改性透辉石对饮用水中余氯的吸附机理
|
摘要
将透辉石和碳酸钙在高温下反应活化,对透辉石进行改性,探讨了改性透辉石对余氯的吸附性能。利用X射线衍射(XRD)、扫描电镜(SEM)和X射线光电子能谱(XPS)对吸附前后的改性透辉石进行表征。考察了此吸附过程的吸附平衡、动力学和热力学。实验结果表明,吸附后的残渣XRD图谱出现了带羟基的Ca_4(Si_3O_9)(OH)_2,吸附前后的SEM图表面发生明显变化,吸附残渣的XPS图中有+1价的Cl。Freundlich和Langmuir方程都呈现良好的拟合度,改性透辉石的单分子层最大吸附量是6.974 mg·g-1,热力学平衡方程计算的ΔG0<0,ΔS0>0,说明吸附是自发进行的、熵增反应;从293 K至303 K时ΔH0值为3.43 k J·mol-1,该阶段的吸附反应是吸热的;温度303 K至313 K阶段,ΔH0值为-9.00 k J·mol-1,吸附反应是放热的。对余氯的吸附机理是斜方硅钙石Ca_4(Si_3O_9)(OH)_2的羟基和Cl O-发生交换作用。
Modified diopside was prepared by activating diopside and Ca CO3 at high temperatures. The adsorption capacity of residual chlorine onto adsorbents was discussed. The modified diopside before and after adsorption was characterized by X-ray diffraction( XRD),scanning electron microscopy( SEM),and X-ray photoelectron spectroscopy( XPS). The equilibrium adsorption,kinetic parameters,and thermodynamics of this adsorption were evaluated in detail. The results were as follows: kilchoanite appeared in the XRD patterns of the adsorption residues,the surface of the modified diopside before and after adsorption changed obviously,and Cl Owas observed in the XPS of the adsorption residues. The equilibrium data showed a preferable correlation to both the Freundlich and Langmuir isotherm models,and the maximum monolayer adsorption capacity was 6. 974 mg·g- 1. Thermodynamic analysis indicated that the sorption process was spontaneous and caused entropy generation.From 293 to 303 K,the ΔH0= 3. 43 k J·mol- 1,making the process endothermic; on the other hand,from 303 to 313 K,the ΔH0=- 9. 00 k J·mol- 1,making this process exothermic. The adsorption mechanism of residual chlorine is the exchange between the hydroxyl of kilchoanite and Cl O-.
Modified diopside was prepared by activating diopside and Ca CO3 at high temperatures. The adsorption capacity of residual chlorine onto adsorbents was discussed. The modified diopside before and after adsorption was characterized by X-ray diffraction( XRD),scanning electron microscopy( SEM),and X-ray photoelectron spectroscopy( XPS). The equilibrium adsorption,kinetic parameters,and thermodynamics of this adsorption were evaluated in detail. The results were as follows: kilchoanite appeared in the XRD patterns of the adsorption residues,the surface of the modified diopside before and after adsorption changed obviously,and Cl Owas observed in the XPS of the adsorption residues. The equilibrium data showed a preferable correlation to both the Freundlich and Langmuir isotherm models,and the maximum monolayer adsorption capacity was 6. 974 mg·g- 1. Thermodynamic analysis indicated that the sorption process was spontaneous and caused entropy generation.From 293 to 303 K,the ΔH0= 3. 43 k J·mol- 1,making the process endothermic; on the other hand,from 303 to 313 K,the ΔH0=- 9. 00 k J·mol- 1,making this process exothermic. The adsorption mechanism of residual chlorine is the exchange between the hydroxyl of kilchoanite and Cl O-.
引文
[1]SADIQ R,RODRIGUEZ M J.Disinfection by-products(DBPs)in drinking water and predictive models for their occurrence:A review[J].Science of the Total Environment,2004,321(1/2/3):21-46
[2]GOPAL K,TRIPATHY S S,BERSILLON J L,et al.Chlorination byproducts,their toxicodynamics and removal from drinking water[J].Journal of Hazardous Materials,2007,140(1/2):1-6
[3]叶卿萍,桂芳.氯化消毒副产物的形成及转化过程研究进展[J].甘肃科技,2010,26(22):94-97
[4]NIEUWENHUIJSEN M J,TOLEDANO M B,EATON N E,et al.Chlorination disinfection byproducts in water and their association with adverse reproductive outcomes:A review[J].Occupational and Environmental Medicine,2000,57(2):73-85
[5]KEEGAN T,WHITAKER H,NIEUWENHUIJSEN M J,et al.Use of routinely collected data on trihalomethane in drinking water for epidemiological purposes[J].Occupational and Environmental Medicine,2001,58(7):447-452
[6]MORRIS R D,AUDET A M,ANGELILLO I F,et al.Chlorination,chlorination by-products,and cancer:A meta-analysis[J].American Journal of Public Health,1992,82(7):955-963
[7]SUIDAN M T,KIM B R,SNOEYINK V L.Reduction of free and combined chlorine with granular activated carbon[C]//SUFFET I H,MCGUIRE M J.Activated Carbon Adsorption of Organics From the Aqueous Phase[J].Ann Arbor:Ann Arbor Science,1980:397-424
[8]黄建东,王小平.水质有机物污染与余氯处理的研究[J].山西电力技术,1998,78(1):28-32,46
[9]张怀旭,刘婉冬,李冰璟,等.活性炭去除水中余氯的研究[J].环境污染与防治,2008,30(5):63-68
[10]曹瑞钰.氯消毒机理、危害及脱氯[J].中国给水排水,1995,11(4):36-39
[11]HESKETT D E.Method of treating fluids:US,4642192[P].1987-10-02
[12]张寿恺,邱梅.应用KDF55过滤介质从水中除氯[J].给水排水,2001,27(8):37-38
[13]马红娜.改性树脂制备及其去除饮用供水中余氯机理与工艺研究[D].西安:长安大学,2005
[14]李宇亮,刘建,石旭东,等.载铁(Fe2+)螯合树脂的制备及其去除水中余氯的研究[J].应用化工,2010,39(1):1-3
[15]ITO M,MORIOKA M.Growth of diopside(Ca Mg Si2O6)single crystal by the Czochralski technique[J].Geochemical Journal,2006,40(6):625-629
[16]赵珊茸,边秋娟,凌其聪.结晶学及矿物学[M].北京:高等教育出版社,2004
[17]耿谦.从透辉石的结构特征探析其在陶瓷中的应用[J].江苏陶瓷,2002,35(4):8-10
[18]徐晓军,方和平,高卫勇.硅灰石和透辉石表面化学特性及浮选分离研究[J].有色金属,1995,47(4):43-48
[19]WARREN B,BRAGG W L.XII.The structure of diopside,Ca Mg(Si O3)2[J].Zeitschrift für Kristallographie-Crystalline Materials,1929,69(1/2/3/4/5/6):168-193
[20]CARTER S,PONTON C B,RAWLINGS R D,et al.Microstructure,chemistry,elastic properties and internal friction of silceram glass-ceramics[J].Journal of Materials Science,1988,23(7):2622-2630
[21]WISNIEWSKI W,OTTO K,RSSEL C.Oriented nucleation of diopside crystals in glass[J].Crystal Growth&Design,2012,12(10):5035-5041
[22]KARNIS A,GAUTRON L.Promising immobilization of cadmium and lead inside Ca-rich glass-ceramics[J].International Journal of Civil and Environmental Engineering,2009,3(4):100-103
[23]DONALD I W,METCALFE B L,TAYLOR R N J.The immobilization of high level radioactive wastes using ceramics and glasses[J].Journal of Materials Science,1997,32(22):5851-5887
[24]GOEL A,TULYAGANOV D U,PASCUAL M J,et al.Development and performance of diopside based glass-ceramic sealants for solid oxide fuel cells[J].Journal of Non-Crystalline Solids,2010,356(20/21/22):1070-1080
[25]方燕,陈翠.次氯酸钠溶液标定要点分析[J].工程质量,2014,32(7):69-70
[26]中华人民共和国卫生部,中国国家标准化管理委员会.GB/T 5750.11-2006生活饮用水标准检验方法消毒剂指标[S].北京:中国标准出版社,2007
[27]张吉喆,张倩.DPD分光光度法测定水质中余氯的方法研究[J].黑龙江环境通报,2014,38(1):29-31
[28]ONUMA K,YAMAMOTO M.Crystallization in the silica-undersaturated portion of the system diopside-nepheline-akermanitesilica and its bearing on the formation of melilitites and nephelinites[J].Journal of the Faculty of Science,Hokkaido University.Series 4,Geology and Mineralogy,1976,17(2):347-355
[29]BERNARDO E,CARLOTTI J F,DIAS P M,et al.Novel akermanite-based bioceramics from preceramic polymers and oxide fillers[J].Ceramics International,2014,40(1):1029-1035
[30]FJELLVEG H,KAREN P,KJEKSHUS A,et al.Carbonatization of YBa2Cu3O6+x[J].Acta Chemica Scandinavica A,1988,42:178-184
[31]ONUMA K,YAGI K.The system diopside-akermanite-nepheline[J].The American Mineralogist,1967,52:227-243
[32]HUANG Ruihua,YANG Bingchao,LIU Qian,et al.Removal of fluoride ions from aqueous solutions using protonated crosslinked chitosan particles[J].Journal of Fluorine Chemistry,2012,141:29-34
[33]KONDO S,ISHIKAWA T,ABE I.Adsorption Science[J].Beijing:Chemical Industry,2005:84-85
[34]LANGMUIR I.The constitution and fundamental properties of solids and liquids[J].Part I.Solids.Journal of the American Chemical Society,1916,38(11):2221-2295
[35]FREUNDLICH H M F.Over the adsorption in solution[J].Journal of Physical Chemistry,1906,57(385):385-470
[36]YOON S,MOON J,BAE S,et al.Chloride adsorption by calcined layered double hydroxides in hardened Portland cement paste[J].Materials Chemistry and Physics,2014,145(3):376-386
[37]PERRIN J.Brownian Movement and Molecular Reality[M].Mineola,New York:Dover Publications,2013
[38]VON OEPEN B,KORDEL W,KLEIN W.Sorption of nonpolar and polar compounds to soils:Processes,measurements and experience with the applicability of the modified OECD-guideline 106[J].Chemosphere,1991,22(3/4):285-304
[39]汤宣林.改性硅酸盐水泥对水中氟化物的吸附特性研究[D].北京:中国地质大学(北京),2013
[40]INCILI G K,AYCIK G A.Adsorption thermodynamic and desorption studies of U(VI)on modified silica gel(Si APMS-HL)[J].Journal of Radioanalytical and Nuclear Chemistry,2014,302(1):79-85
[2]GOPAL K,TRIPATHY S S,BERSILLON J L,et al.Chlorination byproducts,their toxicodynamics and removal from drinking water[J].Journal of Hazardous Materials,2007,140(1/2):1-6
[3]叶卿萍,桂芳.氯化消毒副产物的形成及转化过程研究进展[J].甘肃科技,2010,26(22):94-97
[4]NIEUWENHUIJSEN M J,TOLEDANO M B,EATON N E,et al.Chlorination disinfection byproducts in water and their association with adverse reproductive outcomes:A review[J].Occupational and Environmental Medicine,2000,57(2):73-85
[5]KEEGAN T,WHITAKER H,NIEUWENHUIJSEN M J,et al.Use of routinely collected data on trihalomethane in drinking water for epidemiological purposes[J].Occupational and Environmental Medicine,2001,58(7):447-452
[6]MORRIS R D,AUDET A M,ANGELILLO I F,et al.Chlorination,chlorination by-products,and cancer:A meta-analysis[J].American Journal of Public Health,1992,82(7):955-963
[7]SUIDAN M T,KIM B R,SNOEYINK V L.Reduction of free and combined chlorine with granular activated carbon[C]//SUFFET I H,MCGUIRE M J.Activated Carbon Adsorption of Organics From the Aqueous Phase[J].Ann Arbor:Ann Arbor Science,1980:397-424
[8]黄建东,王小平.水质有机物污染与余氯处理的研究[J].山西电力技术,1998,78(1):28-32,46
[9]张怀旭,刘婉冬,李冰璟,等.活性炭去除水中余氯的研究[J].环境污染与防治,2008,30(5):63-68
[10]曹瑞钰.氯消毒机理、危害及脱氯[J].中国给水排水,1995,11(4):36-39
[11]HESKETT D E.Method of treating fluids:US,4642192[P].1987-10-02
[12]张寿恺,邱梅.应用KDF55过滤介质从水中除氯[J].给水排水,2001,27(8):37-38
[13]马红娜.改性树脂制备及其去除饮用供水中余氯机理与工艺研究[D].西安:长安大学,2005
[14]李宇亮,刘建,石旭东,等.载铁(Fe2+)螯合树脂的制备及其去除水中余氯的研究[J].应用化工,2010,39(1):1-3
[15]ITO M,MORIOKA M.Growth of diopside(Ca Mg Si2O6)single crystal by the Czochralski technique[J].Geochemical Journal,2006,40(6):625-629
[16]赵珊茸,边秋娟,凌其聪.结晶学及矿物学[M].北京:高等教育出版社,2004
[17]耿谦.从透辉石的结构特征探析其在陶瓷中的应用[J].江苏陶瓷,2002,35(4):8-10
[18]徐晓军,方和平,高卫勇.硅灰石和透辉石表面化学特性及浮选分离研究[J].有色金属,1995,47(4):43-48
[19]WARREN B,BRAGG W L.XII.The structure of diopside,Ca Mg(Si O3)2[J].Zeitschrift für Kristallographie-Crystalline Materials,1929,69(1/2/3/4/5/6):168-193
[20]CARTER S,PONTON C B,RAWLINGS R D,et al.Microstructure,chemistry,elastic properties and internal friction of silceram glass-ceramics[J].Journal of Materials Science,1988,23(7):2622-2630
[21]WISNIEWSKI W,OTTO K,RSSEL C.Oriented nucleation of diopside crystals in glass[J].Crystal Growth&Design,2012,12(10):5035-5041
[22]KARNIS A,GAUTRON L.Promising immobilization of cadmium and lead inside Ca-rich glass-ceramics[J].International Journal of Civil and Environmental Engineering,2009,3(4):100-103
[23]DONALD I W,METCALFE B L,TAYLOR R N J.The immobilization of high level radioactive wastes using ceramics and glasses[J].Journal of Materials Science,1997,32(22):5851-5887
[24]GOEL A,TULYAGANOV D U,PASCUAL M J,et al.Development and performance of diopside based glass-ceramic sealants for solid oxide fuel cells[J].Journal of Non-Crystalline Solids,2010,356(20/21/22):1070-1080
[25]方燕,陈翠.次氯酸钠溶液标定要点分析[J].工程质量,2014,32(7):69-70
[26]中华人民共和国卫生部,中国国家标准化管理委员会.GB/T 5750.11-2006生活饮用水标准检验方法消毒剂指标[S].北京:中国标准出版社,2007
[27]张吉喆,张倩.DPD分光光度法测定水质中余氯的方法研究[J].黑龙江环境通报,2014,38(1):29-31
[28]ONUMA K,YAMAMOTO M.Crystallization in the silica-undersaturated portion of the system diopside-nepheline-akermanitesilica and its bearing on the formation of melilitites and nephelinites[J].Journal of the Faculty of Science,Hokkaido University.Series 4,Geology and Mineralogy,1976,17(2):347-355
[29]BERNARDO E,CARLOTTI J F,DIAS P M,et al.Novel akermanite-based bioceramics from preceramic polymers and oxide fillers[J].Ceramics International,2014,40(1):1029-1035
[30]FJELLVEG H,KAREN P,KJEKSHUS A,et al.Carbonatization of YBa2Cu3O6+x[J].Acta Chemica Scandinavica A,1988,42:178-184
[31]ONUMA K,YAGI K.The system diopside-akermanite-nepheline[J].The American Mineralogist,1967,52:227-243
[32]HUANG Ruihua,YANG Bingchao,LIU Qian,et al.Removal of fluoride ions from aqueous solutions using protonated crosslinked chitosan particles[J].Journal of Fluorine Chemistry,2012,141:29-34
[33]KONDO S,ISHIKAWA T,ABE I.Adsorption Science[J].Beijing:Chemical Industry,2005:84-85
[34]LANGMUIR I.The constitution and fundamental properties of solids and liquids[J].Part I.Solids.Journal of the American Chemical Society,1916,38(11):2221-2295
[35]FREUNDLICH H M F.Over the adsorption in solution[J].Journal of Physical Chemistry,1906,57(385):385-470
[36]YOON S,MOON J,BAE S,et al.Chloride adsorption by calcined layered double hydroxides in hardened Portland cement paste[J].Materials Chemistry and Physics,2014,145(3):376-386
[37]PERRIN J.Brownian Movement and Molecular Reality[M].Mineola,New York:Dover Publications,2013
[38]VON OEPEN B,KORDEL W,KLEIN W.Sorption of nonpolar and polar compounds to soils:Processes,measurements and experience with the applicability of the modified OECD-guideline 106[J].Chemosphere,1991,22(3/4):285-304
[39]汤宣林.改性硅酸盐水泥对水中氟化物的吸附特性研究[D].北京:中国地质大学(北京),2013
[40]INCILI G K,AYCIK G A.Adsorption thermodynamic and desorption studies of U(VI)on modified silica gel(Si APMS-HL)[J].Journal of Radioanalytical and Nuclear Chemistry,2014,302(1):79-85