摘要
当前,水环境污染已经成为困扰民生的一个非常重要的问题。工业废水和生活污水中的磷处理不完全或者未经处理就直接排入到水体,导致了水环境中营养物质的超标,给水体带来富营养化,造成了严重的危害。由于传统的二级生化处理工艺除磷结果远不能达到国家二级排放标准,并不能够全面解决营养物质对水体的污染和富营养化危害的问题,因此,有必要寻求新的处理材料和方法,对二级处理后的低浓度磷进行后续除磷。本课题主要研究了类水滑石对模拟含磷环境水中低浓度磷的去除效果,初步分析了其作用机理,探讨了其实际应用的可行性。
水滑石也称层状双氢氧化物(Layer Double Hydroxide,简称LDH)、阴离子粘土。水滑石在很多领域,特别是在水处理领域,因其具有独特的孔结构和阴离子的可交换性、吸附催化特性以及较高的耐酸碱能力和热稳定性,显示出了非常广阔的应用前景。本实验制各水滑石。采用双滴定法,按照既定配比混合盐溶液、双滴定、培养、水洗、静置沉淀、定容生产工艺合成液态水滑石,实验制备了Mn:Fe=3:1、Mg:Mn=3:1、Ca:Fe=3:1时的水滑石,分别记为Mn-Fe-LDH、Mg-Mn-LDH、Ca-Fe-LDH、借助环境扫描电镜、FT-IR分析等测试手段,研究了材料的表面形态、吸附机理;同时对其可行性进行了研究,通过改变吸附时间、pH和含磷环境水浓度及掺加共存无机阴离子等因素探讨了材料对磷的去除效果。
得出以下结论:
(1)材料微孔间交错相通,孔隙结构发达,有良好的结晶度,具有层状双氢氧化物的片状结构,是良好的吸附材料。
(2)与吸附前的水滑石相比,吸附后的Ca-Fe-LDH红外光谱在1132 cm-1、1068 cm-1、986 cm-1处出现了P-O振动吸收峰,Mg-Mn-LDH在1068cm-1、1020 cm-1处出现了P-O振动吸收峰,Mn-Fe-LDH在1068cm-1、1014 cm-1处出现了P-O振动吸收峰,说明有P043-或HPO42-或H2PO4-的吸收,从而验证了有磷酸根离子作为附加阴离子进入水滑石层间,并以水滑石沉淀的形式从水中去除。
(3)材料用量1 ml,处理2 mg/L的40 mL含磷废水,处理时间1 h,此时Mn-Fe-LDH、Mg-Mn-LDH、Ca-Fe-LDH对磷去除率分别达到97.41%、82.41%和97.00%。
(4)吸附体系的pH值对材料除磷效果影响较小。Langmuir模型能够很好的描述材料对含磷废水的吸附过程,Mn-Fe-LDH、Mg-Mn-LDH、Ca-Fe-LDH三种材料除磷的最大饱和吸附容量分别为6.18 mg/g、35.29 mg/g、25.50 mg/g。
(5)共存离子对材料的除磷效果有不同程度的影响。随着氯离子浓度的增大,Mg-Mn-LDH对磷的去除率明显降低,Ca-Fe-LDH和Mn-Fe-LDH对磷的去除率则变化不大。随着硫酸根离子浓度的增大,Ca-Fe-LDH对磷的去除率变化不大,Mn-Fe-LDH对磷的去除率有所增大,Mg-Mn-LDH对磷的去除呈先增大后减小趋势。腐植酸的存在会严重阻碍水滑石对磷的吸附。
利用水滑石处理含磷废水,操作工艺简单,去除磷效果好,近年来在解决水体富营养化方面逐渐成为研究热点。本实验合成液态未分离水滑石作为吸附剂吸附废水中的磷,此方法省去了水滑石合成中复杂的固液分离和干燥操作,成本低,为含磷环境水的处理提供了新的思路。同时,本实验着重研究水滑石对低浓度含磷环境水的吸附效果,能更好的模拟富营养化水体,填补了国内外在此方面的研究空白,对开拓水滑石功能、开发水滑石新的应用领域具有重要意义。
At present, environmental pollution has become a very important issue affecting the livelihood. Nitrogen and phosphorus contained in industrial wastewater and domestic sewage, is the main cause of eutrophication in the water. Nitrogen, phosphorus and other pollutants exceeded will make water eutrophication. How to reduce emissions of nitrogen and phosphorus, has become an critical project to protect the water environment. In this research project, the phosphorus removal of simulated environmental water with phosphorus using LDH was mainly researched, the mechanism of action was preliminary analysised and the feasibility of its practical application was explored.
Layered double hydroxides (Layer Double Hydroxide, referred to as LDH), also known as hydrotalcite, anionic clay. Especially in the field of water treatment, LDH has a unique pore structure and exchangeable anions, absorption catalysis, higher acid and alkali properties and thermal stability, so LDH show a very wide range of applications. In this study, liquid LDH were prepared by double titration method. Production processes were as follows, in accordance with the established ratio of mixed salt solutions, two-titration, training, washing, static settlement, constant volume. LDHs (Mn:Fe=3:1,Mg:Mn=3:1, Ca:Fe=3:1)were prepared in this experiment. Surface morphology and adsorption mechanism were studyed via environmental scanning electron microscopy, FT-IR analysis. Besides, the feasibility was also studyed, with changing the adsorption time, pH and concentration of phosphorus in water and mixed with coexistence of inorganic anions and other factors to research the removal of phosphorus.
The following conclusions:
(1)The material had connected porous, developed pore structure, good crystallinity, liminated structure of a layered double hydroxide.
(2)Compare to LDH before adsorption,,after adsorption, Ca-Fe-LDH occurred the PO vibration absorption peak respectively IR 1132 cm-1,1068 cm-1 and 986 cm-1,Mg-Mn-LDH, occurred the PO vibration absorption peak respectively IR 1068 cm-1 and 1020 cm-1, Mn-Fe-LDH occurred the PO vibration absorption peak respectively IR 1068 cm-1 and 1014 cm-1,This indicated the absorption of PO433- HPO42- or H2PO4-, verified PO4or HPO4 or H2PO4 anion as an additional anion into the LDH interlayer, PO ions removed from the water in the form of LDH precipitation.
(3)Mn-Fe-LDH, Mg-Mn-LDH, Ca-Fe-LDH on phosphorus removal rate can reached 97.41%, 82.41%and 97.00% on conditiongs of material amount 1 ml,40 mL phosphorus wastewater of 2 mg/L, processing time 1 h.
(4)The pH of adsorption system, had little effect on the phosphorus removal.Langmuir model could well describe the material on the process of phosphorus adsorption, the maximum phosphorus adsorption capacity of three materials (Mn-Fe-LDH, Mg-Mn-LDH, Ca-Fe-LDH) were 6.18 mg/g, 35.29 mg/g,25.50 mg/g.
(5)Coexisting ions effected on phosphorus removal.With the increasing concentration of chloride ions, Mg-Mn-LDH significantly reduced the removal rate of phosphorus, Ca-Fe-LDH and Mn-Fe-LDH removal rate of phosphorus was not changed much. With the increasing concentration of sulfate ions, Ca-Fe-LDH removal rate of phosphorus changed little, Mn-Fe-LDH has increased the removal rate of phosphorus, Mg-Mn-LDH to phosphorus removal rate increased first and then decreased. Humic acid can hinder the adsorption of phosphorus.
Environmental water with phosphorus was treated by using LDH, simplicity in operation, better phosphorus removal.In recent years, it gradually becomed a hot research area in resolving the eutrophication. In this study, liquid unseparated LDH as adsorbents in wastewater phosphorus were synthesised. This method eliminated complex solid-liquid separation and drying operation in the prosess of LDH synthesis and low cost, which provided a new thinking.for the treatment of phosphorus in water.
引文
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