载锆玉米秸秆生物炭的结构表征及磷吸附效果
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摘要
以玉米秸秆为原料,利用氧氯化锆浸渍-限氧热解法制备一种新型的载锆生物炭阴离子吸附剂.采用场发射扫描电镜(FE-SEM)、傅里叶变换红外光谱(FT-IR)、X射线光电子能谱(XPS)和比表面积测定(BETN2)等手段,对空白生物炭(BC)及载锆生物炭(Zr-BC)的形貌、组成及结构进行表征.结果表明:热解后的生物炭表面形貌粗糙,均发育有裂纹和蜂窝状大孔结构;与BC相比,Zr-BC比表面积和平均孔径都有降低,且表面元素含C量大幅降低,含O量显著增加,Zr质量分数达到15.7%;Zr-BC表面主要官能团有羟基(-OH)、羧基(-COOH)、锆羟基氧化物等,构成吸附性能的结构基础;当pH值为2时,Zr-BC对磷酸盐吸附效果最显著,符合Freundlich等温吸附线模型.通过多种阴离子混合吸附测试发现,Zr-BC对水中磷酸盐有较高吸附量,且选择性较高.
A novel anion adsorbent,zirconium-impregnated biochar(Zr-BC),was prepared from corn stalk by using zirconium oxychloride impregnation-limited oxygen pyrolysis method.Field emission scanning electron microscopy(FE-SEM),Fourier transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),and BET-N_2 specific surface were employed to characterize the surface morphology,element composition and structure of the zirconium-impregnated biochar(Zr-BC)and the blank biochar(BC).The results showed that Zr-BC had rough surface with plenty of cracks and macropore structure,and its specific surface area and medium pore size were both decreased in contrast to BC.Moreover,Zr-BC surface contained much more O and less C element than that of BC,and Zr content reached 15.7%.Major surface functional groups of Zr-BC included hydroxyl(-OH),carboxyl(-COOH),and particularly zirconium oxyhydroxide,underlying the structural basis for anion adsorption.The adsorption of phosphate by Zr-BC was highly dependent on pH value,and the optimum pH value was 2.The equilibrium isotherm data of phosphate on Zr-BC were well fitted to the Freundlich isotherm models.Adsorption experiments with mixed anions solution showed that Zr-BC had a higher adsorption capacity for phosphate and exhibited high selectivity.
A novel anion adsorbent,zirconium-impregnated biochar(Zr-BC),was prepared from corn stalk by using zirconium oxychloride impregnation-limited oxygen pyrolysis method.Field emission scanning electron microscopy(FE-SEM),Fourier transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),and BET-N_2 specific surface were employed to characterize the surface morphology,element composition and structure of the zirconium-impregnated biochar(Zr-BC)and the blank biochar(BC).The results showed that Zr-BC had rough surface with plenty of cracks and macropore structure,and its specific surface area and medium pore size were both decreased in contrast to BC.Moreover,Zr-BC surface contained much more O and less C element than that of BC,and Zr content reached 15.7%.Major surface functional groups of Zr-BC included hydroxyl(-OH),carboxyl(-COOH),and particularly zirconium oxyhydroxide,underlying the structural basis for anion adsorption.The adsorption of phosphate by Zr-BC was highly dependent on pH value,and the optimum pH value was 2.The equilibrium isotherm data of phosphate on Zr-BC were well fitted to the Freundlich isotherm models.Adsorption experiments with mixed anions solution showed that Zr-BC had a higher adsorption capacity for phosphate and exhibited high selectivity.
引文
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[19]薛娟琴,党龙涛,刘瑶,等.锆负载交联壳聚糖树脂的制备及硫酸根吸附性能[J].环境化学,2014,33(9):1553-1557.DOI:10.7524/j.issn.0254-6108.2014.09.004.
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[25]CUI Hang,LI Qi,GAO Shi′an,et al.Strong adsorption of arsenic species by amorphous zirconium oxide nanoparticles[J].Journal of Industrial and Engineering Chemistry,2012,18(4):1418-1427.DOI:10.1016/j.jiec.2012.01.045.
[26]CHEN Pinghua,ZHANG Weibo,LI Menglin,et al.Facile synthesis of magnetic La-Zr composite as high effective adsorbent for fluoride removal[J].Rsc Advances,2016,6(42):35859-35867.DOI:10.1039/C5RA27929A.
[27]梅燕,阎建平,聂祚仁.焙烧条件对Ce离子态影响的XPS研究[J].光谱学与光谱分析,2010,30(1):270-273.DOI:10.3964/j.issn.1000-0593(2010)01-0270-04.
[28]王秀荣.纳米复合材料ZrO2-rGO的制备及其对磷的吸附性能研究[D].武汉:武汉理工大学,2015.
[29]WANG Zhanghong,SHEN Dekui,SHEN Fei,et al.Phosphate adsorption on lanthanum loaded biochar[J].Chemosphere,2016,150:1-7.DOI:10.1016/j.chemosphere.2016.02.004.
[30]LI Guoliang,SHEN Boxiong,LI Fukuan,et al.Elemental mercury removal using biochar pyrolyzed from municipal solid waste[J].Fuel Processing Technology,2015,133:43-50.DOI:10.1016/j.fuproc.2014.12.042.
[31]郑雯婧,林建伟,詹艳慧,等.锆-十六烷基三甲基氯化铵改性活性炭对水中硝酸盐和磷酸盐的吸附特性[J].环境科学,2015(6):2185-2194.DOI:10.13227/j.hjkx.2015.06.036.
[32]HUANG Weiya,LI Dan,LIU Zhaoqing,et al.Kinetics,isotherm,thermodynamic,and adsorption mechanism studies of La(OH)3-modified exfoliated vermiculites as highly efficient phosphate adsorbents[J].Chemical Engineering Journal,2014,236(2):191-201.DOI:10.1016/j.cej.2013.09.077.
[33]王章鸿,郭海艳,沈飞,等.热解条件对生物炭性质和氮、磷吸附性能的影响[J].环境科学学报,2015,35(9):2805-2812.DOI:10.13671/j.hjkxxb.2014.1062.
[34]OHE K,NAGAE Y,NAKAMURA S,et al.Removal of nitrate anion by carbonaceous materials prepared from bamboo and coconut shell[J].Journal of Chemical Engineering of Japan,2003,36(4):511-515.DOI:10.1252/jcej.36.511.
[2]ZHAO Fengliang,YANG Weidong,ZENG Zheng,et al.Nutrient removal efficiency and biomass production of different bioenergy plants in hypereutrophic water[J].Biomass and Bioenergy,2012,42(7):212-218.DOI:10.1016/j.biombioe.2012.04.003.
[3]MA Zuohao,LI Qian,YUE Qinyan,et al.Adsorption removal of ammonium and phosphate from water by fertilizer controlled release agent prepared from wheat straw[J].Chemical Engineering Journal,2011,171(3):1209-1217.DOI:10.1016/j.cej.2011.05.027.
[4]高利伟,马林,张卫峰,等.中国作物秸秆养分资源数量估算及其利用状况[J].农业工程学报,2009,25(7):173-179.DOI:10.3969/j.issn.1002-6819.2009.07.032.
[5]张继义,蒲丽君,李根.秸秆生物碳质吸附剂的制备及其吸附性能[J].农业工程学报,2011,27(增刊2):104-109.DOI:10.3969/j.issn.1002-6819.2011.z2.021.
[6]LEHMANN J,JOSEPH S.Biochar for environmental management:An introduction[M]∥Biochar for environmental management:Science and technology.London:Earthscan Ltd,2009:1-10.
[7]CUI Xiaoqiang,DAI Xi,KHAN K Y,et al.Removal of phosphate from aqueous solution using magnesium-alginate/chitosan modified biochar microspheres derived fromThalia dealbata[J].Bioresource Technology,2016,218:1123-1132.DOI:10.1016/j.biortech.2016.07.072.
[8]CHEN Baoliang,CHEN Zaiming.Sorption of naphthalene and 1-naphthol by biochars of orange peels with different pyrolytic temperatures[J].Chemosphere,2009,76(1):127-133.DOI:10.1016/j.chemosphere.2009.02.004.
[9]UCHIMIYA M,WARTELLE L H,KLASSON K T,et al.Influence of pyrolysis temperature on biochar property and function as a heavy metal sorbent in soil[J].Journal of Agricultural and Food Chemistry,2011,59(6):2501-2510.DOI:10.1021/jf104206c.
[10]HOLLISTER C C,BISOGNI J J,LEHMANN J.Ammonium,nitrate,and phosphate sorption to and solute leaching from biochars prepared from corn stover(Zea mays L.)and oak wood(Quercus spp.)[J].Journal of Environmental Quality,2013,42(1):137-144.DOI:10.2134/jeq2012.0033.
[11]YAO Ying,GAO Bin,ZHANG Ming,et al.Effect of biochar amendment on sorption and leaching of nitrate,ammonium,and phosphate in a sandy soil[J].Chemosphere,2012,89(11):1467-1471.DOI:10.1016/j.chemosphere.2012.06.002.
[12]万霞,梅昌艮,何俐臻,等.磁性生物炭的制备、表征及对磷的吸附特性[J].安全与环境学报,2017,17(3):1069-1075.DOI:10.13637/j.issn.1009-6094.2017.03.050.
[13]GAN Chao,LIU Yunguo,TAN Xiaofei,et al.Effect of porous zinc-biochar nanocomposites on Cr(Ⅵ)adsorption from aqueous solution[J].Rsc Advances,2015,5(44):35107-35115.DOI:10.1039/c5ra04416b.
[14]XUE Lihong,GAO Bin,WAN Yongshan,et al.High efficiency and selectivity of MgFe-LDH modified wheat-straw biochar in the removal of nitrate from aqueous solutions[J].Journal of the Taiwan Institute of Chemical Engineers,2016,63:312-317.DOI:10.1016/j.jtice.2016.03.021.
[15]LIU Honglei,SUN Xiaofei,YIN Chengqing,et al.Removal of phosphate by mesoporous ZrO2[J].Journal of Hazardous Materials,2008,151(2):616-622.DOI:10.1016/j.jhazmat.2007.06.033.
[16]CHITRAKAR R,TEZUKA S,SONODA A,et al.Selective adsorption of phosphate from seawater and wastewater by amorphous zirconium hydroxide[J].Journal of Colloid and Interface Science,2006,297(2):426-433.DOI:10.1016/j.jcis.2005.11.011.
[17]林建伟,詹艳慧,陆霞.锆改性沸石对水中磷酸盐和铵的吸附特性[J].中国环境科学,2012,32(11):2023-2031.DOI:10.3969/j.issn.1000-6923.2012.11.015.
[18]YU Zhichao,XU Chonghe,YUAN Kangkang,et al.Characterization and adsorption mechanism of ZrO2 mesoporous fibers for health-hazardous fluoride removal[J].Journal of Hazardous Materials,2017,346:82-92.DOI:10.1016/j.jhazmat.2017.12.024.
[19]薛娟琴,党龙涛,刘瑶,等.锆负载交联壳聚糖树脂的制备及硫酸根吸附性能[J].环境化学,2014,33(9):1553-1557.DOI:10.7524/j.issn.0254-6108.2014.09.004.
[20]KEILUWEIT M,NICO P S,JOHNSON M G,et al.Dynamic molecular structure of plant biomass-derived black carbon(biochar)[J].Environmental Science and Technology,2010,44(4):1247-1253.DOI:10.1021/es9031419.
[21]谢奕明,吴季怀.膨润土/聚丙烯酸钠超吸水性复合材料的表征[J].华侨大学学报(自然科学版),2007,28(3):282-286.DOI:10.3969/j.issn.1000-5013.2007.03.016.
[22]CHEN Baoliang,ZHOU Dandan,ZHU Lizhong.Tansitional adsorption and partition of nonpolar and polar aromatic contaminants by biochars of pine needles with different pyrolytic temperatures[J].Environmental Science and Technology,2008,42(14):5137-5143.DOI:10.1021/es8002684.
[23]ZIMEN D,ERSOY-MERIBOYU A.Characterization of biochar and bio-oil samples obtained from carbonization of various biomass materials[J].Renewable Energy,2010,35(6):1319-1324.DOI:10.1016/j.renene.2009.11.042.
[24]俞花美,陈淼,邓惠,等.蔗渣基生物炭的制备、表征及吸附性能[J].热带作物学报,2014,35(3):595-602.DOI:10.3969/j.issn.1000-2561.2014.03.029.
[25]CUI Hang,LI Qi,GAO Shi′an,et al.Strong adsorption of arsenic species by amorphous zirconium oxide nanoparticles[J].Journal of Industrial and Engineering Chemistry,2012,18(4):1418-1427.DOI:10.1016/j.jiec.2012.01.045.
[26]CHEN Pinghua,ZHANG Weibo,LI Menglin,et al.Facile synthesis of magnetic La-Zr composite as high effective adsorbent for fluoride removal[J].Rsc Advances,2016,6(42):35859-35867.DOI:10.1039/C5RA27929A.
[27]梅燕,阎建平,聂祚仁.焙烧条件对Ce离子态影响的XPS研究[J].光谱学与光谱分析,2010,30(1):270-273.DOI:10.3964/j.issn.1000-0593(2010)01-0270-04.
[28]王秀荣.纳米复合材料ZrO2-rGO的制备及其对磷的吸附性能研究[D].武汉:武汉理工大学,2015.
[29]WANG Zhanghong,SHEN Dekui,SHEN Fei,et al.Phosphate adsorption on lanthanum loaded biochar[J].Chemosphere,2016,150:1-7.DOI:10.1016/j.chemosphere.2016.02.004.
[30]LI Guoliang,SHEN Boxiong,LI Fukuan,et al.Elemental mercury removal using biochar pyrolyzed from municipal solid waste[J].Fuel Processing Technology,2015,133:43-50.DOI:10.1016/j.fuproc.2014.12.042.
[31]郑雯婧,林建伟,詹艳慧,等.锆-十六烷基三甲基氯化铵改性活性炭对水中硝酸盐和磷酸盐的吸附特性[J].环境科学,2015(6):2185-2194.DOI:10.13227/j.hjkx.2015.06.036.
[32]HUANG Weiya,LI Dan,LIU Zhaoqing,et al.Kinetics,isotherm,thermodynamic,and adsorption mechanism studies of La(OH)3-modified exfoliated vermiculites as highly efficient phosphate adsorbents[J].Chemical Engineering Journal,2014,236(2):191-201.DOI:10.1016/j.cej.2013.09.077.
[33]王章鸿,郭海艳,沈飞,等.热解条件对生物炭性质和氮、磷吸附性能的影响[J].环境科学学报,2015,35(9):2805-2812.DOI:10.13671/j.hjkxxb.2014.1062.
[34]OHE K,NAGAE Y,NAKAMURA S,et al.Removal of nitrate anion by carbonaceous materials prepared from bamboo and coconut shell[J].Journal of Chemical Engineering of Japan,2003,36(4):511-515.DOI:10.1252/jcej.36.511.