聚合铝混凝过程研究:不同形态硅酸的影响作用

研究了不同形态硅酸对聚合铝混凝过程的影响作用 .实验结果表明经预制形成的具有不同形态分布组成的硅酸与聚合铝 ,在投加后相互间发生了十分复杂的物理化学作用 ,并受溶液pH值的影响 ,从而最终决定了混凝效果 .反应过程中所生成的形态产物及其物化特征 ,很大程度上取决于聚合铝碱化度以及所投加的Si Al比 .其中碱化度越高 ,最终产物所带电荷越高 .而不同硅酸所起影响作用分别取决于聚合程度 ,在与聚合铝反应过程中表现出一定的规律性 .单体硅酸与单体铝迅速发生较强的络合作用 ,抑制了多聚水解铝阳离子的形成 .聚合硅酸则倾向于与聚合铝形态相互作用形成一定的胶状化合物 ,从而在溶液中稳定存在 .对于胶体硅酸 ,在聚合铝作用下迅速凝聚形成更大的聚集体 ,在颗粒物间架桥形成粗大的絮体 .所得结果对混凝机理的解释与复合混凝剂的发展提供了一定的参考作用     

混凝沉淀过程中铝系混凝剂的形态转化规律

研究了模拟配水中硫酸铝和氯化铝2种传统铝凝聚剂和2种聚合氯化铝(PAC)絮凝剂在混凝过程中的形态转化规律以及原水浊度和溶解性有机碳(DOC)对残余铝形态分布的影响.结果表明,在低浊体系中,投加铝系混凝剂是导致出水余铝升高的主要原因;但在高浊体系中,铝系混凝剂,尤其是聚合铝具有一定的除铝功能;混凝沉淀过程中传统铝凝聚剂的残余铝总量明显高于聚合铝混凝剂的残余铝总量;聚合铝混凝剂的残余铝全部为悬浮态铝,传统铝混凝剂的残余铝中还存在着胶体态铝和溶解态铝.原水浊度和DOC浓度增加,会提高残余铝中胶体态铝和溶解态铝的含量.     

水体中Cr (Ⅵ)对不同混凝剂混凝过程的影响

研究了工业废水中Cr(Ⅵ)在不同颗粒物浓度影响下对不同铝形态混凝剂的影响过程,通过考察浊度去除率以及出水余铝、余铬浓度甄别了混凝效率,并利用混凝过程中剩余p H值、Zeta电位以及絮体性质揭示水中Cr(Ⅵ)在不同浊度下的混凝机制.结果表明,在低浊度条件下,Cr(Ⅵ)对高聚合态Alb的混凝过程具有较大影响,而对低聚合态Ala无明显影响;在高浊度条件下,水中浊度较高时颗粒物会吸附部分Cr(Ⅵ)从而降低其与Alb之间的作用.Alb在混凝中主要发挥电中和作用,其对颗粒的脱稳和絮体的再生具有重要的作用,Ala水解形成的部分Alc在混凝中主要发挥架桥网捕作用,其对絮体的生产和强度因子具有重要作用.同时Cr(Ⅵ)的存在会增强Al13絮体的强度因子,但其消耗了部分正电荷会导致絮体恢复因子降低.     

纳米复合聚硅酸铝的颗粒粒度效应:Al_(13)与氧化硅的相互作用及其混凝特征

为了研究纳米复合聚硅酸铝(PASC)混凝剂的颗粒粒度效应,以实验室提纯的Al13溶液和活化水玻璃为原料,制备一系列不同粒度分布的PASC.以Al-Ferron法测定的铝水解形态表明,在该混凝剂中,Al13作为混凝优势形态具有较好的稳定性.氧化硅聚集度的测定和粒度分析结果表明,活化硅酸的加入能显著提高混凝剂的平均粒度,同时,Si/Al比(物质的量比)是影响平均粒度的主要因素.在活化硅酸不过量的前提下,Si/Al比和混凝剂的平均粒度呈正相关.混凝实验结果表明,在保证电中和能力的前提下,混凝剂的颗粒粒度越大,混凝剂的除浊能力越强.     

高浓度聚硅氯化铝(PASC)中铝的水解-聚合特性研究

以铝酸钠为碱化剂,采用缓慢滴碱法合成了高浓度(2.0mol.L-1左右)具有不同Si/Al摩尔比的聚硅氯化铝复合混凝剂(PASC).采用Al-Ferron逐时络合比色法、碱式滴定法和红外光谱分析,研究了铝的形态分布、水解-聚合历程及铝硅间的相互作用.实验结果表明,Al-Ferron络合动力学符合At=A0+A1[1-exp(-kb1t]+A2[-exp(-kb2t)];在PASC中,硅酸钠和铝的水解产物间存在着相互作用,这种作用对铝的水解-聚合历程和形态分布有不同程度的影响.用铝酸钠制备PASC时有利于Al的形态由低聚物向中、高聚物转化,且随着PASC中Si/Al比的增加生成多核羟铝配合物的能力逐渐增强.     

活性羟基铝聚合体形态的Al-Ferron反应动力学与核磁共振光谱分析

依据不同形态结构铝与Ferron络合反应动力学差异,采用A1-Ferron络合反应动力学曲线拟和计算模式将不同温度下(25℃和80℃)制备的不同碱化度(B=0.5～2.5)的羟基聚合铝溶液中羟基铝分成单体铝(A1a)、活性羟基聚合铝(A1b)和惰性凝胶高聚体铝(A1c)3种形态.此外,结合NMR光谱,Alb进一步分成六圆环结构的快速反应聚合铝(Alb1)和以Al13为主体的慢速反应聚合铝(Alb2).A1bl和Alh2与Ferron络合反应动力学差异明显,动力学常数分别为(1-3)×10-2和(0.6～3)×10-3.Al-Ferron络合反应动力学拟和计算模式可替代核磁共振光谱对溶液中的Al13含量进行测定分析.     

利用凝胶层析分离测定胶体态铝和溶解态铝的研究

利用凝胶层析柱分别对高浓度(5.4g·L-1)和低浓度(0.27mg·L-1)的聚合氯化铝溶液和氯化铝溶液进行了层析分离,测定了洗脱流出液的电导率和pH值,并采用Al-Ferron逐时络合比色分析了洗脱流出液中的铝形态分布.结果表明,高浓度和低浓度铝水样中的胶体态铝和溶解态铝浓度均可采用凝胶层析法进行分离测定.利用凝胶层析装置对2.5mL铝水样以1mL·min-1的速度进行洗脱,40～60mL间的洗脱流出液即为胶体态铝,剩余部分为溶解态铝.     

聚硅氯化铝混凝剂中Al(Ⅲ)水解聚合历程及铝硅作用特性研究

采用共聚与复合两种制备工艺，制备出了系列具有不同碱化度和不同Ａｌ／Ｓｉ摩尔比的聚硅氯化铝混凝剂，分析研究了ＰＡＳＣ中Ａｌ（Ⅲ）的水解－聚合历程以及聚硅酸与铝水解聚合产物的相互作用，探讨了ＰＡＳＣ溶液的酸解聚。     

聚合铝形态分布特征及转化规律

采用多种实验方法,对Al(Ⅲ)的水解—聚合—沉淀反应特征及其转化规律、形态分布及规范分子量大小进行了研究,同时应用X-射线衍射光谱仪和红外光谱仪对聚合铝形态进行了表征。由研究结果似可推断,Al(Ⅲ)水解—聚合过程的形态转化过程为线型→环型→体型。其聚合形态分布取决于翔/铝比值或pH值以及其它因素。在一定羟/铝比值时,聚合铝溶液中可划分为三种类型的形态分布。提出了相应的形态转化模式来表达聚合铝的形态及转化规律。     

PSAA水溶液中铝形态分布研究

PSAA是一种含有铝离子的聚硅酸絮凝剂。本文用²⁷Al－NMR法和Al－Ferron逐时络合比色法研究了PSAA水溶液中铝的形态分布情况,考察了SiO₂/Al³⁺摩尔比,温度及稀释作用对铝的形态分布的影响。结果表明,PSAA水溶液中的铝主要是以单核羟铝络合物形式存在,聚硅酸的存在对铝的形态分布影响不大,温度对铝的形态分布无影响,稀释作用对铝的形态分布有一定的影响。     

Deposition behavior of residual aluminum in drinking water distribution system: Effect of aluminum speciation

Finished drinking water usually contains some residual aluminum.The deposition of residual aluminum in distribution systems and potential release back to the drinking water could significantly influence the water quality at consumer taps.A preliminary analysis of aluminum content in cast iron pipe corrosion scales and loose deposits demonstrated that aluminum deposition on distribution pipe surfaces could be excessive for water treated by aluminum coagulants including polyaluminum chloride（PACl）.In this work,the deposition features of different aluminum species in PACl were investigated by simulated coil-pipe test,batch reactor test and quartz crystal microbalance with dissipation monitoring.The deposition amount of non-polymeric aluminum species was the least,and its deposition layer was soft and hydrated,which indicated the possible formation of amorphous Al（OH）₃.Al₁₃ had the highest deposition tendency,and the deposition layer was rigid and much less hydrated,which indicated that the deposited aluminum might possess regular structure and self-aggregation of Al₁₃could be the main deposition mechanism.While for Al₃₀,its deposition was relatively slower and deposited aluminum amount was relatively less compared with Al₁₃.However,the total deposited mass of Al₃₀ was much higher than that of Al₁₃,which was attributed to the deposition of particulate aluminum matters with much higher hydration state.Compared with stationary condition,stirring could significantly enhance the deposition process,while the effect of pH on deposition was relatively weak in the near neutral range of 6.7 to 8.7.     

酸性铬深蓝-示波吸附计时电位法快速测定土壤溶液中不同形态铝

报道了酸性铬深蓝-示波吸附计时电位法分别在酸性和碱性条件下直接检测土壤溶液中的无机单核铝[AIi]和总单核铝[AIa]浓度，并用该法测定了酸消化水样中的总铝[AIT]．由[AI8]-[AIi]间接得到有机单核铝[AIo]，[AIT]-[AIa]得到酸溶态铝[AIr]，从而实现了土壤溶液中5种AI形态的电化学测定测定了十多个实际土壤水样，与Driscoll方法所获结果进行了对照，结果基本一致。     

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.     

Effects of alkalinity on interaction between EPS and hydroxy-aluminum with different speciation in wastewater sludge conditioning with aluminum based inorganic polymer flocculant

Extracellular polymeric substances (EPS) form a stable gel-like structure to combine with water molecules through steric hindrance, making the mechanical dewatering of wastewater sludge considerably difficult. Coagulation/flocculation has been widely applied in improving the sludge dewatering performance, while sludge properties (organic fraction and solution chemistry conditions) are highly changeable and have important effects on sludge flocculation process. In this work, the alkalinity effects on sludge conditioning with hydroxy-aluminum were comprehensively investigated, and the interaction mechanisms between EPS and hydroxy-aluminum with different speciation were unraveled. The results showed that the effectiveness of hydroxy-aluminum conditioning gradually deteriorated with increase in alkalinity. Meanwhile, the polymeric hydroxy-aluminum (Al₁₃) and highly polymerized hydroxy-aluminum (Al₃₀) were hydrolysed and converted into amorphous aluminum hydroxide (Al(OH)₃), which changed the flocculation mechanism from charge neutralization and complexing adsorption to hydrogen bond interaction. Additionally, both Al₁₃ and Al₃₀ showed higher binding capacity for proteins and polysaccharides in EPS than monomeric aluminum and Al(OH)₃. Al₁₃ and Al₃₀ coagulation changed the secondary structure of proteins in EPS, which caused a gelation reaction to increase molecular hydrophobicity of proteins and consequently sludge dewaterability. This study provided a guidance for optimizing the hydroxy-aluminum flocculation conditioning of sludge with high solution alkalinity.     

聚硅氯化铝(PASC)混凝剂的颗粒大小及分子量分布

采用共聚与复合两种制备工艺,研制出碱化度（B） 为2.0 的具有不同 Al/Si 摩尔比的聚硅氯化铝（ 简称 PASC） 混凝剂．一种方法是将 NaCl加入到不同 Al/Si摩尔比的 AlCl₃6H₂O和聚硅酸混合液中;另一种方法是按一定的Al/Si 摩尔比将聚硅酸加入到聚合氯化铝液中．应用光子相关光谱（PCS） 和超滤膜过滤方法对 PASC 及聚合氯化铝（PAC） 的颗粒大小及分子量分布进行对比测定．结果表明,在PASC中,由于聚硅酸与铝水解聚合产物间的相互作用,生成了聚集体更大的聚合物,显著提高了聚集体的粒径,这种提高以共聚法最为明显; Al/Si摩尔比影响PASC的聚集度,Al/Si摩尔比越小, PASC 的聚集度就越大．     

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.     

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.     

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.