玉米秸秆和小麦秸秆生物炭的热稳定性及化学稳定性
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摘要
为探究秸秆类农业废弃物所制备生物炭的稳定性,以玉米秸秆和小麦秸秆为原料,分别在200℃和500℃下制备生物炭,通过元素分析、傅里叶红外光谱分析、热重及差热分析等分别探究了生物炭的理化性质及热稳定性。结果表明:玉米秸秆因木质素含量较小麦秸秆高,相同温度下制备的生物炭的热稳定性更高。NaClO、H_2O_2和KMnO4三种氧化剂对生物炭的氧化结果表明,秸秆类生物炭的抗氧化性不仅与高木质素含量有关,且受矿物保护的影响。尤其是在KMnO4体系中,木质素和纤维素含量低、灰分含量高的麦秆及其生物炭的化学稳定性更强,表现出了与热稳定性不同的规律。此外,较高温度下制备的生物炭表现出较强的抗氧化能力,具有较大的碳封存潜力。
The objective of this study is to explore the chemical properties and thermal stability of biochars prepared from corn and wheat stalks, which are agricultural wastes. The biochars were prepared at 200 ℃ and 500 ℃. Physical and chemical properties and thermal sta?bility of the biochars were investigated by elemental analysis, fourier transformed infrared spectroscopy(FTIR), and thermo-gravimetric(TGA-DTA)analysis. The results showed that the relative heat stability of corn stalk biochar was higher than that of wheat stalk biocharprepared at the same temperature, which was attributed to the higher lignin content of the former. In addition, biochars prepared from thesame raw materials at a higher temperature showed better thermal stability due to rise in aromaticity. Oxidation of the biochars by NaClO,H_2 O_2, and KMnO4 was minimal. In addition to a high lignin content, mineral protection in stalk biochars prevented oxidation. Particularly,in the KMnO4 system, the wheat stalk biochar, despite lower lignin content, showed stronger chemical stability due to the high ash content,hence, showing a different mode of thermal stability. Besides, the biochars prepared at higher temperatures exhibited a rise in the antioxi?dant capacity and carbon sequestration potential. This study provides valuable insights regarding the practical application and stability of straw biochars.
The objective of this study is to explore the chemical properties and thermal stability of biochars prepared from corn and wheat stalks, which are agricultural wastes. The biochars were prepared at 200 ℃ and 500 ℃. Physical and chemical properties and thermal sta?bility of the biochars were investigated by elemental analysis, fourier transformed infrared spectroscopy(FTIR), and thermo-gravimetric(TGA-DTA)analysis. The results showed that the relative heat stability of corn stalk biochar was higher than that of wheat stalk biocharprepared at the same temperature, which was attributed to the higher lignin content of the former. In addition, biochars prepared from thesame raw materials at a higher temperature showed better thermal stability due to rise in aromaticity. Oxidation of the biochars by NaClO,H_2 O_2, and KMnO4 was minimal. In addition to a high lignin content, mineral protection in stalk biochars prevented oxidation. Particularly,in the KMnO4 system, the wheat stalk biochar, despite lower lignin content, showed stronger chemical stability due to the high ash content,hence, showing a different mode of thermal stability. Besides, the biochars prepared at higher temperatures exhibited a rise in the antioxi?dant capacity and carbon sequestration potential. This study provides valuable insights regarding the practical application and stability of straw biochars.
引文
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[11]文方园,陈建,田路萍,等.过氧化氢氧化对生物炭表面性质的改变及其对双酚A吸附的影响[J].生态毒理学报,2016,11(2):628-635.WEN Fang-yuan,CEHN Jian,TIAN Lu-ping,et al.Chemical oxidation of biochars and the impact on bisphenol A sorption[J].Asian Journal of Ecotoxicology,2016,11(2):628-635.
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[17]顾博文,曹心德,赵玲,等.生物质内源矿物对热解过程及生物炭稳定性的影响[J].农业环境科学学报,2017,36(3):591-597.GU Bo-wen,CAO Xin-de,ZHAO Ling,et al.Influence of inherent minerals on biomass pyrolysis and carbon stability in biochar[J].Journal of Agro-Environment Science,2017,36(3):591-597.
[18]Yang Y,Sun K,Han L,et al.Effect of minerals on the stability of biochar[J].Chemosphere,2018,204:310-317.
[19]Chun Y,Sheng G,Chiou C T,et al.Compositions and sorptive properties of crop residue-derived chars[J].Environmental Science&Technology,2004,38(17):4649-4655.
[20]薛惠琴,杭怡琼,陈谊.稻草秸秆中木质素、纤维素测定方法的研讨[J].上海畜牧兽医通讯,2001(2):15.XUE Hui-qin,HANG Yi-qiong,CHEN Yi.Study on determination methods of lignin and cellulose in wheat straw[J].Shanghai Journal of Animal Husbandry and Veterinary Medicine,2001(2):15.
[21]Brodowski S,Amelung W,Haumaier L,et al.Morphological and chemical properties of black carbon in physical soil fractions as revealed by scanning electron microscopy and energy-dispersive X-ray spectroscopy[J].Geoderma,2005,128(1):116-129.
[22]Fornara D A,Tilman D.Plant functional composition influences rates of soil carbon and nitrogen accumulation[J].Journal of Ecology,2008,96(2):314-322.
[23]王刚,李文,薛钦昭,等.生物质化学组分在空气和合成气下的热重行为研究[J].燃料化学学报,2009,37(2):170-176.WANG Gang,LI Wen,XUE Qin-zhao,et al.Thermogravimetric behaviors of biomass′chemical components under air or syngas[J].Journal of Fuel Chemistry and Technology,2009,37(2):170-176.
[24]Han L,Ro K S,Wang Y,et al.Oxidation resistance of biochars as a function of feedstock and pyrolysis condition[J].Science of the Total Environment,2017,616/617:335-344.
[25]Bavel B V.Comparison of Fenton′s reagent and ozone oxidation of polycyclic aromatic hydrocarbons in aged contaminated soils[J].Journal of Soils&Sediments,2006,6(4):208-214.
[26]Singh B,Singh B P,Cowie A L,et al.Characterisation and evaluation of biochars for their application as a soil amendment[J].Soil Research,2010,48(7):516-525.
[27]徐佳,刘荣厚.不同慢速热裂解工艺条件下棉花秸秆生物炭的理化特性分析[J].上海交通大学学报(农业科学版),2017,35(2):19-24.XU Jia,LIU Rong-hou.Physicochemical properties of cotton stalk biochar under different slow pyrolysis conditions[J].Journal of Shanghai Jiaotong University(Agricultural Science),2017,35(2):19-24.
[28]Chen B,Zhou D,Zhu L.Transitional adsorption and partition of nonpolar and polar aromatic contaminants by biochars of pine needles with different pyrolytic temperatures[J].Environmental Science&Technology,2008,42(14):5137-5143.
[29]Uchimiya M,Lima I M,Klasson K T,et al.Immobilization of heavy metal ions(CuⅡ,CdⅡ,NiⅡ,and PbⅡ)by broiler litter-derived biochars in water and soil[J].Journal of Agricultural and Food Chemistry,2010,58(9):5538-5544.
[30]Chen B,Chen Z.Sorption of naphthalene and 1-naphthol by biochars of orange peels with different pyrolytic temperatures[J].Chemosphere,2009,76(1):127-133.
[31]刘朝霞,牛文娟,楚合营,等.秸秆热解工艺优化与生物炭理化特性分析[J].农业工程学报,2018,34(5):196-203.LIU Zhao-xia,NIU Wen-juan,CHU He-ying,et al.Process optimization for straws pyrolysis and analysis of biochar physiochemical properties[J].Transactions of the Chinese Society of Agricultural Engineering,2018,34(5):196-203.
[32]朱恂,李刚,冯云鹏,等.重庆地区7种生物质的成分分析及热重实验[J].重庆大学学报(自然科学版),2006,29(8):44-48.ZHU Xun,LI Gang,FENG Yun-peng,et al.Thermogravimetric experiments and component analysis of biomass in Chongqing[J].Journal of Chongqing University(Natural Science Edition),2006,29(8):44-48.
[33]Mikutta R,Kleber M,Kaiser K,et al.Review:Organic matter removal from soils using hydrogen peroxide,sodium hypochlorite,and disodium peroxodisulfate[J].Soil Science Society of America Journal,2005,69(1):120-135.
[34]Xiang Q,Lee Y Y.Oxidative cracking of precipitated hardwood lignin by hydrogen peroxide[J].Applied Biochemistry&Biotechnology,2000,84-86(1-9):153-162.
[35]Goldstone J V,Pullin M J,Bertilsson S,et al.Reactions of hydroxyl radical with humic substances:Bleaching,mineralization,and production of bioavailable carbon substrates[J].Environmental Science&Technology,2002,36(3):364-372.
[36]傅晓燕,栾连军,朱炜,等.双氧水降解残留农药效果及对苦参有效成分的影响[J].中国中药杂志,2007,32(20):2098-2102.FU Xiao-yan,LUAN Lian-jun,ZHU Wei,et al.Influence of H2O2 on degradation of residual pesticides and constituents in radix sophorae flavescentis[J].China Journal of Chinese Materia Medica,2007,32(20):2098-2102.
[37]Jin J,Sun K,Wang Z,et al.Effects of chemical oxidation on phenanthrene sorption by grass-and manure-derived biochars[J].Science of the Total Environment,2017,598:789-796.
[38]余伟光,黎吉辉,王敦,等.香蕉茎秆生物炭的制备及其对铜离子的吸附特性[J].化工进展,2017,36(4):1499-1505.YU Wei-guang,LI Ji-hui,WANG Dun,et al.The preparation of biochar from pre-oxidation of banana stem and its adsorption of Cu2+[J].Chemical Industry and Engineering Progress,2017,36(4):1499-1505.
[39]许可,贲伟伟,强志民.高锰酸钾氧化降解水中微量有机污染物的研究进展[J].环境化学,2017,36(1):16-26.XU Ke,BEN Wei-wei,QIANG Zhi-min.Oxidative degradation of micro-organic pollutants by potassium permanganate in water:A review[J].Environmental Chemistry,2017,36(1):16-26.
[2]Spokas K A.Review of the stability of biochar in soils:Predictability of O∶C molar ratios[J].Carbon Management,2010,1(2):289-303.
[3]方明,任天志,赖欣,等.花生壳生物炭对潮土和红壤理化性质和温室气体排放的影响[J].农业环境科学学报,2018,37(6):1300-1310.FANG Ming,REN Tian-zhi,LAI Xin,et al.Effects of peanut shell biochar on physico-chemical properties and greenhouse gas emission in fluvo-aquic soil and red soil[J].Journal of Agro-Environment Science,2018,37(6):1300-1310.
[4]Mikutta R,Kleber M,Torn M S,et al.Stabilization of soil organic matter:Association with minerals or chemical recalcitrance?[J].Biogeochemistry,2006,77(1):25-56.
[5]林庆毅,姜存仓,张梦阳.生物炭老化后理化性质及微观结构的表征[J].环境化学,2017,36(10):2107-2114.LIN Qing-yi,JIANG Cun-cang,ZHANG Meng-yang.Characterization of the physical and chemical structures of biochar under simulated aging condition[J].Environmental Chemistry,2017,36(10):2107-2114.
[6]Fang S E,Tsang D C W,Zhou F,et al.Stabilization of cationic and anionic metal species in contaminated soils using sludge-derived biochar[J].Chemosphere,2016,149:263-271.
[7]Ameloot N,Graber E R,Fga V,et al.Interactions between biochar stability and soil organisms:Review and research needs[J].European Journal of Soil Science,2013,64(4):379-390.
[8]Lehmann J.A handful of carbon[J].Nature,2007,447(7141):143-144.
[9]邓金环,郜礼阳,周皖婉,等.不同温度制备香根草生物炭对Cd的吸附特性与机制[J].农业环境科学学报,2018,37(2):340-349.DENG Jin-huan,GAO Li-yang,ZHOU Wan-wan,et al.Adsorption characteristics and mechanisms of Cd2+in biochar derived from vetiver grass under different pyrolysis temperatures[J].Journal of Agro-Environment Science,2018,37(2):340-349.
[10]陆海楠,胡学玉,刘红伟.不同裂解条件对生物炭稳定性的影响[J].环境科学与技术,2013,36(8):11-14.LU Hai-nan,HU Xue-yu,LIU Hong-wei.Influence of pyrolysis conditions on stability of biochar[J].Environmental Science and Technology,2013,36(8):11-14.
[11]文方园,陈建,田路萍,等.过氧化氢氧化对生物炭表面性质的改变及其对双酚A吸附的影响[J].生态毒理学报,2016,11(2):628-635.WEN Fang-yuan,CEHN Jian,TIAN Lu-ping,et al.Chemical oxidation of biochars and the impact on bisphenol A sorption[J].Asian Journal of Ecotoxicology,2016,11(2):628-635.
[12]申磊,荆延德,鞠文亮,等.施加不同种类生物质炭及冻融交替后土壤吸附Cu(Ⅱ)的变化[J].土壤通报,2017,48(4):975-981.SHEN Lei,JING Yan-de,JU Wen-liang,et al.Changes of soil adsorption of Cu(Ⅱ)after the application of different kinds of biochar and freeze-thawing[J].Chinese Journal of Soil Science,2017,48(4):975-981.
[13]Zhao R,Coles N,Wu J.Carbon mineralization following additions of fresh and aged biochar to an infertile soil[J].Catena,2015,125:183-189.
[14]Li F,Cao X,Zhao L,et al.Effects of mineral additives on biochar formation:Carbon retention,stability,and properties[J].Environmental Science&Technology,2014,48(19):11211-11217.
[15]Woolf D,Amonette J E,Streetperrott F A,et al.Sustainable biochar to mitigate global climate change[J].Nature Communications,2010,1(5):56.
[16]陈温福,张伟明,孟军.生物炭与农业环境研究回顾与展望[J].农业环境科学学报,2014,33(5):821-828.CHEN Wen-fu,ZHANG Wei-ming,MENG Jun.Biochar and agroecological environment:Review and prospect[J].Journal of Agro-Environment Science,2014,33(5):821-828.
[17]顾博文,曹心德,赵玲,等.生物质内源矿物对热解过程及生物炭稳定性的影响[J].农业环境科学学报,2017,36(3):591-597.GU Bo-wen,CAO Xin-de,ZHAO Ling,et al.Influence of inherent minerals on biomass pyrolysis and carbon stability in biochar[J].Journal of Agro-Environment Science,2017,36(3):591-597.
[18]Yang Y,Sun K,Han L,et al.Effect of minerals on the stability of biochar[J].Chemosphere,2018,204:310-317.
[19]Chun Y,Sheng G,Chiou C T,et al.Compositions and sorptive properties of crop residue-derived chars[J].Environmental Science&Technology,2004,38(17):4649-4655.
[20]薛惠琴,杭怡琼,陈谊.稻草秸秆中木质素、纤维素测定方法的研讨[J].上海畜牧兽医通讯,2001(2):15.XUE Hui-qin,HANG Yi-qiong,CHEN Yi.Study on determination methods of lignin and cellulose in wheat straw[J].Shanghai Journal of Animal Husbandry and Veterinary Medicine,2001(2):15.
[21]Brodowski S,Amelung W,Haumaier L,et al.Morphological and chemical properties of black carbon in physical soil fractions as revealed by scanning electron microscopy and energy-dispersive X-ray spectroscopy[J].Geoderma,2005,128(1):116-129.
[22]Fornara D A,Tilman D.Plant functional composition influences rates of soil carbon and nitrogen accumulation[J].Journal of Ecology,2008,96(2):314-322.
[23]王刚,李文,薛钦昭,等.生物质化学组分在空气和合成气下的热重行为研究[J].燃料化学学报,2009,37(2):170-176.WANG Gang,LI Wen,XUE Qin-zhao,et al.Thermogravimetric behaviors of biomass′chemical components under air or syngas[J].Journal of Fuel Chemistry and Technology,2009,37(2):170-176.
[24]Han L,Ro K S,Wang Y,et al.Oxidation resistance of biochars as a function of feedstock and pyrolysis condition[J].Science of the Total Environment,2017,616/617:335-344.
[25]Bavel B V.Comparison of Fenton′s reagent and ozone oxidation of polycyclic aromatic hydrocarbons in aged contaminated soils[J].Journal of Soils&Sediments,2006,6(4):208-214.
[26]Singh B,Singh B P,Cowie A L,et al.Characterisation and evaluation of biochars for their application as a soil amendment[J].Soil Research,2010,48(7):516-525.
[27]徐佳,刘荣厚.不同慢速热裂解工艺条件下棉花秸秆生物炭的理化特性分析[J].上海交通大学学报(农业科学版),2017,35(2):19-24.XU Jia,LIU Rong-hou.Physicochemical properties of cotton stalk biochar under different slow pyrolysis conditions[J].Journal of Shanghai Jiaotong University(Agricultural Science),2017,35(2):19-24.
[28]Chen B,Zhou D,Zhu L.Transitional adsorption and partition of nonpolar and polar aromatic contaminants by biochars of pine needles with different pyrolytic temperatures[J].Environmental Science&Technology,2008,42(14):5137-5143.
[29]Uchimiya M,Lima I M,Klasson K T,et al.Immobilization of heavy metal ions(CuⅡ,CdⅡ,NiⅡ,and PbⅡ)by broiler litter-derived biochars in water and soil[J].Journal of Agricultural and Food Chemistry,2010,58(9):5538-5544.
[30]Chen B,Chen Z.Sorption of naphthalene and 1-naphthol by biochars of orange peels with different pyrolytic temperatures[J].Chemosphere,2009,76(1):127-133.
[31]刘朝霞,牛文娟,楚合营,等.秸秆热解工艺优化与生物炭理化特性分析[J].农业工程学报,2018,34(5):196-203.LIU Zhao-xia,NIU Wen-juan,CHU He-ying,et al.Process optimization for straws pyrolysis and analysis of biochar physiochemical properties[J].Transactions of the Chinese Society of Agricultural Engineering,2018,34(5):196-203.
[32]朱恂,李刚,冯云鹏,等.重庆地区7种生物质的成分分析及热重实验[J].重庆大学学报(自然科学版),2006,29(8):44-48.ZHU Xun,LI Gang,FENG Yun-peng,et al.Thermogravimetric experiments and component analysis of biomass in Chongqing[J].Journal of Chongqing University(Natural Science Edition),2006,29(8):44-48.
[33]Mikutta R,Kleber M,Kaiser K,et al.Review:Organic matter removal from soils using hydrogen peroxide,sodium hypochlorite,and disodium peroxodisulfate[J].Soil Science Society of America Journal,2005,69(1):120-135.
[34]Xiang Q,Lee Y Y.Oxidative cracking of precipitated hardwood lignin by hydrogen peroxide[J].Applied Biochemistry&Biotechnology,2000,84-86(1-9):153-162.
[35]Goldstone J V,Pullin M J,Bertilsson S,et al.Reactions of hydroxyl radical with humic substances:Bleaching,mineralization,and production of bioavailable carbon substrates[J].Environmental Science&Technology,2002,36(3):364-372.
[36]傅晓燕,栾连军,朱炜,等.双氧水降解残留农药效果及对苦参有效成分的影响[J].中国中药杂志,2007,32(20):2098-2102.FU Xiao-yan,LUAN Lian-jun,ZHU Wei,et al.Influence of H2O2 on degradation of residual pesticides and constituents in radix sophorae flavescentis[J].China Journal of Chinese Materia Medica,2007,32(20):2098-2102.
[37]Jin J,Sun K,Wang Z,et al.Effects of chemical oxidation on phenanthrene sorption by grass-and manure-derived biochars[J].Science of the Total Environment,2017,598:789-796.
[38]余伟光,黎吉辉,王敦,等.香蕉茎秆生物炭的制备及其对铜离子的吸附特性[J].化工进展,2017,36(4):1499-1505.YU Wei-guang,LI Ji-hui,WANG Dun,et al.The preparation of biochar from pre-oxidation of banana stem and its adsorption of Cu2+[J].Chemical Industry and Engineering Progress,2017,36(4):1499-1505.
[39]许可,贲伟伟,强志民.高锰酸钾氧化降解水中微量有机污染物的研究进展[J].环境化学,2017,36(1):16-26.XU Ke,BEN Wei-wei,QIANG Zhi-min.Oxidative degradation of micro-organic pollutants by potassium permanganate in water:A review[J].Environmental Chemistry,2017,36(1):16-26.