巯基改性稻壳炭吸附Zn(Ⅱ)的性能
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摘要
[目的]通过稻壳炭表面的—OH和巯基乙酸上的—COOH发生酯化反应,制备成一种新型吸附剂(RD550),去除废水中的锌。[方法]利用改性前、后吸附材料研究溶液的pH值、投加量、反应时间、反应温度以及解吸对吸附效果的影响,并采用扫描电子显微镜(SEM)、傅里叶变换红外光谱仪(FTIR)和X-射线光电子能谱(XPS)等对改性前、后稻壳炭的外貌形态进行表征和官能团分析。[结果]通过SEM图谱、XPS和FTIR图谱可知,巯基已被成功嫁接在稻壳炭上,能够增大稻壳炭孔隙和提高S含量以及对锌的吸附性能。巯基改性稻壳炭吸附Zn(Ⅱ)的适用pH值为6.50,在360 min内达到吸附平衡,且符合拟二级动力学方程。从吸附效率和节约成本的角度考虑,吸附材料用量为0.10 g时,吸附效果最佳。整个吸附过程符合单分子Langmuir吸附模型,巯基改性稻壳炭吸附Zn(Ⅱ)的最大吸附量为68.03 mg·g~(-1),结合解吸试验可知相对于未改性的稻壳炭,巯基改性稻壳炭吸附Zn(Ⅱ)更加牢固,解吸率为2.91%～13.12%。[结论]通过化学改性可把功能基团—SH键合在稻壳炭上,并利用S对重金属的亲和性,可以有效提高吸附剂的吸附性能,对去除废水中的Zn(Ⅱ)具有重要意义。
[Objectives]A new adsorbent( RD550) was prepared by esterification of —OH on rice husk carbon and —COOH on thioglycolic acid to remove zinc from wastewater. [Methods]The effects of pH value,dosage,reaction time,reaction temperature and desorption on the adsorption were studied by using the adsorbent materials before and after modification. The morphology and functional groups of the modified rice husk carbon were characterized by scanning electron microscopy( SEM),fourier transform infrared spectroscopy( FTIR) and X-ray photoelectron spectroscopy( XPS). [Results]The results of SEM,XPS and FTIR showed that the sulfhydryl group had been grafted onto rice husk carbon successfully. The porosity of rice husk charcoal increased,and the content of S also increased,which was beneficial to the adsorption of zinc. The suitable pH for the adsorption of Zn(Ⅱ) by thioglycolated rice husk carbon was 6.50,and the adsorption equilibrium reached within 360 min,which accorded with the pseudo-second-order kinetic equation.From the perspective of adsorption efficiency and cost saving,when the amount of adsorption material was 0.10 g,the adsorption effect was the best. The adsorption process accorded with Langmuir adsorption model. The maximum adsorption capacity of Zn( Ⅱ) on sulfhydryl rice husk carbon was 68.03 mg·g~(-1). Combined with desorption experiment,the adsorption of Zn(Ⅱ) on sulfhydryl rice husk charcoal was stronger than that on unmodified rice husk carbon,and the desorption rate was 2. 91%-13. 12%. [Conclusions]By chemical modification,the functional group —SH can be bonded to rice husk carbon,and the affinity of S to heavy metals can be used to improve the adsorption performance of the adsorbent,which is of great significance for the removal of Zn(Ⅱ) from wastewater.
[Objectives]A new adsorbent( RD550) was prepared by esterification of —OH on rice husk carbon and —COOH on thioglycolic acid to remove zinc from wastewater. [Methods]The effects of pH value,dosage,reaction time,reaction temperature and desorption on the adsorption were studied by using the adsorbent materials before and after modification. The morphology and functional groups of the modified rice husk carbon were characterized by scanning electron microscopy( SEM),fourier transform infrared spectroscopy( FTIR) and X-ray photoelectron spectroscopy( XPS). [Results]The results of SEM,XPS and FTIR showed that the sulfhydryl group had been grafted onto rice husk carbon successfully. The porosity of rice husk charcoal increased,and the content of S also increased,which was beneficial to the adsorption of zinc. The suitable pH for the adsorption of Zn(Ⅱ) by thioglycolated rice husk carbon was 6.50,and the adsorption equilibrium reached within 360 min,which accorded with the pseudo-second-order kinetic equation.From the perspective of adsorption efficiency and cost saving,when the amount of adsorption material was 0.10 g,the adsorption effect was the best. The adsorption process accorded with Langmuir adsorption model. The maximum adsorption capacity of Zn( Ⅱ) on sulfhydryl rice husk carbon was 68.03 mg·g~(-1). Combined with desorption experiment,the adsorption of Zn(Ⅱ) on sulfhydryl rice husk charcoal was stronger than that on unmodified rice husk carbon,and the desorption rate was 2. 91%-13. 12%. [Conclusions]By chemical modification,the functional group —SH can be bonded to rice husk carbon,and the affinity of S to heavy metals can be used to improve the adsorption performance of the adsorbent,which is of great significance for the removal of Zn(Ⅱ) from wastewater.
引文
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[15]陈云嫩,吴叶,刘海兵,等.巯基/羧基改性麦糟吸附水中三价砷的研究[J].有色金属工程,2017,7(4):96-101.Chen Y N,Wu Y,Liu H B,et al. Adsorption of As(Ⅲ)in water by thiol/carboxyl modified spent grain[J]. Nonferrous Metals Engineering,2017,7(4):96-101(in Chinese with English abstract).
[16]邓华,严发,陆志诚,等.巯基改性木薯秸秆对Cd(Ⅱ)吸附性能的研究[J].水处理技术,2018,44(6):57-61.Deng H,Yan F,Lu Z C,et al. Study on the adsorption of Cd(Ⅱ)by sulfydryl modified cassava straw[J]. Technology of Water Treatment,2018,44(6):57-61(in Chinese with English abstract).
[17] Liang X F,Xu Y M,Sun G H,et al. Preparation and characterization of mercapto functionalized sepiolite and their application for sorption of lead and cadmium[J]. Chemical Engineering Journal,2011,174(1):436-444.
[18]王英惠,杨旻,胡林潮,等.不同温度制备的生物质炭对土壤有机碳矿化及腐殖质组成的影响[J].农业环境科学学报,2013,32(8):1585-1591.Wang Y H,Yang M,Hu L C,et al. Effects of biochar amendments synthesized at varying temperatures on soil organic carbon mineralization and humus composition[J]. Journal of Agro-Environment Science,2013,32(8):1585-1591(in Chinese with English abstract).
[19] Arslanoglu H,Altundogan H S,Tumen F. Heavy metals binding properties of esterified lemon[J]. Journal of Hazardous Materials,2009,164(2/3):1406-1413.
[20] Tran L,Wu P X,Zhu Y J,et al. Highly enhanced adsorption for the removal of Hg(Ⅱ)from aqueous solution by Mercaptoethylamine/Mercaptopropyltrimethoxysilane functionalized vermiculites[J]. Journal of Colloid and Interface Science,2015,445:348-356.
[21]秦庆东.功能化介孔材料MCM-41选择性吸附水中污染物的性能研究[D].哈尔滨:哈尔滨工业大学,2009.Qin Q D. Study on selective adsorption of pollutants in water by functionalized mesoporous material MCM-41[D]. Harbin:Harbin University of Technology,2009(in Chinese with English abstract).
[22] Krishnani K,Meng X,Christodoulatos C,et al. Biosorption mechanism of nine different heavy metals onto biomatrix from rice husk[J]. Journal of Hazardous Materials,2008,153(3):1222-1234.
[23] Chang M Y,Juang R S. Adsorption of tannic acid,humic acid,and dyes from water using the composite of chitosan and activated clay[J].Journal of Colloid and Interface Science,2004,278(1):18-25.
[24] Han R P,Zhang L J,Song C,et al. Characterization of modified wheat straw,kinetic and equilibrium study about copper ion and methylene blue adsorption in batch mode[J]. Carbohydrate Polymers,2010,79(4):1140-1149.
[25] Sciban M,Klasnja M,Skrbic B. Modified softwood sawdust as adsorbent of heavy metal ions from water[J]. Journal of Hazardous Materials,2006,136(2):266-271.
[26] Amuda O S,Giwa A A,Bello I A. Removal of heavy metal from industrial wastewater using modified activated coconut shell carbon[J].Biochemical Engineering Journal,2007,36(2):174-181.
[27]李珊珊,冯燕,段莲,等.改性玉米秸秆对重金属吸附性能研究[J].黑龙江畜牧兽医,2017(7):150-153.Li S S,Feng Y,Duan L,et al. Adsorption of heavy metals by modified corn straw[J]. Heilongjiang Animal Science and Veterinary Medicine,2017(7):150-153(in Chinese with English abstract).
[2] Hong K K,Kim Y G. The critical success factors for ERP implementation:an organizational fit perspective[J]. Information and Management,2002,40(1):25-40.
[3] Sharma A,Sharma A,Arya R K. Removal of mercury(Ⅱ)from aqueous solution:a review of recent work[J]. Separation Science and Technology,2015,50(9):1310-1320.
[4]李青竹,覃文庆,柴立元,等.巯基化改性麦糟对Zn(Ⅱ)的吸附特性[J].中国有色金属学报,2014,24(4):1076-1083.Li Q Z,Qin W Q,Chai L Y,et al. Adsorption characteristics of Zn(Ⅱ)on thiol-functionalized spent grain[J]. The Chinese Journal of Nonferrous Metals,2014,24(4):1076-1083(in Chinese with English abstract).
[5] Qin Y C,Guan X H,Yin R,et al. Preliminary research on Cd2+removal from wastewater by Sphaerotilus natans[J]. Chemical Research in Chinese Universities,2005,21(6):654-657.
[6]谢婧如,陈本寿,张进忠,等.巯基改性海泡石吸附水中的Hg(Ⅱ)[J].环境科学,2016,37(6):2188-2194.Xie J R,Chen B S,Zhang J Z,et al. Adsorption of Hg(Ⅱ)in water by sulfydryl-modified sepiolite[J]. Chinese Journal of Environmental Science,2016,37(6):2188-2194(in Chinese with English abstract).
[7] Chinoune K,Bentaleb K,Bouberka Z,et al. Adsorption of reactive dyes from aqueous solution by dirty bentonite[J]. Applied Clay Science,2016,123:64-75.
[8]刘延志,田胜艳,商平,等.蒙脱石吸附Cr3+、Cd2+、Cu2+、Pb2+、Zn2+的研究:p H值和有机酸的影响[J].生态环境,2005,14(3):353-356.Liu Y Z,Tian S Y,Shang P,et al. Adsorption of heavy metals on Na-montmorillonite:effects of p H and organic acid[J]. Ecology and Environment,2005,14(3):353-356(in Chinese with English abstract).
[9]王静,陈光辉,陈建,等.巯基改性活性炭对水溶液中汞的吸附性能研究[J].环境工程学报,2009,3(2):220-222.Wang J,Chen G H,Chen J,et al. Investigation on aqueous Hg(Ⅱ)adsorption properties by thiol-modified activated carbon[J]. Chinese Journal of Environmental Engineering,2009,3(2):220-222(in Chinese with English abstract).
[10]李媛媛,董泳秀,刘文华,等.巯基化膨润土对As3+的吸附解吸性能研究[J].环境保护科学,2015,41(1):104-108.Li Y Y,Dong Y X,Liu W H,et al. Adsorption and desorption properties of thiol-functionalized bentonite towards As3+[J]. Environmental Protection Science,2015,41(1):104-108(in Chinese with English abstract).
[11]吕娟,王明峰,蒋恩臣,等.不同热解温度下稻壳炭的理化特性分析[J].可再生能源,2017,35(10):1488-1453.LüJ,Wang M F,Jiang E C,et al. Physicochemical characteristics of rice husk carbon at different pyrolysis temperatures[J]. Renewable Energy,2017,35(10):1488-1453(in Chinese with English abstract).
[12]许继星,黄维秋,王翊红,等.稻壳基脱硅活性炭的制备及其对油气吸附性能研究[J].化工新型材料,2017,45(9):212-214,217.Xu J X,Huang W Q,Wang Y H,et al. Preparation of activated carbon from the desilication residue of rice husk and adsorption of oil vapor[J].New Chemical Materials,2017,45(9):212-214,217(in Chinese with English abstract).
[13]唐伟,郭悦,吴景贵,等.老化的生物质炭性质变化及对菲吸持的影响[J].环境科学,2014,35(7):2604-2611.Tang W,Guo Y,Wu J G,et al. Structural changes of aged biochar and the influence on phenanthrene adsorption[J]. Chinese Journal of Environmental Science,2014,35(7):2604-2611(in Chinese with English abstract).
[14] Zhang C,Sui J H,Li J,et al. Efficient removal of heavy metal ions by thiol-functionalized superparamagnetic carbon nanotubes[J]. Chemical Engineering Journal,2012,210:45-52.
[15]陈云嫩,吴叶,刘海兵,等.巯基/羧基改性麦糟吸附水中三价砷的研究[J].有色金属工程,2017,7(4):96-101.Chen Y N,Wu Y,Liu H B,et al. Adsorption of As(Ⅲ)in water by thiol/carboxyl modified spent grain[J]. Nonferrous Metals Engineering,2017,7(4):96-101(in Chinese with English abstract).
[16]邓华,严发,陆志诚,等.巯基改性木薯秸秆对Cd(Ⅱ)吸附性能的研究[J].水处理技术,2018,44(6):57-61.Deng H,Yan F,Lu Z C,et al. Study on the adsorption of Cd(Ⅱ)by sulfydryl modified cassava straw[J]. Technology of Water Treatment,2018,44(6):57-61(in Chinese with English abstract).
[17] Liang X F,Xu Y M,Sun G H,et al. Preparation and characterization of mercapto functionalized sepiolite and their application for sorption of lead and cadmium[J]. Chemical Engineering Journal,2011,174(1):436-444.
[18]王英惠,杨旻,胡林潮,等.不同温度制备的生物质炭对土壤有机碳矿化及腐殖质组成的影响[J].农业环境科学学报,2013,32(8):1585-1591.Wang Y H,Yang M,Hu L C,et al. Effects of biochar amendments synthesized at varying temperatures on soil organic carbon mineralization and humus composition[J]. Journal of Agro-Environment Science,2013,32(8):1585-1591(in Chinese with English abstract).
[19] Arslanoglu H,Altundogan H S,Tumen F. Heavy metals binding properties of esterified lemon[J]. Journal of Hazardous Materials,2009,164(2/3):1406-1413.
[20] Tran L,Wu P X,Zhu Y J,et al. Highly enhanced adsorption for the removal of Hg(Ⅱ)from aqueous solution by Mercaptoethylamine/Mercaptopropyltrimethoxysilane functionalized vermiculites[J]. Journal of Colloid and Interface Science,2015,445:348-356.
[21]秦庆东.功能化介孔材料MCM-41选择性吸附水中污染物的性能研究[D].哈尔滨:哈尔滨工业大学,2009.Qin Q D. Study on selective adsorption of pollutants in water by functionalized mesoporous material MCM-41[D]. Harbin:Harbin University of Technology,2009(in Chinese with English abstract).
[22] Krishnani K,Meng X,Christodoulatos C,et al. Biosorption mechanism of nine different heavy metals onto biomatrix from rice husk[J]. Journal of Hazardous Materials,2008,153(3):1222-1234.
[23] Chang M Y,Juang R S. Adsorption of tannic acid,humic acid,and dyes from water using the composite of chitosan and activated clay[J].Journal of Colloid and Interface Science,2004,278(1):18-25.
[24] Han R P,Zhang L J,Song C,et al. Characterization of modified wheat straw,kinetic and equilibrium study about copper ion and methylene blue adsorption in batch mode[J]. Carbohydrate Polymers,2010,79(4):1140-1149.
[25] Sciban M,Klasnja M,Skrbic B. Modified softwood sawdust as adsorbent of heavy metal ions from water[J]. Journal of Hazardous Materials,2006,136(2):266-271.
[26] Amuda O S,Giwa A A,Bello I A. Removal of heavy metal from industrial wastewater using modified activated coconut shell carbon[J].Biochemical Engineering Journal,2007,36(2):174-181.
[27]李珊珊,冯燕,段莲,等.改性玉米秸秆对重金属吸附性能研究[J].黑龙江畜牧兽医,2017(7):150-153.Li S S,Feng Y,Duan L,et al. Adsorption of heavy metals by modified corn straw[J]. Heilongjiang Animal Science and Veterinary Medicine,2017(7):150-153(in Chinese with English abstract).