铝污泥酸化提取液改性沸石的除磷特性及机制
|
摘要
为了提高沸石的除磷能力并降低改性成本,以给水厂铝污泥为铝源,采用酸化提取液合成层状双氢氧化物(LDHs)覆膜于沸石表面制备改性沸石,分别测定原沸石、Al-Zn改性沸石及铝污泥改性沸石的表面特性和化学组分,分析等温吸附及吸附动力学特性,探讨铝污泥改性沸石的除磷性能及除磷机制.结果表明,最佳酸化提取条件为60 min、150 r·min~(-1)和p H1. 0,该条件下1 g铝污泥(干重)可提取77 mg的铝;改性沸石的饱和吸附容量和解吸性能较原沸石显著提高,尤其是铝污泥改性沸石,其理论最大吸附量从30. 24 mg·kg~(-1)提升至170. 40 mg·kg~(-1);改性使得沸石对磷酸盐的主要吸附类型由物理吸附向化学吸附转变.以铝污泥为铝源改性沸石能有效地提高其对磷酸盐的吸附能力及再生能力,在降低磷浓度过高引发的水体富营养化风险的同时,实现以废治废的目的.
To improve the capacity for phosphorus removal and to reduce the cost of treatment,alum sludge from a water supply plant was obtained to prepare modified zeolite coated with layered double hydroxide( LDHs),which was synthesized using an acidified extraction liquid. The surface characteristics and chemical composition of raw zeolites,Al-Zn modified zeolites,and alum sludge modified zeolites were determined,and the isothermal adsorption and adsorption kinetics were analyzed. The performance and mechanism of phosphorus removal by the alum sludge modified zeolites were evaluated. The results showed that the optimum conditions for acidification extraction were 60 min treatment time,150 r·min~(-1),and p H 1. 0,which achieved 77 mg aluminum extraction rate per gram of alum sludge. Compared to raw zeolites,the maximum saturated adsorption capacity and the desorption performance of the zeolites were significantly increased by this modification. In addition,the theoretical maximum adsorption capacity of alum sludge modified zeolites was increased from 30. 24 mg·kg~(-1) to 170. 40 mg·kg~(-1). The modification changed the main mode of phosphate adsorption by zeolite from physical adsorption to chemical adsorption. Alum sludge modification could improve the efficiency of phosphate adsorption and the regeneration capacity of zeolite,which could reduce the risk of water eutrophication caused by high phosphate concentrations,and could achieve the purpose of waste control by waste.
To improve the capacity for phosphorus removal and to reduce the cost of treatment,alum sludge from a water supply plant was obtained to prepare modified zeolite coated with layered double hydroxide( LDHs),which was synthesized using an acidified extraction liquid. The surface characteristics and chemical composition of raw zeolites,Al-Zn modified zeolites,and alum sludge modified zeolites were determined,and the isothermal adsorption and adsorption kinetics were analyzed. The performance and mechanism of phosphorus removal by the alum sludge modified zeolites were evaluated. The results showed that the optimum conditions for acidification extraction were 60 min treatment time,150 r·min~(-1),and p H 1. 0,which achieved 77 mg aluminum extraction rate per gram of alum sludge. Compared to raw zeolites,the maximum saturated adsorption capacity and the desorption performance of the zeolites were significantly increased by this modification. In addition,the theoretical maximum adsorption capacity of alum sludge modified zeolites was increased from 30. 24 mg·kg~(-1) to 170. 40 mg·kg~(-1). The modification changed the main mode of phosphate adsorption by zeolite from physical adsorption to chemical adsorption. Alum sludge modification could improve the efficiency of phosphate adsorption and the regeneration capacity of zeolite,which could reduce the risk of water eutrophication caused by high phosphate concentrations,and could achieve the purpose of waste control by waste.
引文
[1]Smith V H,Wood S A,Mc Bride C G,et al.Phosphorus and nitrogen loading restraints are essential for successful eutrophication control of lake rotorua,new zealand[J].Inland Waters,2016,6(2):273-283.
[2]唐朝春,吴庆庆,段先月,等.利用吸附法处理废水中磷酸盐的研究进展[J].长江科学院院报,2018,35(4):18-23.Tang C C,Wu Q Q,Duan X Y,et al.Advances in the removal of phosphate from wastewater by adsorption method[J].Journal of Yangtze River Scientific Research Institute,2018,35(4):18-23.
[3]Babatunde A O,Zhao Y Q.Constructive approaches toward water treatment works sludge management:an international review of beneficial reuses[J].Critical Reviews in Environmental Science and Technology,2007,37(2):129-164.
[4]Hou Q J,Meng P P,Pei H Y,et al.Phosphorus adsorption characteristics of alum sludge:adsorption capacity and the forms of phosphorus retained in alum sludge[J].Materials Letters,2018,229:31-35.
[5]Zahari N M,Hua C K,Sidek L M.Behaviour of waterworks alum sludge for phosphate removal[J].Advanced Materials Research,2015,1113:764-769.
[6]仇付国,许俊挺,卢超,等.给水厂污泥在水体净化领域中的应用研究进展[J].环境科学与技术,2018,41(5):111-119.Qiu F G,Xu J T,Lu C,et al.Progress on application of water treatment residual in water purification[J].Environmental Science&Technology,2018,41(5):111-119.
[7]赵晓红,赵亚乾,王文科,等.人工湿地系统以铝污泥为基质的几个关键问题[J].中国给水排水,2015,31(11):131-136.Zhao X H,Zhao Y Q,Wang W K,et al.Several key issues to consider in using alum sludge as substrate in constructed wetland[J].China Water&Wastewater,2015,31(11):131-136.
[8]胡沅胜,赵亚乾,Babatunde A,等.铝污泥基质潮汐流人工湿地强化除污中试[J].中国给水排水,2015,31(13):116-122.Hu R S,Zhao Y Q,Babatunde A,et al.Pilot study on enhanced pollutants removal in alum sludge-based tidal flow constructed wetlands[J].China Water&Wastewater,2015,31(13):116-122.
[9]Soleha M Y,Ong K K,Wan Yunus W M Z,et al.Characterization of raw and thermally treated alum sludge[J].Key Engineering Materials,2016,701:138-142.
[10]耿雅妮,任雪盈,巨龙,等.热改性铝污泥吸附除磷的动力学和热力学研究[J].应用化工,2018,47(7):1377-1381.Geng Y N,Ren X Y,Ju L,et al.Kinetics and thermodynamics of phosphate removal by heat modified alum sludge[J].Applied Chemical Industry,2018,47(7):1377-1381.
[11]赵晓红,赵亚乾,杨永哲,等.铝污泥人工湿地污水处理系统小试研究[J].中国给水排水,2015,31(13):110-115.Zhao X H,Zhao Y Q,Yang Y Z,et al.Use of alum sludge as main substrate in constructed wetland for wastewater treatment:lab trials[J].China Water&Wastewater,2015,31(13):110-115.
[12]赵亚乾,杨永哲,Babatunde A,等.以给水厂铝污泥为基质的人工湿地研发概述[J].中国给水排水,2015,31(11):124-130.Zhao Y Q,Yang Y Z,Babatunde A,et al.Overview of development of alum sludge-based constructed wetland for wastewater treatment[J].China Water&Wastewater,2015,31(11):124-130.
[13]Zhang X L,Guo L,Huang H L,et al.Removal of phosphorus by the core-shell bio-ceramic/Zn-layered double hydroxides(LDHs)composites for municipal wastewater treatment in constructed rapid infiltration system[J].Water Research,2016,96:280-291.
[14]Yang K,Yan L G,Yang Y M,et al.Adsorptive removal of phosphate by Mg-Al and Zn-Al layered double hydroxides:kinetics,isotherms and mechanisms[J].Separation and Purification Technology,2014,124:36-42.
[15]胡锋平,罗文栋,彭小明,等.层状双金属氢氧化物去除水中污染物研究进展[J].水处理技术,2019,45(1):17-22.Hu F P,Luo W D,Peng X M,et al.Research progress in layered double hydroxides for the pollutants removal in wastewater[J].Technology of Water Treatment,2019,45(1):17-22.
[16]陈巧珍,张翔凌,阮聪颖,等.Zn Co-LDHs改性人工湿地沸石基质对城市污水的净化效果[J].安全与环境学报,2016,16(4):338-342.Chen Q Z,Zhang X L,Ruan C Y,et al.Purification effect of modified zeolite substrates coated with Zn Co-LDHs in the simulated vertical-flow constructed wetlands[J].Journal of Safety and Environment,2016,16(4):338-342.
[17]向洋,张翔凌,雷雨,等.不同合成条件对Zn Al-LDHs覆膜改性生物陶粒除磷效果的影响[J].环境科学,2018,39(5):2184-2194.Xiang Y,Zhang X L,Lei Y,et al.Influencing factors for phosphorus removal by modified bio-ceramic substrates coated with ZnAl-LDHs synthesized by different modification conditions[J].Environmental Science,2018,39(5):2184-2194.
[18]张翔凌,陈俊杰,郭露,等.垂直流人工湿地LDHs覆膜改性沸石基质强化除磷效果及其机制[J].环境科学,2014,35(12):4553-4559.Zhang X L,Chen J J,Guo L,et al.Analysis on the removal efficiency and mechanisms of phosphorus by modified zeolites substrates coated with LDHs reacted by different metal compounds in laboratory-scale vertical-flow constructed wetlands[J].Environmental Science,2014,35(12):4553-4559.
[19]张翔凌,黄华玲,郭露,等.Zn系LDHs覆膜改性人工湿地沸石基质除磷机制[J].环境科学,2016,37(8):3058-3066.Zhang X L,Huang H L,Guo L,et al.Mechanisms of phosphorus removal by modified zeolites substrates coated with Zn-LDHs in laboratory-scale vertical-flow constructed wetlands[J].Environmental Science,2016,37(8):3058-3066.
[20]Ayoub M,Abdelfattah A.A parametric study of alum recovery from water treatment sludge[J].Water Science&Technology,2016,74(2):516-523.
[21]Keeley J,Smith A D,Judd S J,et al.Acidified and ultrafiltered recovered coagulants from water treatment works sludge for removal of phosphorus from wastewater[J].Water Research,2016,88:380-388.
[22]Nair A T,Ahammed M M.Influence of sludge characteristics on coagulant recovery from water treatment sludge:a preliminary study[J].Journal of Material Cycles and Waste Management,2017,19(3):1228-1234.
[23]国家环境保护总局.水和废水监测分析方法[M].(第四版).北京:中国环境科学出版社,2002.243-246.
[24]Chen Y J,Wang W M,Wei M J,et al.Effects of Al-coagulant sludge characteristics on the efficiency of coagulants recovery by acidification[J].Environmental Technology,2012,33(22):2525-2530.
[25]Evuti A M,Lawal M.Recovery of coagulants from water works sludge:a review[J].Advances in Applied Science Research,2011,2(6):410-417.
[26]Xu G R,Yan Z C,Wang Y C,et al.Recycle of alum recovered from water treatment sludge in chemically enhanced primary treatment[J].Journal of Hazardous Materials,2009,161(2-3):663-669.
[27]Azim A A,Abdel Halim H,Helmy E.Comparison between applying acidification method for alum recovery of different clarifier type[J].Journal of Applied Sciences Research,2013,9(8):4723-4733.
[28]王晨晔.钢渣制备层状双金属氢氧化物及应用基础研究[D].北京:北京科技大学,2018.6-13.Wang C Y.Basic study on preparation technology and application of layered double hydroxides using steelmaking slag as raw material[D].Beijing:University of Science and Technology Beijing,2018.6-13.
[29]章萍,曾宪哲,马若男,等.三维层状双金属氢氧化物(3D-LDHs)的制备及应用概述[J].人工晶体学报,2018,47(11):2255-2259.Zhang P,Zeng X Z,Ma R N,et al.Review on the synthesis and applications of three-dimensional layered double hydroxides(3D-LDHs)[J].Journal of Synthetic Crystals,2018,47(11):2255-2259.
[30]González M A,Pavlovic I,Barriga C.Cu(Ⅱ),Pb(Ⅱ)and Cd(Ⅱ)sorption on different layered double hydroxides.A kinetic and thermodynamic study and competing factors[J].Chemical Engineering Journal,2015,269:221-228.
[31]Jeon E K,Ryu S,Park S W,et al.Enhanced adsorption of arsenic onto alum sludge modified by calcination[J].Journal of Cleaner Production,2018,176:54-62.
[32]姜博汇,林建伟,詹艳慧,等.不同锆负载量锆改性膨润土对水中磷酸盐吸附作用的对比[J].环境科学,2017,38(6):2400-2411.Jiang B H,Lin J W,Zhan Y H,et al.Comparison of phosphate adsorption onto zirconium-modified bentonites with different zirconium loading levels[J].Environmental Science,2017,38(6):2400-2411.
[33]王丹赫,张宏华,林建伟,等.四氧化三铁改性沸石改良底泥对水中磷酸盐的吸附作用[J].环境科学,2018,39(11):5024-5035.Wang D H,Zhang H H,Lin J W,et al.Adsorption of phosphate from aqueous solutions on sediments amended with magnetitemodified zeolite[J].Environmental Science,2018,39(11):5024-5035.
[2]唐朝春,吴庆庆,段先月,等.利用吸附法处理废水中磷酸盐的研究进展[J].长江科学院院报,2018,35(4):18-23.Tang C C,Wu Q Q,Duan X Y,et al.Advances in the removal of phosphate from wastewater by adsorption method[J].Journal of Yangtze River Scientific Research Institute,2018,35(4):18-23.
[3]Babatunde A O,Zhao Y Q.Constructive approaches toward water treatment works sludge management:an international review of beneficial reuses[J].Critical Reviews in Environmental Science and Technology,2007,37(2):129-164.
[4]Hou Q J,Meng P P,Pei H Y,et al.Phosphorus adsorption characteristics of alum sludge:adsorption capacity and the forms of phosphorus retained in alum sludge[J].Materials Letters,2018,229:31-35.
[5]Zahari N M,Hua C K,Sidek L M.Behaviour of waterworks alum sludge for phosphate removal[J].Advanced Materials Research,2015,1113:764-769.
[6]仇付国,许俊挺,卢超,等.给水厂污泥在水体净化领域中的应用研究进展[J].环境科学与技术,2018,41(5):111-119.Qiu F G,Xu J T,Lu C,et al.Progress on application of water treatment residual in water purification[J].Environmental Science&Technology,2018,41(5):111-119.
[7]赵晓红,赵亚乾,王文科,等.人工湿地系统以铝污泥为基质的几个关键问题[J].中国给水排水,2015,31(11):131-136.Zhao X H,Zhao Y Q,Wang W K,et al.Several key issues to consider in using alum sludge as substrate in constructed wetland[J].China Water&Wastewater,2015,31(11):131-136.
[8]胡沅胜,赵亚乾,Babatunde A,等.铝污泥基质潮汐流人工湿地强化除污中试[J].中国给水排水,2015,31(13):116-122.Hu R S,Zhao Y Q,Babatunde A,et al.Pilot study on enhanced pollutants removal in alum sludge-based tidal flow constructed wetlands[J].China Water&Wastewater,2015,31(13):116-122.
[9]Soleha M Y,Ong K K,Wan Yunus W M Z,et al.Characterization of raw and thermally treated alum sludge[J].Key Engineering Materials,2016,701:138-142.
[10]耿雅妮,任雪盈,巨龙,等.热改性铝污泥吸附除磷的动力学和热力学研究[J].应用化工,2018,47(7):1377-1381.Geng Y N,Ren X Y,Ju L,et al.Kinetics and thermodynamics of phosphate removal by heat modified alum sludge[J].Applied Chemical Industry,2018,47(7):1377-1381.
[11]赵晓红,赵亚乾,杨永哲,等.铝污泥人工湿地污水处理系统小试研究[J].中国给水排水,2015,31(13):110-115.Zhao X H,Zhao Y Q,Yang Y Z,et al.Use of alum sludge as main substrate in constructed wetland for wastewater treatment:lab trials[J].China Water&Wastewater,2015,31(13):110-115.
[12]赵亚乾,杨永哲,Babatunde A,等.以给水厂铝污泥为基质的人工湿地研发概述[J].中国给水排水,2015,31(11):124-130.Zhao Y Q,Yang Y Z,Babatunde A,et al.Overview of development of alum sludge-based constructed wetland for wastewater treatment[J].China Water&Wastewater,2015,31(11):124-130.
[13]Zhang X L,Guo L,Huang H L,et al.Removal of phosphorus by the core-shell bio-ceramic/Zn-layered double hydroxides(LDHs)composites for municipal wastewater treatment in constructed rapid infiltration system[J].Water Research,2016,96:280-291.
[14]Yang K,Yan L G,Yang Y M,et al.Adsorptive removal of phosphate by Mg-Al and Zn-Al layered double hydroxides:kinetics,isotherms and mechanisms[J].Separation and Purification Technology,2014,124:36-42.
[15]胡锋平,罗文栋,彭小明,等.层状双金属氢氧化物去除水中污染物研究进展[J].水处理技术,2019,45(1):17-22.Hu F P,Luo W D,Peng X M,et al.Research progress in layered double hydroxides for the pollutants removal in wastewater[J].Technology of Water Treatment,2019,45(1):17-22.
[16]陈巧珍,张翔凌,阮聪颖,等.Zn Co-LDHs改性人工湿地沸石基质对城市污水的净化效果[J].安全与环境学报,2016,16(4):338-342.Chen Q Z,Zhang X L,Ruan C Y,et al.Purification effect of modified zeolite substrates coated with Zn Co-LDHs in the simulated vertical-flow constructed wetlands[J].Journal of Safety and Environment,2016,16(4):338-342.
[17]向洋,张翔凌,雷雨,等.不同合成条件对Zn Al-LDHs覆膜改性生物陶粒除磷效果的影响[J].环境科学,2018,39(5):2184-2194.Xiang Y,Zhang X L,Lei Y,et al.Influencing factors for phosphorus removal by modified bio-ceramic substrates coated with ZnAl-LDHs synthesized by different modification conditions[J].Environmental Science,2018,39(5):2184-2194.
[18]张翔凌,陈俊杰,郭露,等.垂直流人工湿地LDHs覆膜改性沸石基质强化除磷效果及其机制[J].环境科学,2014,35(12):4553-4559.Zhang X L,Chen J J,Guo L,et al.Analysis on the removal efficiency and mechanisms of phosphorus by modified zeolites substrates coated with LDHs reacted by different metal compounds in laboratory-scale vertical-flow constructed wetlands[J].Environmental Science,2014,35(12):4553-4559.
[19]张翔凌,黄华玲,郭露,等.Zn系LDHs覆膜改性人工湿地沸石基质除磷机制[J].环境科学,2016,37(8):3058-3066.Zhang X L,Huang H L,Guo L,et al.Mechanisms of phosphorus removal by modified zeolites substrates coated with Zn-LDHs in laboratory-scale vertical-flow constructed wetlands[J].Environmental Science,2016,37(8):3058-3066.
[20]Ayoub M,Abdelfattah A.A parametric study of alum recovery from water treatment sludge[J].Water Science&Technology,2016,74(2):516-523.
[21]Keeley J,Smith A D,Judd S J,et al.Acidified and ultrafiltered recovered coagulants from water treatment works sludge for removal of phosphorus from wastewater[J].Water Research,2016,88:380-388.
[22]Nair A T,Ahammed M M.Influence of sludge characteristics on coagulant recovery from water treatment sludge:a preliminary study[J].Journal of Material Cycles and Waste Management,2017,19(3):1228-1234.
[23]国家环境保护总局.水和废水监测分析方法[M].(第四版).北京:中国环境科学出版社,2002.243-246.
[24]Chen Y J,Wang W M,Wei M J,et al.Effects of Al-coagulant sludge characteristics on the efficiency of coagulants recovery by acidification[J].Environmental Technology,2012,33(22):2525-2530.
[25]Evuti A M,Lawal M.Recovery of coagulants from water works sludge:a review[J].Advances in Applied Science Research,2011,2(6):410-417.
[26]Xu G R,Yan Z C,Wang Y C,et al.Recycle of alum recovered from water treatment sludge in chemically enhanced primary treatment[J].Journal of Hazardous Materials,2009,161(2-3):663-669.
[27]Azim A A,Abdel Halim H,Helmy E.Comparison between applying acidification method for alum recovery of different clarifier type[J].Journal of Applied Sciences Research,2013,9(8):4723-4733.
[28]王晨晔.钢渣制备层状双金属氢氧化物及应用基础研究[D].北京:北京科技大学,2018.6-13.Wang C Y.Basic study on preparation technology and application of layered double hydroxides using steelmaking slag as raw material[D].Beijing:University of Science and Technology Beijing,2018.6-13.
[29]章萍,曾宪哲,马若男,等.三维层状双金属氢氧化物(3D-LDHs)的制备及应用概述[J].人工晶体学报,2018,47(11):2255-2259.Zhang P,Zeng X Z,Ma R N,et al.Review on the synthesis and applications of three-dimensional layered double hydroxides(3D-LDHs)[J].Journal of Synthetic Crystals,2018,47(11):2255-2259.
[30]González M A,Pavlovic I,Barriga C.Cu(Ⅱ),Pb(Ⅱ)and Cd(Ⅱ)sorption on different layered double hydroxides.A kinetic and thermodynamic study and competing factors[J].Chemical Engineering Journal,2015,269:221-228.
[31]Jeon E K,Ryu S,Park S W,et al.Enhanced adsorption of arsenic onto alum sludge modified by calcination[J].Journal of Cleaner Production,2018,176:54-62.
[32]姜博汇,林建伟,詹艳慧,等.不同锆负载量锆改性膨润土对水中磷酸盐吸附作用的对比[J].环境科学,2017,38(6):2400-2411.Jiang B H,Lin J W,Zhan Y H,et al.Comparison of phosphate adsorption onto zirconium-modified bentonites with different zirconium loading levels[J].Environmental Science,2017,38(6):2400-2411.
[33]王丹赫,张宏华,林建伟,等.四氧化三铁改性沸石改良底泥对水中磷酸盐的吸附作用[J].环境科学,2018,39(11):5024-5035.Wang D H,Zhang H H,Lin J W,et al.Adsorption of phosphate from aqueous solutions on sediments amended with magnetitemodified zeolite[J].Environmental Science,2018,39(11):5024-5035.