Al13形态在混凝中的作用机制

从铝的水解形态转化角度考察了铝盐在高碱度和高有机物浓度水体中的混凝行为.结果表明,铝盐的混凝效能是与混凝过程中的Al13含量成正比.高投药量时氯化铝(AlCl3)既可以有效调节水体pH值又能在混凝过程中原位水解产生较多的Al13形态,因而混凝效能要高于聚合氯化铝(PACl).在铝盐混凝中,调节pH值到6～7之间可以控制铝形态分布从而达到提高混凝效能和减少残留铝的目的.在调节pH值强化混凝的方法中使用传统铝盐的效果要好于无机高分子絮凝剂.     

铝系混凝剂优势形态分析及其混凝特性

聚合氯化铝（PACl）是常用的水处理混凝剂,在应用过程中通常表现出比传统铝盐更为优异的效果.研究表明,这种优异性能主要得益于其特殊的组成,特别是高分子聚合物Al₁₃和Al₃₀独特的物化特性.Al₁₃和Al₃₀是铝离子水解过程中的中间产物,在地球科学和环境化学等领域有着重要的研究价值.于水处理而言,二者的结构和分子特性是研究者关注的重点,大量研究基于此展开,很多重要的发现为实际应用奠定了基础.基于对PACl及其组成性质的研究,本文对PACl的混凝特性及其优势形态分子的分析进行了综合阐述.     

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.     

聚合氯化铝中纳米Al13电荷特性及其混凝效果

采用聚丙烯酰胺凝胶柱层析法分离纯化聚合氯化铝(PAC)中的Al₁₃形态,并采用Al-Ferron逐时络合比色法和ZATESIZER 3000HSA测定仪对分离所得纳米Al₁₃形态以及AlCl₃和PAC进行了分析表征和电荷特性的对比性研究;采用烧杯实验法对3个样品处理实际和模拟水样的混凝效果进行了对比性研究.Al-Ferron逐时络合比色法的结果表明,采用层析法分离可得到含量99%左右的纳米Al₁₃形态;电荷特性和混凝效果研究结果表明纳米Al₁₃形态较其它两者具有更好的除浊、除腐殖酸和脱色效果并且具有更强的电中和能力,因此Al₁₃形态是一种具有较高正电荷和较高的水解稳定性,在给水和废水处理中的一种较为有效的Al形态.     

Al13形态的凝胶层析分离及分离级分特性对比

采用聚丙烯酰胺凝胶柱层析法分离纯化聚合氯化铝(PAC)中的Al₁₃形态,并采用Al- Ferron逐时络合比色法、透射电镜(TEM)和ZATESIZER测定仪对分离纯化过程中所得3个级分进行了分析表征和电荷特性的研究;采用烧杯实验法对3个级分处理实际和模拟水样的混凝效果进行了对比性研究.Al- Ferron逐时络合比色法和TEM结果表明,在层析法分离中级分随着洗脱时间延长按分子的大小依次洗脱下来,因此截取中间组分即可得到含量95 %左右的纳米Al₁₃形态;电荷特性和混凝效果研究结果表明,第3个级分其他两者具有更好的除浊、除腐殖酸和脱色效果,并且具有更强的电中和能力,因此Al₁₃形态是一种具有较高正电荷和较高的水解稳定性以及宽的pH适用范围,在给水和废水处理中是一种较为有效的Al形态.     

聚合氯化铝中Alb形态去除腐殖酸的效果及机制研究

Al_b形态［Al₁₂AlO₄(OH)₂₄⁷⁺］是聚合氯化铝（polyaluminium chloride, PAC）水解-聚合作用中形成的一种粒度小、所带正电荷多、聚集程度高及分子量大的多核羟基配合物.本试验采用乙醇-丙酮混合沉淀法分离PAC溶液中各种铝形态,提纯出Al_b形态（Al_b絮凝剂）.研究投加量、pH及无机离子对Al_b絮凝剂处理腐殖酸模拟水样絮凝效果的影响,并利用光散射颗粒分析仪（PDA2000）测定Al_b絮凝剂对腐殖酸絮凝过程中絮体的形成与增长过程的动态变化,结合絮体的Zeta电位,对Al_b絮凝剂的絮凝机制进行了初步探讨.结果表明,当投加量为4.3～6.3 mg/L、pH值为3.0～6.0时,Al_b絮凝剂处理腐殖酸模拟水样达到最佳絮凝效果;NH⁺₄、SiO^2-₃、H₂PO^-₄的存在明显抑制其絮凝性能.絮凝动力学过程和絮体Zeta电位表明,Al_b絮凝剂在水处理中主要是通过电中和作用和吸附网捕卷扫作用共同起絮凝作用的.     

聚硅酸铁水解规律及混凝机理的探讨

以水玻璃、硫酸亚铁及氯酸钠为原料,用共聚法制备聚硅酸铁混凝剂(PSF),同时研究PSF的水解过程以及PSF与聚合硫酸铁(PFS)、复合铝铁(PFA)的微观品质(微观结构、形态尺寸及Zeta电位)及混凝性能,并结合水解形态分布及微观品质对PSF的混凝机理进行初步探讨.结果表明,PSF是由许多链节样物种连接而成的分维数很大的敞开式枝状结构,其平均粒径比PFS、PFA分别大近5、11倍,而PFS、PFA是由一些低分维数及尺寸很小的棒状或球状形态组成,PSF、PFS的Zeta电位相近,远远低于PFA(为PFA的1/20左右),PSF的形态尺寸及Zeta电位分布不均.在较宽的pH范围内(浊度为5.5～12 NTU,UV₂₅₄为5.5～10 cm^-1),PSF的混凝效果明显优于PFS、PFA.PSF在纯水中的水解可以代表在地表水中的水解过程.PSF具有的特征微观品质使其在不同pH值范围内具有不同的水解形态分布,导致混凝机理差异很大.在宽泛的pH范围内(53、Fe(OH)²⁺及Fe³⁺稳定存在于水体中,是PSF在较宽pH范围内具有优异混凝性能的根本原因,也是PSF同时具有增强电中和/脱稳及架桥混凝机理的内在原因.微观品质、水解形态分布及混凝效果的对比合理解释了电中和/脱稳是混凝的前提条件,架桥是必要条件,二者要紧密配合才能取得高效的混凝效果.     

共价键型硅铝复合絮凝剂的铝形态分布及其絮凝性能研究

利用3种硅烷偶联剂——正硅酸乙酯（TEOS）、二乙氧基二甲基硅烷（DEDMS）、γ氨丙基二乙氧基甲基硅烷（APDES）分别与氯化铝合成了共价键型硅铝复合絮凝剂,利用²⁷肁l NMR研究了其铝形态分布,并试验了其对腐殖酸配水的混凝效果.²⁷肁l NMR结果表明,硅源、碱化度（B茫i/Al摩尔比对铝形态都有影响.以TEOS为硅源的产品中,未检出的铝形态含量较多.而以APDES为硅源的产品中,Al₁₃玫暮拷细撸⑺鍿i/Al摩尔比的增大而增多.碱化度对3种产品中铝形态的影响相似,表现为Al单含量随着B弥档脑龃蠖档?当Si/Al摩尔比为0.4时,以TEOS为硅源的产品中一直未出现Al₁₃茫訢EDMS为硅源的产品在高B弥担?.5）下出现Al₁₃茫訟PDES为硅源的产品在低B弥担?.5）下即出现Al₁₃?混凝实验结果表明,在酸性条件下,以APDES为硅源的产品的最佳投药范围较宽,处理效果最好.而碱性条件下以TEOS为硅源的产品的处理效果略优于另外2种硅铝复合絮凝剂.     

铝盐混凝除砷影响因素及机制研究

铝盐混凝法被广泛应用于饮用水除砷工程.本研究选取三氯化铝(AlCl3)和富含Al13的聚合氯化铝(PACl)为絮凝剂,考察铝形态、pH值、腐殖酸(HA)以及共存阴离子对砷去除的影响与机制.结果表明,2种絮凝剂对As(Ⅲ)去除效能较低,对As(Ⅴ)去除率可达到近100%.pH影响混凝过程中铝形态分布,从而对铝盐混凝除砷效能产生重要影响.铝盐除砷效能与混凝过程中的Al13形态含量呈正相关关系.由于竞争吸附作用,HA和部分共存阴离子对砷的混凝去除产生负面影响.HA对混凝效能影响与絮凝剂投药量相关,投药量越低,则影响越大.PO34-和F-对混凝除砷效能影响显著,SiO23-、CO23-和SO24-对混凝除砷效能影响较小.本研究将对饮用水强化混凝去除原水中砷具有指导意义.     

Al13改性羟基磷灰石的除氟性能研究

为了提高羟基磷灰石（HAP）的除氟效果,采用化学沉淀法合成3种不同Al/Ca值的Al₁₃改性后的HAP吸附材料,并对其进行XRD、FTIR、SEM、BET等表征,考察吸附过程中pH的影响,同时通过吸附热力学、吸附动力学等探讨了其除氟性能.结果表明,Al₁₃-HAP材料比HAP更加疏松多孔,当Al/Ca=0.7时,比表面积增大到了137.2 m²·g^-1,孔容增大到0.8217 cm³·g^-1.FTIR结果表明,Al₁₃的掺入给吸附材料中带入了大量—OH.根据Al₁₃-HAP吸附F^-前后的表征,F^-主要通过配体交换取代Al₁₃-HAP中的—OH从环境中被去除.当Al/Ca=0.4时,Al₁₃-HAP最大除氟效果达到5.03 mg·L^-1;零电荷点pH_PZC为8.46,大于HAP的pH_PZC,具体表现为对天然水体pH值适用性较广.吸附过程与Langmuir吸附模型以及拟二级动力学模型契合度高,这也证实了化学吸附为主要作用,吸附热力学结果表明Al₁₃-HAP吸附氟是自发的吸热过程.     

Purification and characterization of Al13 species in coagulant polyaluminum chloride

Nano-Al₁₃ was separated and purified by four methods to investigate its characteristic, and was analyzed by Al-Ferron timed complexation spectrophotometer,²⁷ Al-NMR (nuclear magnetic resonance), and transmission electron microscopy (TEM). Coagulation efficiency of nano-Al₁₃, polyaluminum chloride (PAC), and AlCl₃ in synthetic water were also investigated by jar test. The dynamic process and aggregation state of kaolin suspensions coagulating with nano-Al₁₃, PAC, and AlCl₃ were also investigated. The experimental results indicated that the efficiency of gel column chromatography method was the highest for separating PAC solution with low Al concentration. Ethanol and acetone method was simple and could separated PAC solution with different Al concentrations, while silicon alkylation white block column chromatography method could separate PAC solution only with low Al concentration. The SO₄²−/Ba²⁺ displacement method could separate PAC solution with high Al concentration, but extra inorganic cation and anion could be introduced into the solution during the separation. The coagulation efficiency and dynamic experimental results showed that nano- Al₁₃ with a high positive-charged species was the main species of electric neutralization in coagulation process, and it could reduce the turbidity and increase the effective particles collision rate efficiently in coagulation process. Its coagulation speed and the particle size of coagulant formed were of greatest value in this study.     

不同铝形态去除水中腐殖酸的混凝特性

制备了碱化度为2.4、以Al13,为主要成分的聚合铝PAC-All13和碱化度为2.4、以Al30为主要成分的高聚聚合铝PAC-Al30.采用烧杯混凝实验,通过絮体颗粒生长、电中和能力、pH和混凝剂投量对混凝效果的影响,比较了PAC-Al30、PAC-Al13,和AIC3,混凝去除水中腐殖酸的行为,并考察了水中残留铝的含量.实验结果表明,3种混凝剂的絮体形成能力由强到弱为PAC-Al30>PAC-Al13>AlCl3.与AlCl3相比, PAC-Al13和PAC-Al30的适用pH范围更宽,为5.0～8.0.PAC-Al30和PAC-Al13,的电中和能力差别不明显;由于更强的吸附和架桥作用,在低投量下PAC-Al30表现出更好的混凝效果,而且PAC-Al30比AlCl3和PAC-Al13有更宽的有效投量范围,为0.08～0.64mmol/L.对于腐殖酸含量为10m/L的水样,在pH为7.0,投量为0.16mmol/L下, PAC-Al30对腐殖酸去除率达到98.5%,此时出水残留铝浓度为0.066mg/L.结果证实Al30是可用于水中腐殖酸去除的一种新型的混凝/絮凝活性成.     

从铝形态转化角度分析AlCl3的混凝性能

应用Ferron逐时络合比色法,从铝形态转化角度对AlCl₃混凝性能进行了研究. 结果表明,AlCl₃的混凝性能与其发生二次水解反应后水解产物形态中的Al_b所占比例成正比,而影响AlCl₃水解产物中Al_b所占比例的主要因素是体系中的pH. 混凝过程中的水系组成及浓度和AlCl₃投加量的不同均会引起体系pH变化,从而影响AlCl₃水解产物中Al_b所占比例,最终影响AlCl₃的混凝效果.AlCl₃在混凝过程中所表现出的水解程度大、产生H+多的特征,使其在高碱度体系和高浓度有机酸体系的污水处理中效率更高.      

Separating method and dynamic processes of Nano-Al13

In order to investigate the characteristics of pure Nano-Al₁₃, Nano-Al₁₃ was separated and purified from a series of poly-aluminum chloride (PAC) solutions which had the same Al₁₃ percentage but different total Al concentrations, by using column chromatography, ethanol-acetone resolving and SO²⁻ ₄/Ba²⁺ displacement. The Al₁₃ species yield was characterized by Al-ferron timed complexation spectrophotometry and ²⁷Al-NMR (nuclear magnetic resonance). The coagulation efficiency of Nano-Al₁₃, PAC and AlCl₃ in synthetic water was also investigated by Jar tests. The dynamic process and aggregation state of kaolin suspensions coagulating with Nano-Al₁₃, PAC and AlCl₃ were similarly investigated using a photometric dispersion analyzer 2000 (PDA2000). The experimental results indicated that the ethanol-acetone resolving method was simple and could separate the PAC solution at different concentrations, while column chromatography could separate PAC solutions at low concentrations. The SO₄ ²⁻/Ba²⁺ displacement method could separate PAC solutions at high concentrations. However, extra inorganic cation and anion could be added in the solution during separation. The coagulation efficiency and dynamic experimental results showed that Nano-Al₁₃ with high positive-charged species was effective in removing turbidity and color. The dynamic process results showed that Nano-Al₁₃ also had the best recovery capability after shearing compared with PAC and AlCl₃ because the Nano-Al₁₃ conformation is more effective in charge neutralization. Translated from Acta Scientiae Circumstantiae, 2005, 25(6): 767–772 [译自: 环境科学学报]     

Preparation of high concentration polyaluminum chloride with high content of Alb or Alc

A novel membrane distillation concentration method was used to prepare high concentration polyaluminum chloride (PACl) with high content of Al_b or Al_c. 2.52 mol/L PACl₁ with 88% Al_b and 2.38 mol/L PACl₂ with 61% Al_c were successfully prepared. Three coagulants, AlCl₃, PACl₁ and PACl₂ were investigated on their hydrolysis behavior and speciation under different conditions. The effects of pH and dilution ratio on Al species distribution were investigated by ferron assay. Experimental result showed that pH had a significant effect on Al species distribution for the three coagulants. Dilution ratio had little effects on Al_b and Al_c distribution in whole dilution process except the beginning for PACl₁ and PACl₂. The results indicated that transformation of Al depends largely on their original composition. AlCl₃ was the most unstable coagulant among these three coagulants during hydrolysis process. PACl₁ and PACl₂ with significant amounts of highly charged and stable polynuclear aluminum hydrolysis products were less affected by the hydrolysis conditions and could maintain high speciation stability under various conditions.     

不同铝聚合形态对聚合铝混凝效果的影响

通过氯化铝(铝单体或初聚物形态Ala)、高Alb含量聚合铝(中等聚合形态Alb)、高Alc含量聚合铝(铝溶胶等高聚合形态Alc)和工业PACl(不同聚合度铝的混合形态Alabc)对某水厂沉后水实际水样进行烧杯混凝实验,依据絮体生长状况、浊度、UV254、颗粒数和过滤指数等参数综合评价不同铝形态的混凝作用效果,从而得出铝的最佳混凝形态.结果表明,高Alb含量聚合铝对浊度去除较好;而高Alc含量聚合铝对于颗粒物和UV254的去除效果较佳.     

Synchronous removal of CuO nanoparticles and Cu2+ by polyaluminum chloride-Enteromorpha polysaccharides: Effect of Al species and pH

Copper oxide nanomaterials have been extensively applied and can have serious impacts when discharged into the aquatic environment, especially when complexed with humic acid (HA) to form composite contaminants. As an innovative recycled coagulant aid, Enteromorpha polysaccharides (Ep) were associated with polyaluminum chloride (PACl) (denoted as PACl-Ep) to simultaneously remove CuO nanoparticles, Cu²⁺ and HA in this study. The influence of different Al species coagulants (AlCl₃, PACl_b and PACl_c) and water pH on coagulation performance, floc properties and reaction mechanisms was investigated in detail. Results showed that in the three PACl-Ep systems, PACl_b-Ep gave the highest removal efficiencies for turbidity and Cu²⁺, and the best UV₂₅₄ removal effect was reached by using PACl_c-Ep. Higher contents of Al_b and Al_c contributed to great coagulation performance because of their stronger bridging and sweeping effects. For all the Al species coagulants, alkalescent conditions were more conducive to removing Cu and HA compared to acidic conditions. Additionally, smaller and more agminated flocs with great recovery ability were formed by PACl_b-Ep and PACl_c-Ep systems (bridging and enmeshment effects cooperated with the chelated reticular structure formed by the Ep and Al species). Similarly, due to the increased hydrolysis and hydroxide precipitates, flocs formed under the condition of alkalescence were smaller, denser and stronger compared with weakly acidic conditions.     

铝盐混凝剂的混凝效果与残留铝含量和组分之间的关系研究

研究了氯化铝、硫酸铝、聚合氯化铝(poly-aluminum chloride, PAC)3种铝盐混凝剂在腐殖酸-高岭土模拟水样中的应用,以比较3种混凝剂在该水样中的混凝效果与残留铝含量和组分之间的关系.结果表明, 3种铝盐混凝剂在试验选取的投加量下对浊度和UV254的去除率最高可达90%左右,PAC能在较高的投加量下达到较好的混凝效果;较高投加量下PAC混凝沉淀出水中残留总铝含量为0.9 mg/L左右,余铝率为-3.0%左右,均明显低于传统的铝盐混凝剂;3种混凝剂混凝处理腐殖酸-高岭土模拟水样时,残留铝均大部分以溶解性总铝的形式存在,且溶解性有机铝在总溶解性铝中所占比例较大;PAC在腐殖酸-高岭土混凝沉淀出水中残留总铝的含量下降最快,且能够有效降低出水中毒性较大的溶解性铝的含量,其混凝沉淀出水中残留总溶解性铝含量为0.6 mg/L左右.