Effects of fluoride on the removal of cadmium and phosphate by aluminum coagulation

This study focuses on the effects of p H and fluoride at different molar ratios of fluoride to Al(R F:Al) on the removal of cadmium(Cd~(2+)) and phosphate by Al coagulation. Fluoride at R F:Al≥ 3:1 inhibits the removal of Cd over wide Al dose ranges from 5 to 10 mg/L as Al. The removal of phosphate decreases significantly at high R F:Al of 10:1 whereas at lowered R F:Al(i.e., ≤ 6:1), an adverse effect is observed only at insufficient Al doses below 2 mg/L. Fluoride shows inhibitive effects towards the removal of Cd at p H 7 and 8 and that of phosphate at p H 6. Fluoride decreases the ζ-potential in both systems, and the decreasing extent is positively correlated to the elevated R F:Al. The Al fluoride interactions include the formation of Al–F complexes and the adsorption of fluoride onto Al(OH)_3 precipitates, i.e., the formation of Al(OH)n F m. Al–F complex formation inhibits Al hydrolysis and increases residual Al levels, and a more significant increase was observed at lower p H. Al–F complexes at high R F:Al complicate the coagulation behavior of Al towards both negative and positive ionic species. Moreover, fluoride at low R F:Al shows little effect on Al coagulation behavior towards Cd~(2+)and phosphate, and the spent defluoridation adsorbent,i.e., aluminum(Al) hydro(oxide) with adsorbed fluoride at R F:Al of below 0.1:1, may be reclaimed as a coagulant after being dissolved.     

铝盐混凝去除氟离子的作用机理探讨

在烧杯搅拌实验的基础上，通过絮体的ζ电位测定、X射线粉晶衍射、红外光谱、X射线光电子能谱等实验手段考察了铝盐混凝除氟的作用机理。结果表明，铝盐混除氟的主要作用机理有吸附、离子交换、络合沉降等。对于两种形态的铝盐，从除氟过程和机理上看，单体铝盐中的Al(H2O)6^3 形态要比聚合多中的聚羟铝阳离子形态更有利，因而总体除氟效果和比聚合铝要好。     

Effects of pre-ozonation on organic matter removal by coagulation with IPF-PACI

Ozone plays an important role as a disinfectant and oxidant in potable water treatment practice and is increasingly being used as a pre-oxidant before coagulation. The purpose of this study is to obtain insight into the mechanisms that are operative in pre-ozonized coagulation. Effects ofpre-ozonation on organic matter removal during coagulation with IPF-PAC1 were investigated by using PDA （photometric disperse analysis）, apparent molecular weight distribution and chemical fractionation. The dynamic formation of flocs during coagulation process was detected. Changes of aquatic organic matter （AOM） structure resulted from the influence of pre-ozonation were evaluated. Results show that dosage of O3 and characteristics of AOM are two of the major factors influencing the performance of O3 on coagulation. No significant coagulation-aid effect of O3 was observed for all experiments using either A1C13 or PAC1. On the contrary, with the application of pre-ozonation, the coagulation efficiency of A1C13 was significantly deteriorated, reflected by the retardation of floc formation, and the removal decreases of turbidity, DOC, and UV254. However, if PACl was used instead of AlCl3, the adverse effects of pre-ozonation were mitigated obviously, particularly when the O3 dosage was less than 0.69 （mg O3/mg TOC）. The difference between removals of UV254, and DOC indicated that pre-ozonation greatly changed the molecular structure of AOM, but its capability of mineralization was not remarkable. Only 5% or so DOC was removed by pre-ozonation at 0.6--0.8 mg/L alone. Fractionation results showed that the organic products of pre-ozonation exhibited lower molecular weight and more hydrophilicity, which impaired the removal of DOC in the following coagulation process.     

铁盐和铝盐混凝微滤工艺除As(V)的比较研究

选择FeCl₃和Al₂(SO₄)₃作混凝剂,采用小试规模的混凝微滤膜反应器比较了铁盐和铝盐混凝微滤工艺的除As(V)效果、相关性能指标及适用范围.结果发现,Fe³⁺投加量为4 mg/L、Al₂(SO₄)₃投加量为50 mg/L时,铁盐和铝盐工艺的除As(V)效果大致相当,均可使水中As(V)的浓度从100 μg/L左右降低到10 μg/L以下,最低为1.68 μg/L.出水浊度均小于0.1 NTU,出水中铁、铝和SO^2-₄浓度均符合饮用水标准.铁盐工艺出水pH值比原水大约高0.5,铝盐工艺处理前后水的pH值基本不变.反应器运行结束静沉24 h后,铁盐工艺浓缩比为1 791,是铝盐工艺的2.54倍,污泥中As(V)的含量也大大高于铝盐工艺,去除同等重量的As(V)所产生的污泥量较铝盐工艺少得多.因此,对于仅有砷超标的饮用水,应优先考虑铁盐工艺.按除氟所需混凝剂数量投加Al₂(SO₄)₃,铝盐工艺即可在去除As(V)的同时去除氟,铁盐工艺则不能去除氟.因此,对于砷和氟均超标的饮用水,可采用铝盐工艺同时去除砷和氟.     

初始pH值对连续投加铝盐混凝去除小分子有机物的影响机制

以污水厂二级出水中小分子有机物强化混凝去除为目的,提出了连续投加混凝工艺(CDC),并以水杨酸为模型小分子有机物,研究了初始pH值对CDC工艺去除效果的影响以及铝离子与水杨酸的络合特性.结果表明,初始pH值6时CDC工艺的去除率最高,比常规混凝工艺提升了13.8%.但是初始pH值5和7时CDC工艺的提升效果较小.三维荧光结果表明,不同pH值下水杨酸和铝离子的络合特性不同.X射线光电子能谱和电喷雾质谱结果表明,pH值5时CDC工艺前期主要生成1:1络合物Al(OH)(C₇H₄O₃)(H₂O)₂.其络合作用强烈,稳定性较高,难以从水中去除.pH值6时前期主要生成中等聚合铝(如原位Al₁₃),其与水杨酸形成的络合物可以参与到铝离子的生长过程,最终生成表面崎岖形态松散的珊瑚礁状絮体,强化了水杨酸的去除.pH值7时,主要生成不定形氢氧化铝,通过絮体表面吸附小分子有机物.     

Effects of Ca(OH)2 assisted aluminum sulfate coagulation on the removal of humic acid and the formation potentials of tri-halomethanes and haloacetic acids in chlorination

The effects of addition of calcium hydroxide on aluminum sulphate(or alum) coagulation for removal of natural organic matter(NOM) and its subsequent effect on the formation potentials of two major types of regulated disinfection byproducts(DBPs),haloacetic acids(HAAs) and trihalomethanes(THMs),have been examined.The results revealed several noteworthy phenomena.At the optimal coagulation pH(i.e.6),the coagulation behavior of NOM water solutions versus alum dose,showed large variation and a consequent great change in the formation potentials of the DBPs at certain coagulant doses.However,with addition of a relatively small amount of Ca(OH) 2,although the zeta potential of coagulated flocs remained almost the same,NOM removal became more consistent with alum dose.Importantly,also the detrimental effect of charge reversal on NOM removal at the low coagulant dose disappeared.This resulted in a steady decrease in the formation potentials of DBPs as a function of the coagulant dose.Moreover,the addition of Ca(OH) 2 broadened the pH range of alum coagulation and promoted further reduction of the formation potentials of the DBPs.The enhancement effects of Ca(OH) 2 assisted alum coagulation are especially pronounced at pH 7 and 8.Finally,synchronous fluorescence spectra showed that the reduction in DBPs formation potential by Ca(OH) 2-assisted alum coagulation was connected to an enhanced removal of small hydrophobic and hydrophilic HA molecules.Ca(OH) 2-assistance of alum coagulation appeared to increase substantially the removal of the hydrophilic HA fraction responsible for HAAs formation,prompting further reduction of HAA formation potentials.     

污泥水磷和有机物同步混凝去除的多目标优化技术研究

通过引入多响应值的归一化评分法进行了污泥水磷和有机物同步混凝去除的多目标优化,并利用响应面(RSM)技术考察了Al/P比、聚丙烯酰胺(PAM)投加量和悬浮固体(SS)浓度对污染物去除的单独效应和联合效应.结果表明,复合投加聚合氯化铝和PAM能同步去除污泥水中磷和有机物,并改善沉降效果.归一化后单目标RSM优化显示,对污泥水中磷和有机物同步去除的贡献为Al/P比SS浓度PAM投加量.在最优条件Al/P比为3、PAM浓度为1.22 mg·L~(-1)、SS浓度为3.58 g·~(L-1)的条件下,正磷和总有机碳去除率分别为93.1%和53.9%.与多响应变量优化相比,引入归一化评分法有效解决了变量间数值量级差异的问题,使结果的分析计算变得简单方便.     

Al与F的络合作用对土壤吸附Al和F的影响

研究了Al-F络合作用对土壤吸附Al和F的影响以及吸附前的溶液中铝化学形态的差异。提高Al或F的加入量将人别使分配在土壤溶液中的F或Al的数量增加，即Al-F络合作用地使Al和F在土壤固-液间的分配平衡向液相移动，土壤对Al-F络合物吸附程度很小，吸附前，3种不同F/Al比溶液中Al^3 ，AlF^2 的浓度随着F/Al比的增加逐渐降低，AlF2^ ,AlF3^0的浓度则逐渐升高，与土壤作用后，溶液中Al主要与AlF^2 ,AlF2^ 的形式存在，以AlF^2 的数量居多。     

Effect of AlCl3 concentration on nanoparticle removal by coagulation

In recent years, engineered nanoparticles, as a new group of contaminants emerging in natural water, have been given more attention. In order to understand the behavior of nanoparticles in the conventional water treatment process, three kinds of nanoparticle suspensions, namely multi-walled carbon nanotube-humic acid (MWCNT-HA), multi-walled carbon nanotube-N,N-dimethylformamide (MWCNT-DMF) and nanoTiO₂-humic acid (TiO₂-HA) were employed to investigate their coagulation removal efficiencies with varying aluminum chloride (AlCl₃) concentrations. Results showed that nanoparticle removal rate curves had a reverse “U” shape with increasing concentration of aluminum ion (Al^3 +). More than 90% of nanoparticles could be effectively removed by an appropriate Al^3 + concentration. At higher Al^3 + concentration, nanoparticles would be restabilized. The hydrodynamic particle size of nanoparticles was found to be the crucial factor influencing the effective concentration range (ECR) of Al^3 + for nanoparticle removal. The ECR of Al^3 + followed the order MWCNT-DMF > MWCNT-HA > TiO₂-HA, which is the reverse of the nanoparticle size trend. At a given concentration, smaller nanoparticles carry more surface charges, and thus consume more coagulants for neutralization. Therefore, over-saturation occurred at relatively higher Al^3 + concentration and a wider ECR was obtained. The ECR became broader with increasing pH because of the smaller hydrodynamic particle size of nanoparticles at higher pH values. A high ionic strength of NaCl can also widen the ECR due to its strong potential to compress the electric double layer. It was concluded that it is important to adjust the dose of Al^3 + in the ECR for nanoparticle removal in water treatment.     

混凝和强化混凝对印染废水中锑(Ⅴ)的去除特性

印染废水中锑的排放标准日趋严格,是印染废水处理面临的新挑战.以混凝和强化混凝去除印染废水中锑(Ⅴ)为目标,发现聚硫酸铁(PFS)混凝剂对印染废水中锑(Ⅴ)的去除效率显著优于铁铝复配混凝剂和铝盐混凝剂,去除效率达97.4%,出水锑(Ⅴ)浓度可达4μg·L~(-1).酸性条件(低水解度)有利于PFS生成Fe(a)活性组分和静电吸引、锑(Ⅴ)迁移,且絮体颗粒较小,促进PFS混凝除锑(Ⅴ)效率;酸性条件下PFS除锑(Ⅴ)效率是中性条件的1.27倍,处理出水中锑(Ⅴ)浓度仅为中性条件的33.3%.PFS投加量与除锑(Ⅴ)效率符合反比例模型.在较高锑(Ⅴ)浓度下,提升PFS投加量可提高除锑(Ⅴ)效率,但在较低锑(Ⅴ)浓度下,提升PFS投加量对除锑(Ⅴ)效率的促进较小.PFS絮体回流与混凝沉淀串联或耦合可显著提升印染废水中锑(Ⅴ)的去除效率,其除锑(Ⅴ)效率分别是单一PFS混凝沉淀的1.14倍和1.32倍,可有效降低出水锑(Ⅴ)浓度并节约PFS投加量和减少污泥生成量.其中混凝-絮体回流耦合工艺中,最佳絮体回流比例为100%.