ZnAl和MgAl水滑石吸附废水中磷的研究进展

doi:10.16085/j.issn.1000-6613.2015.01.044

摘要/Abstract

摘要： 简介了 ZnAl 和 MgAl 水滑石的制备方法和除磷原理,制备方法主要有低饱和共沉淀法、尿素分解-均匀共沉淀法、焙烧复原法和水热合成法等,除磷原理主要是表面静电吸附、离子交换、羟基取代、配位络合和水滑石再水合过程的进入等。回顾了水滑石在改性方面的研究,改性水滑石较未改性水滑石除磷效果更佳;详细分析了除磷的各项影响因素,包括制备过程中的不同金属离子摩尔比、焙烧温度、尿素浓度等和反应过程中的 pH 值、共存离子、吸附剂用量、反应温度、吸附时间等,在以上这些因素中都存在一个除磷效果最佳的影响值。简述了在解吸方面所取得的成果,十二烷基苯磺酸钠、十二烷基和1-辛烷等表面活性剂比常规的 Na₂CO₃和 NaCl-NaOH 解吸载磷水滑石效果更优。指出了用纯水滑石除磷存在费用较高的问题,可与廉价材料复合改性解决该问题;总结表明了水滑石吸附除磷今后的热点主要是研究改性后水滑石的除磷效果。

关键词: 水滑石, 废水, 吸附, 磷酸盐

Abstract: This paper introduces ZnAl, MgAl and preparation methods of hydrotalcite and phosphorus removal principles. Hydrotalcite preparation methods are low saturation coprecipitation, urea decomposition-uniform coprecipitation, roasting recovery and hydrothermal synthesis. Phosphorus removal principles are surface electrostatic adsorption, ion exchange, hydroxy group substitution, ligand complex and entry of hydrotalcite rehydration. Modification of hydrotalcite is reviewed. Modified hydrotalcite has better effect of removing phosphorus than common hydrotalcite. Influence factors of phosphorus removal are analyzed, such as molar ratio of metal ions, calcination temperature, concentration of urea, pH, coexisting ions, amount of adsorbent, reaction temperature, and adsorption time. For all these factors, there is a best influence value of removing phosphorus. The achievement of desorption are summarized. Surfactants, for example, sodium dodecyl benzene sulfonate has a better effect than conventional desorption agent for phosphorus hydrotalcite, such as Na₂CO₃ and NaCl-NaOH. The problem of higher cost to remove phosphorus with pure hydrotalcite can be resolved by using cheap composite modified hydrotalcite. Future research will focus on the phosphorus removal performance of modified hydrotalcite.

Key words: hydrotalcite, wastewater, adsorption, phosphate

中图分类号:

X703.1

唐朝春, 陈惠民, 刘名, 叶鑫. ZnAl和MgAl水滑石吸附废水中磷的研究进展[J]. 化工进展, 2015, 34(1): 245-251.

TANG Chaochun, CHEN Huimin, LIU Ming, YE Xin. Advances in adsorption of phosphate in wastewater by ZnAl and MgAl hydrotalcite[J]. Chemical Industry and Engineering Progree, 2015, 34(1): 245-251.

参考文献

[1] 刘连成. 中国湖泊富营养化的现状分析[J]. 灾害学,1997,12(3):61-65.

[2] 方爱红,黄银芝,钱瑾. 浅谈太湖蓝藻暴发的原因、危害及其预防治理[J]. 净水技术,2008,27(3):70-72.

[3] 王海军,王洪铸. 富营养化治理应放宽控氮、集中控磷[J]. 自然科学进展,2009,19(6):599-604.

[4] 管策,郁达伟,郑祥,等. 我国人工湿地在城市污水处理厂尾水脱氮除磷中的研究与应用进展[J]. 农业环境科学学报,2012,31(12):2309-2320.

[5] 张焕朝,张红爱,曹志洪. 太湖地区水稻土磷素径流流失及其 Olsen 磷的"突变点"[J]. 南京林业大学学报:自然科学版,2004,(5):6-10.

[6] 徐轶群,熊慧欣,赵秀兰. 底泥磷的吸附与释放研究进展[J]. 重庆环境科学,2003,25(11):147-149.

[7] 吴燕,安树林. 废水除磷方法的现状与展望[J]. 天津工业大学学报,2001,20(1):74-78.

[8] 邵鹏辉,唐朝春,简美鹏,等. 磷在磁铁矿-针铁矿混合相上的吸附[J]. 环境工程学报,2013,7(9):3433-3438.

[9] Josson As. Fundamental principles of ultrafiltration[J]. Chem. Eng. Process,1990,27:67-81.

[10] Zhang L,Liu J Y,Wan L H,et al. Batch and fixed-bed column performance of phosphate adsorption by lanthanum-doped activated carbon fiber[J]. Water,Air & Soil Pollution,2012,223(9):5893-5902.

[11] Wang Z F,Nie E,Li J H,et al. Equilibrium and kinetics of adsorption of phosphate onto iron-doped activated carbon[J]. Environmental Science and Pollution Research,2012,19(7):2908-2917.

[12] Li G L,Gao S,Zhang G S,et al. Enhanced adsorption of phosphate from aqueous solution by nanostructured iron(Ⅲ)-copper(Ⅱ) binary oxides[J]. Chemical Engineering Journal,2014,235:124-131.

[13] Yoon S Y,Lee C G,Park J A,et al. Kinetic,equilibrium and thermodynamic studies for phosphate adsorption to magnetic iron oxide nanoparticles[J]. Chemical Engineering Journal,2014,236:341-347.

[14] Liana A R,Leandro J M,Luciana S C,et al. Adsorption of phosphate from aqueous solution by hydrous zirconium oxide[J]. Environmental Technology,2012,33(12):1345-1351.

[15] Liu Q,Guo L J,Zhou Y M,et al. Phosphate adsorption on biogenetic calcium carbonate minerals:Effect of a crystalline phase[J]. Desalination and Water Treatment,2012,47(1-3):78-85.

[16] Zhang J D,Shan W P,Ge J F,et al. Kinetic and equilibrium studies of liquid-phase adsorption of phosphate on modified sugarcane bagasse[J]. Journal of Environmental Engineering,2012,138(3):252-258.

[17] Chen W T,Lin C W,Shih P K,et al. Adsorption of phosphate into waste oyster shell:Thermodynamic parameters and reaction kinetics[J]. Desalination and Water Treatment,2012,47(1-3):86-95.

[18] Huang W Y,Li D,Liu Z Q,et al. Kinetics,isotherm,thermodynamic,and adsorption mechanism studies of La(OH)₃-modified exfoliated vermiculites as highly efficient phosphate adsorbents[J]. Chemical Engineering Journal,2014,236:191-201.

[19] Xie J J,Chen T H,Qing C S,et al. Adsorption of phosphate from aqueous solutions by thermally modified palygorskite[J]. Environmental Engineering and Management Journal,2013,12(7):1393-1399.

[20] Yang S J,Ding D H,Zhao Y X,et al. Investigation of phosphate adsorption from aqueous solution using kanuma mud:Behaviors and mechanisms[J]. Journal of Environmental Chemical Engineering,2013,1(3):355-362.

[21] Li D D,Min H Y,Jiang X,et al. One-pot synthesis of aluminum-containing ordered mesoporous silica MCM-41 using coal fly ash for phosphate adsorption[J]. Journal of Colloid and Interface Science,2013,404:42-48.

[22] Huang W Y,Li D,Yang J,et al. One-pot synthesis of Fe(Ⅲ)- coordinated diamino-functionalized mesoporous silica:Effect of functionalization degrees on structures and phosphate adsorption[J]. Microporous & Mesoporous Materials,2013,170:200-210.

[23] Choi J W,Lee S Y,Lee S H,et al. Adsorption of Phosphate by amino-functionalized and Co-condensed SBA-15[J]. Water,Air & Soil Pollution,2012,223(5):2551-2562.

[24] Ren J,Li N,Zhao L,et al. Enhanced adsorption of phosphate by loading nanosized ferric oxyhydroxide on anion resin[J]. Frontiers of Environmental Science & Engineering,2014,8(4):531-538.

[25] Tripti S,Reena S. Reuse of a waste adsorbent poly(AAc/AM/SH)-Cu superabsorbent hydrogel,for the potential phosphate ion removal from waste water:Matrix effects,adsorption kinetics,and thermodynamic studies[J]. Journal of Applied Polymer Science,2013,129(6):3126-3139.

[26] Li N,Ren J,Zhao L,et al. Fixed bed adsorption study on phosphate removal using nanosized FeOOH-modified anion resin[J]. Journal of Nanomaterials,2013,2013:1-5.

[27] Yeddou M N,Bensmaili A. Kinetics and thermodynamic study of phosphate adsorption on iron hydroxide-eggshell waste[J]. Chemical Engineering Journal,2009,147(2-3):87-96.

[28] Rives V,Ulibarri M A. Layered double hydroxides(LDHs) intercalated with metal coordination compounds and oxometalates[J]. Coordin. Chem. Rev.,1999,181(1):61-120.

[29] 杜以波,Evans D G,孙鹏,等. 阴离子型层柱材料研究进展[J]. 化学通报,2000,63(5):20-28.

[30] Allmann R. The crystal structure of pyroaurite[J]. Acta. Cryst.,1968,24(7):927-977.

[31] Koilraj P,Kannan S. Phosphate uptake behavior of ZnAlZr ternary layered double hydroxides through surface precipitation[J]. Journal of Colloid and Interface Science,2010,341:289-297.

[32] 陆英,程翔,邢波,等. 尿素分解共沉淀法中反应时间对 ZnAl类水滑石结构和磷吸附性能的影响[J]. 环境科学,2012,33(8):2868-2874.

[33] Tetsuya S,Shinsuke Y,Katsuhiko T. Photopolymerization of 4-vinylbenzoate and m- and p-phenylenediacrylates in hydrotalcite interlayers[J]. Super. Molecular. Sci.,1998,5(3):303-308.

[34] Zhou J B,Yang S L,Yu J G,et al. Novel hollow microspheres of hierarchical zinc-aluminum layered double hydroxides and their enhanced adsorption capacity for phosphate in water[J]. Journal of Hazardous Materials,2011,192:1114-1121.

[35] Zhang M,Gao B,Yao Y,et al. Phosphate removal ability of biochar/MgAl-LDH ultra-fine composites prepared by liquid-phase deposition[J]. Chemosphere,2013,92:1042-1047.

[36] He H M,Kang H L,Ma S L,et al. High adsorption selectivity of ZnAl layered double hydroxides and the calcined materials toward phosphate[J]. Journal of Colloid and Interface Science,2010,343:225-231.

[37] 邢颖,李殿卿,任玲玲,等. 超分子结构水杨酸根插层水滑石的组装及结构与性能研究[J]. 化学学报,2003,61(2):267-272.

[38] Itaya K. Anion-exchanged hydhydrotalcite-like-clay modified electrodes[J]. Inorg. Chem.,1987,26(5):624-626.

[39] 胡静,吕亮. 镁铝水滑石去除氯离子性能研究[J]. 工业水处理,2008,28(6):59-61.

[40] 赵毅,朱洪涛,申思. 镁铝水滑石在印染废水治理中的应用[J]. 工业水处理,2010,30(2):8-11.

[41] Cheng X,Huang X R,Wang X Z,et al. Influence of calcination on the adsorptive removal of phosphate by Zn-Al layered double hydroxides from excess sludge liquor[J]. Journal of Hazardous Materials,2010,177:516-523.

[42] Cheng X,Wang Y,Sun Z,et al. Pathways of phosphate uptake from aqueous solution by ZnAl layered double hydroxides[J]. Water Science and Technology,2013,67(8):1757-1763.

[43] 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.

[44] Cai P,Zheng H,Wang C,et al. Competitive adsorption characteristics of fluoride and phosphate on calcined Mg-Al-CO₃ layered double hydroxides[J]. Journal of Hazardous Materials,2012,213-214:100-108.

[45] Gan F Q,Zhou J M,Wang H Y,et al. Layered double hydroxide (LDH)-coated attapulgite for phosphate removal from aqueous solution[J]. Water Science & Technology,2011,64(11):2192-2198.

[46] 张海永,景晓燕,张密林,等. 一种新型的纳米功能材料:磁性纳米镁铝水滑石[J]. 无机化学学报,2002,18(2):185-189.

[47] 孙德智,黄新瑞,程翔,等. Zn-Al类水滑石吸附污泥脱水液中磷的研究[J]. 北京林业大学学报,2009,31(2):128-132.

[48] Cheng X,Huang X R,Wang X Z,et al. Phosphate adsorption from sewage sludge filtrate using zinc-aluminum layered double hydroxides[J]. Journal of Hazardous Materials,2009,169:958-964.

[49] Das J,Patra B S,Baliarsingh N,et al. Adsorption of phosphate by layered double hydroxides in aqueous solutions[J]. Applied Clay Science,2006,32:252-260.

[50] Ramesh C,Satoko T,Akinari S,et al. Synthesis and phosphate uptake behavior of Zr⁴⁺ incorporated MgAl-layered double hydroxides[J]. Journal of Colloid and Interface Science,2007,313:53-63.

[51] Odair F P,Oswaldo A L,Daniel G X,et al. Thermal decomposition and structural reconstruction effect on Mg-Fe-based hydrotalcite compounds[J]. Journal of Solid State Chemistry,2004,177:3058-3069.

[52] Chatelet L,Bottero J Y,Yvon J,et al. Competition between monovalent and divalent anions for calcined and uncalcined hydrotalcite:Anion exchange and adsorption sites[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,1996,111(3):167-175.

[53] 陈爱燕,程翔,黄新瑞,等. Zn-Al类水滑石磷吸附剂的制备及其吸附性能[J]. 化工学报,2008,59(9):2270-2275.

[54] Cheng X,Huang X R,Wang X Z,et al. Phosphate adsorption by ZnAlLa layered double hydroxides from excess sludge filtrate[J]. CIESC Journal,2010,61(4):955-962.

[55] Antonio V,Marianna P,Vincenza C,et al. Sorption/desorption of arsenate on/from Mg-Al layered double hydroxides:Influence of phosphate[J]. Journal of Colloid and Interface Science,2009,333:63-70.

[56] 杨思亮,周家斌,成娅,等. Zn-Al水滑石及其焙烧产物对水中磷的吸附研究[J]. 工业水处理,2011,31(10):53-57.

[57] Cheng X,Ye J X,Sun D Z,et al. Influence of synthesis temperature on phosphate adsorption by Zn-Al layered double hydroxides in excess sludge liquor[J]. Chinese Journal of Chemical Engineering,2011,19(3):391-396.

[58] 黄中子,张文启,刘勇弟,等. 水滑石对水中磷的吸附特征及影响因素研究[J]. 水处理技术,2010,36(8):49-52.

[59] Xing K,Wang H Z,Guo L G,et al. Adsorption of tripolyphosphate from aqueous solution by Mg-Al-CO₃-layered double hydroxides[J]. Colloids and Surfaces A,2008,328:15-20.

[60] Akihiro S,Mark I J,James B M. Anionic surfactant enhanced phosphate desorption from Mg/Al-layered double hydroxides by micelle formation[J]. Journal of Colloid and Interface Science,2013,411:1-7.

[61] Akihiro S,Mark I J,Eiji K,et al. Complete desorption of interlayer hydrogen phosphate in Mg/Al-layered double hydroxides by means of anion exchange with 1-octanesulfonate[J]. Journal of Materials Science,2012,47(3):1142-1147.