聚磷氯化铁镁钛混凝剂的制备与表征
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摘要
铁基混凝剂是重要的水处理剂之一,在混凝过程中扮演重要的作用,但其稳定性差,易发生自聚,形成沉淀、失去混凝效能.因此,制备一种稳定高效的铁基复合混凝剂受到广泛的研究.针对以上问题,本研究提出一种新型稳定的铁基复合混凝剂聚磷氯化铁镁钛(PFMTC)的制备方法.以氯化铁、四氯化钛、氯化镁、磷酸氢二钠为原料,单因素法确定PFMTC最优合成条件为:反应温度为50℃,n(Mg)/n(Fe)为1.0,n(Ti)/n(Fe+Mg)为0.5,n(OH)/n(Ti+Mg+Fe)为0.5,n(PO_4~(3-))/n(Fe)为0.3.Ferron逐时络合比色分光光度法分析PFMTC中Fe的形态;红外光谱、X-射线衍射、扫描电镜与能谱对PFMTC结构形貌、组成进行表征分析.Ferron逐时络合比色分光光度法研究显示,PFMTC的混凝性能的优劣受混凝剂多因素(温度、Mg、Ti、碱化度与PO_4~(3-))调控,从而影响混凝剂中Fea、Feb、Fec(Fea表示自由离子铁离子与铁的单核羟基络合物; Feb表示一系列铁的多核羟基络合物或称低聚合度铁的无机高分子; Fec表示铁的高聚物和铁的失稳溶胶或凝胶形态)三者含量的变化.表征分析显示,PFMTC是一种多羟基的铁镁钛聚合物,含有的新基团键(如Ti—P—Ti、Fe—P—Fe、Fe—O—Ti),其有助于延长PFMTC分子链提高其分子量; PFMTC结构单元呈现交联紧密的空间立体网状结构,有助于吸附架桥和网捕卷扫,增强PFMTC的混凝性能.
Iron-based coagulants are important water treatment agents used in coagulation. However,such coagulants are limited by their poor stability due to self-polymerization,precipitation formation,and low coagulation efficiency. Therefore,preparation of stable and efficient iron-based composite coagulants is important. In this study, a new stable iron-based composite coagulant named polychlorinated ferric phosphate,magnesium titanium( PFMTC) was prepared. Ferric chloride,titanium chloride,magnesium chloride,and hydrogen phosphate sodium were used as raw materials for PFMTC preparation. The optimum synthesis conditions of PFMTC were as follow: reaction temperature of 50 ℃,n( Mg)/n( Fe) of 1.0,n( Ti)/n( Fe+Mg) of 0.5,n( OH)/n( Ti+Mg+Fe) of 0.5,and n( PO_4~(3-))/n( Fe) of 0.3. The morphology of Fe in PFMTC was analyzed by Ferron timed complexometric colorimetric spectrophotometry. The structure and composition of PFMTC werecharacterized by FTIR spectroscopy,X-ray diffraction,scanning electron microscopy,and energy spectroscopy. Results of Ferron hourly complexometric colorimetric spectrophotometry showed that the coagulation performance of PFMTC was influenced by many factors( temperature,Mg content,Ti content,basicity, and PO_4~(3-) content), which further influenced the Fea,Feb,and Fec( Fea represented iron ion and a mononuclear hydroxy complex of iron; Febrepresented a series of iron polynuclear hydroxy complexes or inorganic polymers of low degree of polymerization iron; Fec standed for iron polymers and destabilized sol or gel morphology of iron) contents in the coagulant.Characterization analysis showed that PFMTC is a polyhydroxy iron magnesium titanium containing polymer with new bonds( e. g., Ti—P—Ti, Fe—P—Fe, and Fe—O—Ti) that extend the molecular chain of PFMTC and increase its molecular weight. The structural unit of PFMTC has a tightly cross-linked spatial network structure that contributes to the adsorption bridge and net scavenging and enhances the coagulation properties of PFMTC.
Iron-based coagulants are important water treatment agents used in coagulation. However,such coagulants are limited by their poor stability due to self-polymerization,precipitation formation,and low coagulation efficiency. Therefore,preparation of stable and efficient iron-based composite coagulants is important. In this study, a new stable iron-based composite coagulant named polychlorinated ferric phosphate,magnesium titanium( PFMTC) was prepared. Ferric chloride,titanium chloride,magnesium chloride,and hydrogen phosphate sodium were used as raw materials for PFMTC preparation. The optimum synthesis conditions of PFMTC were as follow: reaction temperature of 50 ℃,n( Mg)/n( Fe) of 1.0,n( Ti)/n( Fe+Mg) of 0.5,n( OH)/n( Ti+Mg+Fe) of 0.5,and n( PO_4~(3-))/n( Fe) of 0.3. The morphology of Fe in PFMTC was analyzed by Ferron timed complexometric colorimetric spectrophotometry. The structure and composition of PFMTC werecharacterized by FTIR spectroscopy,X-ray diffraction,scanning electron microscopy,and energy spectroscopy. Results of Ferron hourly complexometric colorimetric spectrophotometry showed that the coagulation performance of PFMTC was influenced by many factors( temperature,Mg content,Ti content,basicity, and PO_4~(3-) content), which further influenced the Fea,Feb,and Fec( Fea represented iron ion and a mononuclear hydroxy complex of iron; Febrepresented a series of iron polynuclear hydroxy complexes or inorganic polymers of low degree of polymerization iron; Fec standed for iron polymers and destabilized sol or gel morphology of iron) contents in the coagulant.Characterization analysis showed that PFMTC is a polyhydroxy iron magnesium titanium containing polymer with new bonds( e. g., Ti—P—Ti, Fe—P—Fe, and Fe—O—Ti) that extend the molecular chain of PFMTC and increase its molecular weight. The structural unit of PFMTC has a tightly cross-linked spatial network structure that contributes to the adsorption bridge and net scavenging and enhances the coagulation properties of PFMTC.
引文
[1]袁霄,李杰,李风亭.新型强化铁盐混凝剂对焦化废水深度处理的研究[J].工业水处理,2016,36(10):65-66.YUAN X,LI J,LI F T. Research on the advanced treatment of coking wastewater bu the novel enhanced ferric coagulant[J]. Industrial Water Treatment,2016,36(10):65-66(in Chinese).
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[3]李辉,王毅力,孙文童.聚合硫酸铁(PFS)混凝腐殖酸(HA)的过程中典型操作因素的影响研究[J].环境科学学报,2012,32(12):2912-2920.LI H,WANG Y L,SUN W D. Study on the effect of typical operating factors on the coagulation of humic acids with polymeric ferric sulfate[J]. Acta Scientiae Circumstantiae,2012,32(12):2912-2920(in Chinese).
[4] HUI X,JIAO R,XIAO F,et al. Enhanced removal for humic-acid(HA)and coagulation process using carbon nanotubes(CNTs)/polyalumium chloride(PACl)composites coagulants[J]. Colloids&Surfaces A Physicochemical&Engineering Aspects,2016,490(2):189-199.
[5] ZHAO Y X,GAO B Y,ZHANG G Z,et al. Coagulation and sludge recovery using titanium tetrachloride as coagulant for real water treatment:A comparison against traditional aluminum and iron salts[J]. Separation&Purification Technology,2014,130(23):19-27.
[6]刘维,吴冰,曹江林,等.钛对聚合硫酸铁制备与性能的影响[J].环境化学,2012,31(4):437-442.LIU W,WU B,CAO J L,et al. Effect of titanium on the preparation and properties of polymerized iron sulfate[J]. Environmental Chemistry,2012,31(4):437-442(in Chinese).
[7]陈伟,郑怀礼,翟俊,等.聚合硫酸铁钛混凝剂的制备及红外、紫外-可见光谱分析[J].光谱学与光谱分析,2016,36(4):1038-1043.CHEN W,ZHENG H L,ZHAI J,et al. Study on the preparation of a new composite coagulant:Poly-ferric-titanium-sulfate and analysis of FTIR spectrum and UV-Vis spectrum[J]. Spectroscopy&Spectral Analysis,2016,36(4):1038-1043(in Chinese).
[8]陈伟.铁钛混凝剂的制备及在除藻和控制藻源膜污染中的应用研究[D].重庆:重庆大学,2016.CHEN W. The preparation of Fe-Ti based coagulant and its application in algae removal and membrane fouling controlling[D]. Chongqing:University of Chongqing,2016(in Chinese).
[9]田宝珍,汤鸿霄. Ferron逐时络合比色法测定Fe(Ⅲ)溶液聚合物的形态[J].环境化学,1989,2(4):27-34.TIAN B Z,TANG H X. Determination of polymeric Fe(Ⅲ)species by ferron complexation timed spectrophotometric method[J].Environmental Chemistry,1989,2(4):27-34(in Chinese).
[10] ZHANG P,ZHANG W,ZHU G C,et al. Preparation of polymeric phosphate aluminum-ferric chloride(PPAFC)and its application in humic acid removal[J]. Journal of Chemical&Pharmaceutical Research,2014,6(6):906-911.
[11] LIAO Y,TANG X,YANG Q,et al. Characterization of an inorganic polymer coagulant and coagulation behavior for humic acid/algaepolluted water treatment:polymeric zinc-ferric-silicate-sulfate coagulant[J]. Rsc Advances,2017,7(32):19856-19862.
[12] MOUSSAS P A,ZOUBOULIS A I. A new inorganic-organic composite coagulant,consisting of polyferric sulphate(PFS)and polyacrylamide(PAA)[J]. Water Research,2009,43(14):3511-3524.
[13] LU R,ZHANG Y,ZHOU F,et al. Novel polyaluminum ferric chloride composite coagulant from Bayer red mud for wastewater treatment[J]. Desalination&Water Treatment,2014,52(40-42):7645-7653.
[14]文彦杰,韩春英,张丽丹,等.聚硅酸铁镁水处理剂的制备及应用研究[J].北京化工大学学报(自然科学版),2012,39(4):90-94.WEN Y J,HAN C Y,ZHANG L D,et al. Preparation and coagulation behavior of a ferric polysilicate coagulant modified with magnesium[J].Journal of Beijing University of Chemical Technology(Natural Science),2012,39(4):90-94(in Chinese).
[15]张景香,陆金仁,单宝田,等.聚硅酸铁镁絮凝剂制备及其脱色作用的研究[J].工业水处理,2009,29(8):56-58.ZHANG J X,LU J R DAN B T,et al. Studies on the preparation and decolorization of ploysilicate ferric magnesium flocculant[J].Industrial Water Treatment,2009,29(8):56-58(in Chinese).
[16] ZHAO Y X,PHUNTSHO S,GAO B Y,et al. Preparation and characterization of novel polytitanium tetrachloride coagulant for water purification.[J]. Environmental Science&Technology,2013,47(22):12966-12975.
[17] CHEKLI L,GALLOUX J,ZHAO Y X,et al. Coagulation performance and floc characteristics of polytitanium tetrachloride and titanium tetrachloride compared with ferric chloride for coal mining wastewater treatment[J]. Separation&Purification Technology,2015,152:94-100.
[18] CHEKLI L,ERIPRET C,Park S H,et al. Coagulation performance and floc characteristics of polytitanium tetrachloride(PTC)compared with titanium tetrachloride(Ti Cl4)and ferric chloride(Fe Cl3)in algal turbid water[J]. Separation&Purification Technology,2017,175:99-106.
[19] WU Y F,LIU W,GAO N Y,et al. A study of titanium sulfate flocculation for water treatment.[J]. Water Research,2011,45(12):3704-3711.
[20]郑怀礼,焦世珺,何强,等.聚磷硫酸铁复合絮凝剂中铁的形态分布研究[J].光谱学与光谱分析,2011,31(2):551-554.ZHENG H L,JIAO S J,HE Q,et al. Study of ferric species distribution in polymeric phosphate ferric sulfate(PPFS)[J]. Spectroscopy&Spectral Analysis,2011,31(2):551-554(in Chinese).
[21] ZHU G C,ZHENG H L,CHEN W,et al. Preparation of a composite coagulant:Polymeric aluminum ferric sulfate(PAFS)for wastewater treatment[J].Desalination,2012,285(1):315-323.
[22]朱国成,柳俊斐,周腾智,等.新型固体聚硅硫酸铁混凝剂的制备及结构表征[J].光谱学与光谱分析,2016,36(8):2455-2461.ZHU G C,LIU J F,ZHOU T Z,et al. The preparation and characterization of a new solid coagulant:Polymeric ferric silicate sulfate[J].Spectroscopy&Spectral Analysis,2016,36(8):2455-2461(in Chinese).
[23] HUANG X,GAO B,WANG Y,et al. Coagulation performance and flocs properties of a new composite coagulant:Polytitanium-silicatesulfate[J]. Chemical Engineering Journal,2014,245(6):173-179.
[2] CHEN W,ZHENG H L,GUO J,et al. Preparation and characterization of a composite coagulant:Polyferric titanium sulfate[J]. Water Air&Soil Pollution,2016,227(3):79-95.
[3]李辉,王毅力,孙文童.聚合硫酸铁(PFS)混凝腐殖酸(HA)的过程中典型操作因素的影响研究[J].环境科学学报,2012,32(12):2912-2920.LI H,WANG Y L,SUN W D. Study on the effect of typical operating factors on the coagulation of humic acids with polymeric ferric sulfate[J]. Acta Scientiae Circumstantiae,2012,32(12):2912-2920(in Chinese).
[4] HUI X,JIAO R,XIAO F,et al. Enhanced removal for humic-acid(HA)and coagulation process using carbon nanotubes(CNTs)/polyalumium chloride(PACl)composites coagulants[J]. Colloids&Surfaces A Physicochemical&Engineering Aspects,2016,490(2):189-199.
[5] ZHAO Y X,GAO B Y,ZHANG G Z,et al. Coagulation and sludge recovery using titanium tetrachloride as coagulant for real water treatment:A comparison against traditional aluminum and iron salts[J]. Separation&Purification Technology,2014,130(23):19-27.
[6]刘维,吴冰,曹江林,等.钛对聚合硫酸铁制备与性能的影响[J].环境化学,2012,31(4):437-442.LIU W,WU B,CAO J L,et al. Effect of titanium on the preparation and properties of polymerized iron sulfate[J]. Environmental Chemistry,2012,31(4):437-442(in Chinese).
[7]陈伟,郑怀礼,翟俊,等.聚合硫酸铁钛混凝剂的制备及红外、紫外-可见光谱分析[J].光谱学与光谱分析,2016,36(4):1038-1043.CHEN W,ZHENG H L,ZHAI J,et al. Study on the preparation of a new composite coagulant:Poly-ferric-titanium-sulfate and analysis of FTIR spectrum and UV-Vis spectrum[J]. Spectroscopy&Spectral Analysis,2016,36(4):1038-1043(in Chinese).
[8]陈伟.铁钛混凝剂的制备及在除藻和控制藻源膜污染中的应用研究[D].重庆:重庆大学,2016.CHEN W. The preparation of Fe-Ti based coagulant and its application in algae removal and membrane fouling controlling[D]. Chongqing:University of Chongqing,2016(in Chinese).
[9]田宝珍,汤鸿霄. Ferron逐时络合比色法测定Fe(Ⅲ)溶液聚合物的形态[J].环境化学,1989,2(4):27-34.TIAN B Z,TANG H X. Determination of polymeric Fe(Ⅲ)species by ferron complexation timed spectrophotometric method[J].Environmental Chemistry,1989,2(4):27-34(in Chinese).
[10] ZHANG P,ZHANG W,ZHU G C,et al. Preparation of polymeric phosphate aluminum-ferric chloride(PPAFC)and its application in humic acid removal[J]. Journal of Chemical&Pharmaceutical Research,2014,6(6):906-911.
[11] LIAO Y,TANG X,YANG Q,et al. Characterization of an inorganic polymer coagulant and coagulation behavior for humic acid/algaepolluted water treatment:polymeric zinc-ferric-silicate-sulfate coagulant[J]. Rsc Advances,2017,7(32):19856-19862.
[12] MOUSSAS P A,ZOUBOULIS A I. A new inorganic-organic composite coagulant,consisting of polyferric sulphate(PFS)and polyacrylamide(PAA)[J]. Water Research,2009,43(14):3511-3524.
[13] LU R,ZHANG Y,ZHOU F,et al. Novel polyaluminum ferric chloride composite coagulant from Bayer red mud for wastewater treatment[J]. Desalination&Water Treatment,2014,52(40-42):7645-7653.
[14]文彦杰,韩春英,张丽丹,等.聚硅酸铁镁水处理剂的制备及应用研究[J].北京化工大学学报(自然科学版),2012,39(4):90-94.WEN Y J,HAN C Y,ZHANG L D,et al. Preparation and coagulation behavior of a ferric polysilicate coagulant modified with magnesium[J].Journal of Beijing University of Chemical Technology(Natural Science),2012,39(4):90-94(in Chinese).
[15]张景香,陆金仁,单宝田,等.聚硅酸铁镁絮凝剂制备及其脱色作用的研究[J].工业水处理,2009,29(8):56-58.ZHANG J X,LU J R DAN B T,et al. Studies on the preparation and decolorization of ploysilicate ferric magnesium flocculant[J].Industrial Water Treatment,2009,29(8):56-58(in Chinese).
[16] ZHAO Y X,PHUNTSHO S,GAO B Y,et al. Preparation and characterization of novel polytitanium tetrachloride coagulant for water purification.[J]. Environmental Science&Technology,2013,47(22):12966-12975.
[17] CHEKLI L,GALLOUX J,ZHAO Y X,et al. Coagulation performance and floc characteristics of polytitanium tetrachloride and titanium tetrachloride compared with ferric chloride for coal mining wastewater treatment[J]. Separation&Purification Technology,2015,152:94-100.
[18] CHEKLI L,ERIPRET C,Park S H,et al. Coagulation performance and floc characteristics of polytitanium tetrachloride(PTC)compared with titanium tetrachloride(Ti Cl4)and ferric chloride(Fe Cl3)in algal turbid water[J]. Separation&Purification Technology,2017,175:99-106.
[19] WU Y F,LIU W,GAO N Y,et al. A study of titanium sulfate flocculation for water treatment.[J]. Water Research,2011,45(12):3704-3711.
[20]郑怀礼,焦世珺,何强,等.聚磷硫酸铁复合絮凝剂中铁的形态分布研究[J].光谱学与光谱分析,2011,31(2):551-554.ZHENG H L,JIAO S J,HE Q,et al. Study of ferric species distribution in polymeric phosphate ferric sulfate(PPFS)[J]. Spectroscopy&Spectral Analysis,2011,31(2):551-554(in Chinese).
[21] ZHU G C,ZHENG H L,CHEN W,et al. Preparation of a composite coagulant:Polymeric aluminum ferric sulfate(PAFS)for wastewater treatment[J].Desalination,2012,285(1):315-323.
[22]朱国成,柳俊斐,周腾智,等.新型固体聚硅硫酸铁混凝剂的制备及结构表征[J].光谱学与光谱分析,2016,36(8):2455-2461.ZHU G C,LIU J F,ZHOU T Z,et al. The preparation and characterization of a new solid coagulant:Polymeric ferric silicate sulfate[J].Spectroscopy&Spectral Analysis,2016,36(8):2455-2461(in Chinese).
[23] HUANG X,GAO B,WANG Y,et al. Coagulation performance and flocs properties of a new composite coagulant:Polytitanium-silicatesulfate[J]. Chemical Engineering Journal,2014,245(6):173-179.