镁-钙羟基磷灰石吸附剂对水中Pb~(2+)的去除
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摘要
选择Mg2+为掺杂离子,通过溶胶-凝胶法制备了不同比例的镁-钙羟基磷灰石吸附剂,研究其对水溶液中Pb~(2+)的去除特性和过程机制.结果表明,吸附剂表面以羟基磷铅矿化合物[Pb10(PO4)6(OH)2]为主,其晶体结构由短棒状转变为针状结构;在温度25℃,p H为5时,镁-钙羟基磷灰石吸附Pb~(2+)在720 min内达到平衡,吸附剂的最佳投加量为0. 6 g·L-1,最大吸附量为813. 17 mg·g-1;热力学实验结果:ΔGθ<0、ΔSθ> 0和ΔHθ> 0,表明镁-钙羟基磷灰石吸附Pb~(2+)的过程是自发的吸热、熵增的过程,升温有利于吸附;吸附过程符合伪二级动力学方程,Langmuir吸附模型能更好地描述等温吸附行为;材料表征与吸附实验分析表明,表面络合与溶解-沉淀是镁-钙羟基磷灰石去除Pb~(2+)的主要机制.
A novel magnesium-calcium hydroxyapatite adsorbent was prepared by the Sol-gel method with different proportions of Mg/( Ca + Mg) using Mg2 +as doped ions,and the removal characteristics and process mechanism of Pb~(2+)on the magnesium-calcium hydroxyapatite in an aqueous solutions were studied. The results show that the surface of the adsorbent is composed mainly of a hydroxyphosphonite compound [Pb10( PO4)6( OH)2],The morphological characteristics of the magnesium-calcium hydroxyapatite adsorbent surface was investigated as crystal structure changes from short rods to needle structures according to scanning electron microscopy( SEM). Testing at a temperature of 25℃ and p H of 5 showed that the adsorption of Pb~(2+)by magnesium-calcium hydroxyapatite reached equilibrium within 720 min. The adsorption capacity was determined to be 813. 17 mg·g-1 at a dosage of 0. 6 g·L-1. The thermodynamic test results of ΔGθ< 0,ΔSθ> 0,and ΔHθ> 0 indicated that the adsorption process of Pb~(2+)by magnesiumcalcium hydroxyapatite is a spontaneous process with endothermic reaction and entropy increments,and higher temperatures were considered be favorable for adsorption at a range of 25-45℃. The adsorption could be effectively described by a pseudo-second-order kinetic equation. The equilibrium data were found to follow the Langmuir adsorption model. Material characterization and adsorption tests showed that surface complexation and dissolution-precipitation were the main mechanisms for the removal of Pb~(2+)by magnesiumcalcium hydroxyapatite in an aqueous solution.
A novel magnesium-calcium hydroxyapatite adsorbent was prepared by the Sol-gel method with different proportions of Mg/( Ca + Mg) using Mg2 +as doped ions,and the removal characteristics and process mechanism of Pb~(2+)on the magnesium-calcium hydroxyapatite in an aqueous solutions were studied. The results show that the surface of the adsorbent is composed mainly of a hydroxyphosphonite compound [Pb10( PO4)6( OH)2],The morphological characteristics of the magnesium-calcium hydroxyapatite adsorbent surface was investigated as crystal structure changes from short rods to needle structures according to scanning electron microscopy( SEM). Testing at a temperature of 25℃ and p H of 5 showed that the adsorption of Pb~(2+)by magnesium-calcium hydroxyapatite reached equilibrium within 720 min. The adsorption capacity was determined to be 813. 17 mg·g-1 at a dosage of 0. 6 g·L-1. The thermodynamic test results of ΔGθ< 0,ΔSθ> 0,and ΔHθ> 0 indicated that the adsorption process of Pb~(2+)by magnesiumcalcium hydroxyapatite is a spontaneous process with endothermic reaction and entropy increments,and higher temperatures were considered be favorable for adsorption at a range of 25-45℃. The adsorption could be effectively described by a pseudo-second-order kinetic equation. The equilibrium data were found to follow the Langmuir adsorption model. Material characterization and adsorption tests showed that surface complexation and dissolution-precipitation were the main mechanisms for the removal of Pb~(2+)by magnesiumcalcium hydroxyapatite in an aqueous solution.
引文
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[9]唐振平,毕玉玺,刘迎九,等.氧化石墨烯/有机改性膨润土复合材料的制备及其对Cd(Ⅱ)的吸附[J].复合材料学报,2018,35(11):3196-3204.Tang Z P,Bi Y X,Liu Y J,et al. Preparation of graphene oxide/organo-modified bentonite composites and their adsorption on Cd(Ⅱ)[J]. Acta Materiae Compositae Sinica,2018,35(11):3196-3204.
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[11]张金利,张林林.重金属Pb(Ⅱ)在黏土上吸附特性研究[J].岩土工程学报,2012,34(9):1584-1589.Zhang J L,Zhang L L. Adsorption behaviors of heavy metal Pb(II)on clay[J]. Chinese Journal of Geotechnical Engineering,2012,34(9):1584-1589.
[12] Zhu R H,Yu R B,Yao J X,et al. Removal of Cd2+from aqueous solutions by hydroxyapatite[J]. Catalysis Today,2008,139(1-2):94-99.
[13] Mousa S M,Ammar N S,Ibrahim H A. Removal of lead ions using hydroxyapatite nano-material prepared from phosphogypsum waste[J]. Journal of Saudi Chemical Society,2016,20(3):357-365.
[14]李超,朱宗强,曹爽,等.桉树遗态结构HAP/C复合材料对水中Cu(Ⅱ)的吸附特征[J].环境科学,2017,38(3):1074-1083.Li C,Zhu Z Q,Cao S,et al. Adsorption characteristics of copper in water by the porous biomorph-genetic composite of HAP/C with eucalyptus wood template[J]. Environmental Science,2017,38(3):1074-1083.
[15]刘伟,杨琦,李博,等.磁性石墨烯吸附水中Cr(Ⅵ)研究[J].环境科学,2015,36(2):537-544.Liu W,Yang Q,Li B,et al. Adsorption of Cr(Ⅵ)on magnetic graphene from aqueous solution[J]. Environmental Science,2015,36(2):537-544.
[16]魏建文,韦真周,廖雷,等.氨基修饰介孔分子筛SBA-15对水中Pb2+吸附性能[J].环境工程学报,2014,8(5):1825-1830.Wei J W,Wei Z Z,Liao L,et al. Aqueous Pb(Ⅱ)removal by adsorption on amine-functionalized mesoporous silica SBA-15[J]. Chinese Journal of Environmental Engineering,2014,8(5):1825-1830.
[17] Huang R H,Wang B,Yang B C,et al. Equilibrium,kinetic and thermodynamic studies of adsorption of Cd(II)from aqueous solution onto HACC-bentonite[J]. Desalination,2011,280(1-3):297-304.
[18] Ren Y M,Li N,Feng J,et al. Adsorption of Pb(II)and Cu(II)from aqueous solution on magnetic porous ferrospinel MnFe2O4[J]. Journal of Colloid And Interface Science,2012,367(1):415-421.
[19] Alshameri A,Yan C J,Al-Ani Y,et al. An investigation into the adsorption removal of ammonium by salt activated Chinese(Hulaodu)natural zeolite:kinetics, isotherms, and thermodynamics[J]. Journal of the Taiwan Institute of Chemical Engineers,2014,45(2):554-564.
[20] Koodyńska D,Wntrzak R,Leahy J J,et al. Kinetic and adsorptive characterization of biochar in metal ions removal[J].Chemical Engineering Journal,2012,197:295-305.
[21] Dong L J,Zhu Z L,Qiu Y L,et al. Removal of lead from aqueous solution by hydroxyapatite/magnetite composite adsorbent[J]. Chemical Engineering Journal,2010,165(3):827-834.
[22] Dong L J,Zhu Z L,Qiu Y L,et al. Removal of lead from aqueous solution by hydroxyapatite/manganese dioxide composite[J]. Frontiers of Environmental Science&Engineering,2016,10(1):28-36.
[23]岳燕丽,褚伟伟,卢真真,等.绣球花状掺锶碳羟基磷灰石对Pb2+的吸附[J].环境化学,2017,36(5):1131-1139.Yue Y L,Chu W W,Lu Z Z,et al. Study on Pb2+adsorption by hydrangea-like strontium-doped carbonate hydroxyapatite[J].Environmental Chemistry,2017,36(5):1131-1139.
[24]唐文清,冯泳兰,李小明.掺硅碳羟基磷灰石的制备及其对Pb2+的吸附性能[J].中国环境科学,2013,33(6):1017-1024.Tang W Q,Feng Y L,Li X M. Adsorption characteristics of Pb2+from aqueous solution and synthetic silicon-substituted carbonate hydroxyapatite particles[J]. China Environmental Science,2013,33(6):1017-1024.
[25] Pham Minh D,Tran N D,Nzihou A,et al. Hydroxyapatite gel for the improved removal of Pb2+ions from aqueous solution[J].Chemical Engineering Journal,2013,232:128-138.
[26]杨慧慧,张浩,黄传军,等.磁性羟基磷灰石的制备及其Pb(Ⅱ)吸附性能[J].材料研究学报,2012,26(6):621-626.Yang H H,Zhang H,Huang C J,et al. Fabrication and Pb(Ⅱ)adsorption properties magnetic hydroxyapatite[J]. Chinese Journal of Materials Research,2012,26(6):621-626.
[27]王建新.掺杂羟基磷灰石的合成及其结构与吸附性能的表征[D].北京:中国地质大学(北京),2014.Wang J X. Synthesis and Characterization of the structure and adsorption properties of doped hydroxyapatite[D]. Beijing:China University of Geosciences(Beijing),2014.
[28] Roh H,Yu M R,Yakkala K,et al. Removal studies of Cd(Ⅱ)and explosive compounds using buffalo weed biochar-alginate beads[J]. Journal of Industrial and Engineering Chemistry,2015,26:226-233.
[29]胥焕岩,刘羽,彭明生.羟基磷灰石的除铅行为及作用机理研究[J].矿物岩石地球化学通报,2007,26(S1):128-130.
[30] Ma Q Y, Traina S J, Logan T J, et al. In situ lead immobilization by apatite[J]. Environmental Science&Technology,1993,27(9):1803-1810.
[31] Xu Y P,Schwartz F W. Lead immobilization by hydroxyapatite in aqueous solutions[J]. Journal of Contaminant Hydrology,1994,15(3):187-206.
[32] Mavropoulos E,Rossi A M,Costa A M,et al. Studies on the mechanisms of lead immobilization by hydroxyapatite[J].Environmental Science&Technology,2002,36(7):1625-1629.
[33] Sttzel C,Müller F A,Reinert F,et al. Ion adsorption behaviour of hydroxyapatite with different crystallinities[J]. Colloids and Surfaces B:Biointerfaces,2009,74(1):91-95.
[34] Smiˇc iklas I,Dimovi'c S,Ple'c aI,et al. Removal of Co2+from aqueous solutions by hydroxyapatite[J]. Water Research,2006,40(12):2267-2274.
[2]李坤权,郑正,蒋剑春,等.铅在棉秆基活性炭上的吸附动力学与热力学[J].环境科学,2010,31(5):1402-1408.Li K Q,Zheng Z,Jiang J C,et al. Adsorption kinetic and thermodynamic studies of lead onto activated carbons from cotton stalk[J]. Environmental Science,2010,31(5):1402-1408.
[3]王智勇.羟基磷灰石微球的可控制备及其吸附Pb2+性能的研究[D].武汉:武汉科技大学,2016.Wang Z Y. Study on the controllable preparation of hydroxyapatite microspheres and their adsorption properties for Pb2+[D]. Wuhan:Wuhan University of Science and Technology,2016.
[4] Kay M I, Young R A, Posner A S. Crystal structure of hydroxyapatite[J]. Nature,1964,204(4963):1050-1052.
[5] Suzuki T, Hatsushika T, Miyake M, et al. Synthetic hydroxyapatites as inorganic cation exchangers. Part 2[J].Journal of the Chemical Society, Faraday Transactions 1:Physical Chemistry in Condensed Phases,1982,78(12):3605-3611.
[6] Suzuki T,Hatsushika T,Hayakawa Y. Synthetic hydroxyapatites employed as inorganic cation-exchangers[J]. Journal of the Chemical Society,Faraday Transactions 1:Physical Chemistry in Condensed Phases,1981,77(5):1059-1062.
[7] Reichert J,Binner J G P. An evaluation of hydroxyapatite-based filters for removal of heavy metal ions from aqueous solutions[J].Journal of Materials Science,1996,31(5):1231-1241.
[8]邹红.镁掺杂改性羟基磷灰石的制备及其对重金属吸附行为的研究[D].徐州:中国矿业大学,2017.Zou H. Preparation of magnesium doped hydroxyapatite and their adsorption of heavy metals ion[D]. Xuzhou:China University of Mining and Technology,2017.
[9]唐振平,毕玉玺,刘迎九,等.氧化石墨烯/有机改性膨润土复合材料的制备及其对Cd(Ⅱ)的吸附[J].复合材料学报,2018,35(11):3196-3204.Tang Z P,Bi Y X,Liu Y J,et al. Preparation of graphene oxide/organo-modified bentonite composites and their adsorption on Cd(Ⅱ)[J]. Acta Materiae Compositae Sinica,2018,35(11):3196-3204.
[10] Zhu Y N,Jiang Y N,Zhu Z Q,et al. Preparation of a porous hydroxyapatite-carbon composite with the bio-template of sugarcane top stems and its use for the Pb(II)removal[J].Journal of Cleaner Production,2018,187:650-661.
[11]张金利,张林林.重金属Pb(Ⅱ)在黏土上吸附特性研究[J].岩土工程学报,2012,34(9):1584-1589.Zhang J L,Zhang L L. Adsorption behaviors of heavy metal Pb(II)on clay[J]. Chinese Journal of Geotechnical Engineering,2012,34(9):1584-1589.
[12] Zhu R H,Yu R B,Yao J X,et al. Removal of Cd2+from aqueous solutions by hydroxyapatite[J]. Catalysis Today,2008,139(1-2):94-99.
[13] Mousa S M,Ammar N S,Ibrahim H A. Removal of lead ions using hydroxyapatite nano-material prepared from phosphogypsum waste[J]. Journal of Saudi Chemical Society,2016,20(3):357-365.
[14]李超,朱宗强,曹爽,等.桉树遗态结构HAP/C复合材料对水中Cu(Ⅱ)的吸附特征[J].环境科学,2017,38(3):1074-1083.Li C,Zhu Z Q,Cao S,et al. Adsorption characteristics of copper in water by the porous biomorph-genetic composite of HAP/C with eucalyptus wood template[J]. Environmental Science,2017,38(3):1074-1083.
[15]刘伟,杨琦,李博,等.磁性石墨烯吸附水中Cr(Ⅵ)研究[J].环境科学,2015,36(2):537-544.Liu W,Yang Q,Li B,et al. Adsorption of Cr(Ⅵ)on magnetic graphene from aqueous solution[J]. Environmental Science,2015,36(2):537-544.
[16]魏建文,韦真周,廖雷,等.氨基修饰介孔分子筛SBA-15对水中Pb2+吸附性能[J].环境工程学报,2014,8(5):1825-1830.Wei J W,Wei Z Z,Liao L,et al. Aqueous Pb(Ⅱ)removal by adsorption on amine-functionalized mesoporous silica SBA-15[J]. Chinese Journal of Environmental Engineering,2014,8(5):1825-1830.
[17] Huang R H,Wang B,Yang B C,et al. Equilibrium,kinetic and thermodynamic studies of adsorption of Cd(II)from aqueous solution onto HACC-bentonite[J]. Desalination,2011,280(1-3):297-304.
[18] Ren Y M,Li N,Feng J,et al. Adsorption of Pb(II)and Cu(II)from aqueous solution on magnetic porous ferrospinel MnFe2O4[J]. Journal of Colloid And Interface Science,2012,367(1):415-421.
[19] Alshameri A,Yan C J,Al-Ani Y,et al. An investigation into the adsorption removal of ammonium by salt activated Chinese(Hulaodu)natural zeolite:kinetics, isotherms, and thermodynamics[J]. Journal of the Taiwan Institute of Chemical Engineers,2014,45(2):554-564.
[20] Koodyńska D,Wntrzak R,Leahy J J,et al. Kinetic and adsorptive characterization of biochar in metal ions removal[J].Chemical Engineering Journal,2012,197:295-305.
[21] Dong L J,Zhu Z L,Qiu Y L,et al. Removal of lead from aqueous solution by hydroxyapatite/magnetite composite adsorbent[J]. Chemical Engineering Journal,2010,165(3):827-834.
[22] Dong L J,Zhu Z L,Qiu Y L,et al. Removal of lead from aqueous solution by hydroxyapatite/manganese dioxide composite[J]. Frontiers of Environmental Science&Engineering,2016,10(1):28-36.
[23]岳燕丽,褚伟伟,卢真真,等.绣球花状掺锶碳羟基磷灰石对Pb2+的吸附[J].环境化学,2017,36(5):1131-1139.Yue Y L,Chu W W,Lu Z Z,et al. Study on Pb2+adsorption by hydrangea-like strontium-doped carbonate hydroxyapatite[J].Environmental Chemistry,2017,36(5):1131-1139.
[24]唐文清,冯泳兰,李小明.掺硅碳羟基磷灰石的制备及其对Pb2+的吸附性能[J].中国环境科学,2013,33(6):1017-1024.Tang W Q,Feng Y L,Li X M. Adsorption characteristics of Pb2+from aqueous solution and synthetic silicon-substituted carbonate hydroxyapatite particles[J]. China Environmental Science,2013,33(6):1017-1024.
[25] Pham Minh D,Tran N D,Nzihou A,et al. Hydroxyapatite gel for the improved removal of Pb2+ions from aqueous solution[J].Chemical Engineering Journal,2013,232:128-138.
[26]杨慧慧,张浩,黄传军,等.磁性羟基磷灰石的制备及其Pb(Ⅱ)吸附性能[J].材料研究学报,2012,26(6):621-626.Yang H H,Zhang H,Huang C J,et al. Fabrication and Pb(Ⅱ)adsorption properties magnetic hydroxyapatite[J]. Chinese Journal of Materials Research,2012,26(6):621-626.
[27]王建新.掺杂羟基磷灰石的合成及其结构与吸附性能的表征[D].北京:中国地质大学(北京),2014.Wang J X. Synthesis and Characterization of the structure and adsorption properties of doped hydroxyapatite[D]. Beijing:China University of Geosciences(Beijing),2014.
[28] Roh H,Yu M R,Yakkala K,et al. Removal studies of Cd(Ⅱ)and explosive compounds using buffalo weed biochar-alginate beads[J]. Journal of Industrial and Engineering Chemistry,2015,26:226-233.
[29]胥焕岩,刘羽,彭明生.羟基磷灰石的除铅行为及作用机理研究[J].矿物岩石地球化学通报,2007,26(S1):128-130.
[30] Ma Q Y, Traina S J, Logan T J, et al. In situ lead immobilization by apatite[J]. Environmental Science&Technology,1993,27(9):1803-1810.
[31] Xu Y P,Schwartz F W. Lead immobilization by hydroxyapatite in aqueous solutions[J]. Journal of Contaminant Hydrology,1994,15(3):187-206.
[32] Mavropoulos E,Rossi A M,Costa A M,et al. Studies on the mechanisms of lead immobilization by hydroxyapatite[J].Environmental Science&Technology,2002,36(7):1625-1629.
[33] Sttzel C,Müller F A,Reinert F,et al. Ion adsorption behaviour of hydroxyapatite with different crystallinities[J]. Colloids and Surfaces B:Biointerfaces,2009,74(1):91-95.
[34] Smiˇc iklas I,Dimovi'c S,Ple'c aI,et al. Removal of Co2+from aqueous solutions by hydroxyapatite[J]. Water Research,2006,40(12):2267-2274.