochar. The results showed that the pyrolysis reactions mainly took place at the temperature range of 360-480℃. The yield and volatile content of biochar gradually decreased with the increase of pyrolysis temperature, while its ash content increased correspondingly. The highest content(18.37%) of fixed carbon in char was obtained at 700℃. The increase of heating rate had led to the increase in the contents of ash and fixed carbon in biochar, as well as result in the reduction in char yield and volatile content in biochar. In the meantime, the yield of biochar decreased gradually with the increase of holding time. The effect of holding time on the contents of ash, volatile and fixed carbon in biochar was insignificant. The calorific values of raw material and biochar were all low. The contents of heavy metals Cd and Pb in the produced biochar were lower than those indicated in the standard of "Organic/inorganic compound fertilizer "(GB18877—2009). Hg and Cr contents in the biochars were low,which was within the limits of harmful heavy metal elements in fertilizers. On the other hand, the contents of elements of Mn and Zn that are beneficial to plant growth were high. This study provides a theoretical basis for using the digestate as raw materials to produce fertilizers.
引文
[1]郭强,牛冬杰,程海静,等.沼渣的综合利用[J].中国资源综合利用,2005(12):11-15.GUO Qiang,NIU Dongjie,CHENG Haijing,et al.Comprehensive utilization of biogas slag[J].China Resources Comprehensive Utilization,2005(12):11-15.
[2]M?LLER J,BOLDRIN A,CHRISTENSEN T H.Anaerobic digestion and digestate use:accouilting of greerlhouse gases and global warming contribution[J].Waste Managemate&Research,2009,27(8):8l3-824.
[3]ZHANG Ruihong,EL-MASHAD H,MARTMAN K,et al.Characterization of food waste as feedstock for anaerobic digestion[J].Bioresource Technology,2007,98(4):929-935.
[4]谢晶,陈理,庞昌乐,等.山东省沼气工程发展调查报告[J].中国沼气,2012,30(4):41-44.XIE Jing,CHEN Li,PANG Changle,et al.Investigation report on biogas project development in Shandong province[J].China Biogas,2012,30(4):41-44.
[5]郝先荣.养殖场废弃物的资源化利用--中国沼气工程发展现状与展望[J].中国畜牧业,2011(12):26-31.HAO Xianrong.Resource utilization of waste in farms:current status and prospects of biogas project development in china[J].China Animal Industry,2011(12):26-31.
[6]蒋旭光,方纯琪,金余其,等.含铬制革废弃物处理的研究现状和研究思路[J].化工进展,2018,37(2):752-760.JIANG Xuguang,FANG Chunqi,JIN Yuqi,et al.Research status and research ideas of chrome tanning waste disposal[J].Chemical Industry and Engineering Progress,2018,37(2):752-760.
[7]石海波,孙姣,陈文义,等.生物质热解炭化反应设备研究进展[J].化工进展,2012,31(10):2130-2136.SHI Haibo,SUN Jiao,CHEN Wenyi,et al.Progress in the study of biomass pyrolysis carbonization reactive equipment[J].Chemical Industry and Engineering Progress,2012,31(10):2130-2136.
[8]JONG W D,PIRONE A,WOJTOWICZ M A.Pyrolysis of miscanthus giganteus and wood pellets:TG-FTIR analysis and reaction kinetics[J].Fuel,2003,82(9):1139-1147.
[9]TAO Ling,ZHAO Guangbo,QIAN Juan,et al.TG-FTIRcharacterization of pyrolysis of waste mixtures of paint and tar slag[J].Journal of Hazardous Materials,2010,175(1/2/3):754-761.
[10]JIANG Xuguang,LI Chunyu,CHI Yong,et al.TG-FTIR study on urea-formaldehyde resin residue during pyrolysis and combustion[J].Journal of Hazardous Materials,2010,173(1):205-210.
[11]于娟,章明川.生物质热解特性的热重分析[J].上海交通大学学报,2002,36(10):1475-1478.YU Juan,ZHANG Mingchuan.Thermogravimetric analysis of biomass pyrolysis characteristics[J].Journal of Shanghai Jiaotong University,2002,36(10):1475-1478.
[12]徐朝芬,向军,胡松,等.热解条件对煤的热解行为的影响[J].实验室研究与探索,2005,24(6):18-20.XU Chaofen,XIANG Jun,HU Song,et al.Influence of pyrolysis conditions on the pyrolysis behavior of coal[J].Research and Exploration in Laborator,2005,24(6):18-20.
[13]李宇宇,李瑞,田启魁,等.热重法研究落叶松热解动力学特性[J].东北林业大学学报,2011,39(7):63-66.LI Yuyu,LI Rui,TIAN Qikui,et al.Thermogravimetric study of pyrolysis kinetics of larch[J].Journal of Northeast Forestry University,2011,39(7):63-66.
[14]RADAWIEC W,DUBICKI M,KARWOWSKA A,et al.Biochar from a digestate as an energy product and soil improver[J].Agricultural Engineering,2014,3(151):149-156.
[15]VAUGHN S F,ELLER F J,EVANGELISTA R L,et al.Evaluation of biochar-anaerobic potato digestate mixtures as renewable components of horticultural potting media[J].Industrial Crops&Products,2015,65:467-471.
[16]马欢欢,周建斌,王刘江,等.秸秆炭基肥料挤压造粒成型优化及主要性能[J].农业工程学报,2014,30(5):270-276.MA Huanhuan,ZHOU Jianbin,WANG Liujiang,et al.Straw carbon based fertilizer granulation molding optimization and its main properties[J].Journal of Agricultural Engineering,2014,30(5):270-276.
[17]孟军,张伟明,王绍斌,等.农林废弃物炭化还田技术的发展与前景[J].沈阳农业大学学报,2011,42(4):387-392.MENG Jun,ZHANG Weiming,WANG Shaobin,et al.Development and prospect of carbonization and returning technology of agro-forestry residue[J].Journal of Shenyang Agricultural University,2011,42(4):387-392.
[18]周建斌,邓丛静,陈金林,等.棉秆炭对镉污染土壤的修复效果[J].生态环境学报,2008,17(5):1857-1860.ZHOU Jianbin,DENG Congjing,CHEN Jinlin,et al.Remediation effects of cotton stalk carbon on cadmium contaminated soil[J].Ecology and Environmental Sciences,2008,17(5):1857-1860.
[19]邓丛静,邹积微,张齐生,等.新型改良剂对土壤性质及小白菜生长的影响[J].科学技术与工程,2015,15(4):171-174.DENG Congjing,ZOU Jiwei,ZHANG Qisheng,et al.Influence of new conditioner on soil physical and chemical properties and growth of Chinese cabbage[J].Science Technology and Engineering,2015,15(4):171-174.
[20]INYANG M,GAO Bin,PULLAMMANAPPALLIIL P,et al.Biochar from anaerobically digested sugarcane bagasse[J].Bioresource Technology,2010,101(22):8868-8872.
[21]MUMME J,ECKERVOGT L,PIELERT J,et al.Hydrothermal carbonization of anaerobically digested maize silage[J].Bioresource Technology,2011,102(19):9255-9260.
[22]NEUMANN J,BINDER S,APFELBACHER A,et al.Production and characterization of a new quality pyrolysis oil,char and syngas from digestate-Introducing the thermo-catalytic reforming process[J].Journal of Analytical&Applied Pyrolysis,2015,113(4):137-142.
[23]罗希韬,王志奇,武景丽,等.基于热重红外联用分析的PE、PS、PVC热解机理研究[J].燃料化学学报,2012,40(9):1147-1152.LUO Xitao,WANG Zhiqi,WU Jingli,et al.Study on the pyrolysis mechanism of polyethylene,polystyrene,and polyvinyl chloride by TGA-FTIR[J].Journal of Fuel Chemistry and Technology,2012,40(9):1147-1152.
[24]徐艺,陈宇,华德润,等.固定床反应器中生物质/废塑料共热解制备燃料油[J].化工进展,2013,32(3):563-569.XU Yi,CHEN Yu,HUA Derun,et al.Co-pyrolysis of biomass and waste plastic for biofuel in fixed-bed reactor[J].Chemical Industry and Engineering Progress,2013,32(3):563-569.
[25]姚燕,王树荣,郑赟,等.基于热红联用分析的木质素热裂解动力学研究[J].燃烧科学与技术,2007,13(1):50-54.YAO Yan,WANG Shurong,ZHENG Yun,et al.Kinetic research of lignin pyrolysis by TGA-FTIR analysis[J].Journal of Combustion Science and Technology,2007,13(1):50-54.
[26]付鹏,胡松,孙路石,等.稻草和玉米秆热解气体产物的释放特性及形成机理[J].中国电机工程学报,2009,29(2):113-118.FU Peng,HU Song,SUN Lushi,et al.Release characteristics and formation mechanism of gas products during rice and maize stalk pyrolysis[J].Proceedings of the CSEE,2009,29(2):113-118.
[27]徐砚,朱群益,宋绍国.采用热重与红外光谱联用研究玉米秸秆热解[J].热能动力工程,2012,27(1):126-129.XU Yan,ZHU Qunyi,SONG Shaoguo.Study of the pyrolysis of corn stalk by combining the thermogravimetric method with the infrared spectrum one[J].Thermal Power Engineering,2012,27(1):126-129.
[28]李飞跃,汪建飞,谢越,等.热解温度对生物质炭碳保留量及稳定性的影响[J].农业工程学报,2015,31(4):266-271.LI Feiyue,WANG Jianfei,XIE Yue,et al.Effects of pyrolysis temperature on carbon retention and stability of biochar[J].Journal of Agricultural Engineering,2015,31(4):266-271.
[29]潘萌娇,孙姣,贺强,等.热解终温和加热速率对棉杆热解生物炭的影响研究[J].河北工业大学学报,2014,43(5):60-66.PAN Mengjiao,SUN Jiao,HE Qiang,et al.The effect of pyrolysis temperature and heating rate on biochar obtained from pyrolysis of cotton stalk[J].Journal of Hebei University of Technology,2014,43(5):60-66.
[30]CHEN Yingquan,YANG Haiping,WANG Xianhua,et al.Biomassbased pyrolytic polygeneration system on cotton stalk pyrolysis:Influence of temperature[J].Bioresource Technology,2012,107:411-418.
[31]刘宁.生物炭的理化性质及其在农业中应用的基础研究[D].沈阳:沈阳农业大学,2014.LIU Ning.The basic research of physicochemical properties of biochar and its application in agriculture[D].Shenyang:Shenyang Agricultural University,2014.
[32]傅庚福.成型生物质炭化及成型炭特性研究[D].南京:南京林业大学,2009.FU Gengfu.Study on carbonization of formed biomass and shaped carbon[D].Nanjing:Nanjing Forestry University,2009.
[33]RONSSE F,VAN HECKE S,DICKINSON D,et al.Production and characterization of slow pyrolysis biochar:influence of feedstock type and pyrolysis conditions[J].GCB Bioenergy,2013,5(2):104-115.
[34]严伟,陈智豪,盛奎川.适宜炭化温度及时间改善生物质成型炭品质[J].农业工程学报,2015,31(24):245-249.YAN Wei,CHEN Zhihao,SHENG Kuichuan.Carbonization temperature and time improving quality of charcoal briquettes[J].Journal of Agricultural Engineering,2015,31(24):245-249.
[35]肖婧,王传杰,黄敏,等.生物质炭对设施大棚土壤性质与果蔬产量影响的整合分析[J].植物营养与肥料学报,2018,24(1):228-236.XIAO Jing,WANG Chuanjie,HUANG Min,et al.Meta-analysis of biochar application effects on soil fertility and yields of fruit and vegetables in greenhouse[J].Journal of Plant Nutrition and Fertilizers,2018,24(1):228-236.
[36]乔志刚.不同生物质炭基肥对不同作物生长、产量及氮肥利用率的影响研究[D].南京:南京农业大学,2013.QIAO Zhigang.Effects of different biochar fertilizer on growth,yield and nitrogen utilizing rate of different crops[D].Nanjing:Nanjing Agricultural University,2013.
[37]孟军,张伟明,王绍斌,等.农林废弃物炭化还田技术的发展与前景[J].沈阳农业大学学报,2011,42(4):387-392.MENG Jun,ZHANG Weiming,WANG Shaobin,et al.Development and prospect of carbonization and returning technology of agro-forestry residue[J].Journal of Shenyang Agricultural University,2011,42(4):387-392.
[38]陈温福,张伟明,孟军,等.生物炭应用技术研究[J].中国工程科学,2011,13(2):83-89.CHEN Wenfu,ZHANG Weiming,MENG Jun,et al.Researches on biochar application technology[J].Engineering Sciences,2011,13(2):83-89.
[39]康日峰,张乃明,史静,等.生物炭基肥料对小麦生长、养分吸收及土壤肥力的影响[J].中国土壤与肥料,2014(6):33-38.KANG Rifeng,ZHANG Naiming,SHI Jing,et al.Effect of biochar based fertilizer on wheat growth,nutrient absorption and soil fertility[J].Soils and Fertilizers Sciences in China,2014(6):33-38.
[40]范世锁,汤婕,程燕,等.污泥基生物炭中重金属的形态分布及潜在生态风险研究[J].生态环境学报,2015(10):1739-1744.FAN Shisuo,TANG Jie,CHENG Yan,et al.Investigation of the speciation of heavy metals in sludge-derived biochar and its potential ecological risk[J].Ecology and Environmental Sciences,2015(10):1739-1744.
[41]JIN Junwei,LI Yanan,ZHANG Jianyun,et al.Influence of pyrolysis temperature on properties and environmental safety of heavy metals in biochars derived from municipal sewage sludge[J].Journal of Hazardous Materials,2016,320:417-426.