Interaction of PACls with sulfate

IntroductionPolyaluminumchloride (PACl)asamainkindofinorganicpolymerflocculantsisanewhighereffectivewaterandwastewatertreatmentreagent.Basedonthetraditionallow molecularaluminum ,ithasbeendevelopedworldwidesincethe 196 0s(Tang,1994 ;1990 ;1987) .PAClistheintermediateproductofthehydrolysis polymerization ageingprocessofAl(III)undersuitableconditions.Atpresent,itisgenerallyknownthattherearemanypossiblespeciesexistintheAl(III)solution ,suchasmonomers,oligomers,Al13 [AlO4Al12 (OH) 2 4(H2 …     

硫酸根离子与聚合铝的反应过程及其产物形态

对不同Al/SO2-4比及碱化度条件下PACl与SO₄^2-的反应过程进行研究,分析了体系中总铝浓度及形态分布变化规律,测定了各沉淀/结晶产物的组成,并对其形貌进行了扫描电镜观察.实验结果表明:碱化度对PACl/SO₄^2-反应体系有较大影响,随着碱化度(B值)的增加,沉淀/结晶的析出速率加快,结果析出物中OH含量逐渐增加,而SO₄^2-/Al比率从0.45～0.30逐渐降低.各聚合铝水解形态与SO₄^2-反应速率上存在明显差异,从而为其混凝优势形态的分离纯化创造了条件.     

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 Alb or Alc. 2.52 mol/L PACl1 with 88% Alb and 2.38 mol/L PACl2 with 61% Alc were successfully prepared. Three coagulants, AlCl3, PACl1 and PACl2 were investigated on their hydrolysis behavior and speciation under di erent conditions. The e ects of pH and dilution ratio on Al species distribution were investigated by ferron assay. Experimental result showed that pH had a significant e ect on Al species distribution for the three coagulants. Dilution ratio had little e ects on Alb and Alc 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 a ected by the hydrolysis conditions and could maintain high speciation stability under various conditions.     

Effect of in-situ formed Al hydrates through long-term aging on enhanced particle destabilization by PACl coagulation

Aging of polyaluminum chloride (PACl) coagulants could significantly influence hydrolyzed Al speciation ruling coagulation performance. The goal of this study was to investigate Al species transformation through long-term aging and its impact on coagulation performance. Two kinds of commercial coagulants (PACl-1 and PACl-2) were stored for in-situ aging tests in six months to evaluate Al species variation with time and the performance of coagulation with natural turbid waters. The results showed that CaSO₄ precipitation easily occur in a commercial PACl coagulant with time as it contains SO₄^2? and Ca²⁺. It also activates the precipitation of gibbsite Al(OH)₃ in PACl with aging. Through 180 days aging, both monomeric Al (Al_a) and polymeric Al (Al_b) substantially transform into colloidal Al (Al_c) and precipitated for both PACl coagulants. At low turbidity (10 NTU), PACl-1 has a superior turbidity reduction rate than PACl-2, while PACl-2 performs a little better turbidity reduction at high turbidity (1000 NTU) regardless of aging time. With aging time, an obvious decrease in turbidity reduction for PACl-1 coagulation is observed at low turbidity of 10 NTU, while the improvement in turbidity reduction for PACl-2 coagulation by enhanced sweep flocculation can be achieved as Al_b mostly transform into Al_c after 150 days aging. It is concluded that dominant in-situ formed Al_c after a long time hydrolysis can improve PACl coagulation efficiency in turbidity reduction by enhanced sweep flocculation, especially for low turbidity water, but the increase in preformed Al_c in PACl would worsen particle destabilization after aging.     

化学沉淀分离-置换法提纯Al13的工艺研究

采用AlCl₃溶液和Na₂CO₃粉末在不同温度下制备了不同浓度的聚合氯化铝(PACl). 以选定的中等浓度、高Al₁₃含量的PACl为原液,研究了Al₁₃与硫酸盐沉淀反应过程中SO₄/Al摩尔比、反应体系起始总铝浓度的影响以及Al₁₃硫酸盐与Ba(NO₃)₂置换反应过程中的Ba/SO₄摩尔比、超声、温度等因素的影响. 实验结果表明,在制备温度为50℃条件下,浓度在0.4～0.6　mol/L范围的PACl含有较高的Al₁₃. 沉淀分离反应的最佳SO₄/Al摩尔比为0.6∶1;生成的 Al₁₃硫酸盐沉淀物为正四面体状晶体. 在Al₁₃硫酸盐与Ba(NO₃)₂溶液置换反应过程中,Ba/SO₄的最佳摩尔比为1∶1,反应温度及超声作用对置换反应的影响较小;提高Ba(NO₃)₂的起始浓度可以得到相应较高浓度的纯化Al₁₃溶液. 所得Al₁₃纯度的统计平均值为92.1％.     

Al(Ⅲ) speciation distribution and transformation in high concentration PACl solutions

Effects of Al(Ⅲ) concentration and pH on the speciation of Al(Ⅲ) in polyaluminum chloride (PACl) solutions especially on the Al13 fraction were investigated. A series of PACl samples were prepared over the range of Al(Ⅲ) concentration from 0.01 to 2.0 mol/L with the B (OH/Al ratio) value from 1.0 to 2.5 by forced hydrolysis of AlCl3. The samples were characterized by ferron assay,pH and 27Al NMR. It was shown that the Al(Ⅲ) concentration had a dramatic effect on the hydrolysis processes and the species distribution of PACl was in relate to the decrease of pH. The fraction of Al species, Alb (or Al13) decreased and Alc increased with increase of total Al(Ⅲ) concentration. Under the condition of Al(Ⅲ) 2.0 mol/L, B = 2.5, the pH value was 2.73 and no Al13 could be detected. During diluting and aging, the species distribution evolved. The Al13 could then be detected again and the amounts increased with time. If the diluted samples were concentrated by freeze dry at -35℃ or heating at 80℃, the pH value and Al13 content would decrease with the increased concentration. It demonstrated that the key factor for formation of Al13 in concentrated PACl was pH value.     

Al(Ⅲ) speciation distribution and transformation in high concentration PACl solutions

Effects of Al（Ⅲ） concentration and pH on the speciation of Al（Ⅲ） in polyaluminum chloride （PACl） solutions especially on the Al13 fraction were investigated. A series of PACl samples were prepared over the range of Al（Ⅲ） concentration from 0.01 to 2.0 mol/L with the B （OH/Al ratio） value from 1.0 to 2.5 by forced hydrolysis of AICl3. The samples were characterized by ferron assay, pH and 27^Al NMR. It was shown that the Al（Ⅲ） concentration had a dramatic effect on the hydrolysis processes and the species distribution of PACl was in relate to the decrease of pH. The fraction of Al species, Alb （or Al13） decreased and Al0 increased with increase of total Al（Ⅲ） concentration. Under the condition of Al（Ⅲ） 2.0 reel/L, B = 2.5, the pH value was 2.73 and no Al13 could be detected. During diluting and aging, the species distribution evoIved. The Al13 could then be detected again and the amounts increased with time. If the diluted samples were concentrated by freeze dry at -35℃ or heating at 80℃, the pH value and Al13 content would decrease with the increased concentration. It demonstrated that the key factor for formation of Al13 in concentrated PACl was pH value.     

Chemical species distribution and transformation in polyaluminum chemical solutions

The hydrolysis polymerization precipitation process of Al(III) was studied with pH titration method, and the prepared polyaluminum solutions were characterized by various experimental methods: acid depolymerization, timed complex-colorimetric procedure, ultrafiltration, X-ray diffraction and infrared absorption spectrum. The results showed that the chemical species transformation and distribution of Al(III) in the hydrolysis-polymerization process depended on B=(OH/Al) ratio, pH and other factors. By their structures, the chemical species can be divided into three categories of monomeric (Ala), polymeric (Alb), sol or gel precipitates (Alc) and the polymeric species may be further divided into three groups such as linear low polymer (Alb1), linear high polymer (Alb2) and high polymer with cyclic structure (Alb3). The nominal molecular weight of polymeric species obtained by ultrafiltration was about 1000-50000 and most of them failed into a range around 10000. A scheme for the chemical speciation model     

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。     

Preparation and characterization of organic polymer modified composite polyaluminum chloride

Compared with traditional aluminum salts, polyaluminum chloride （PACI） has better coagulation-flocculation performance in turbidity removal. However, it is still inferior to organic polymers in terms of bridging function. In order to improve the aggregating property of PACl, different composite PACl flocculants were prepared with various organic polymers. The effect of organic polymer on the distribution or Al（Ⅲ） species in composite flocculants was studied using ^27TAl NMR and Al-ferron complexation methods. The charge neutralization and surface adsorption characteristics of composite flocculants were also investigated. Jar tests were conducted to evaluate the turbidity removal efficacy of organic polymer modified composite flocculants. The study shows that cationic polymer and anionic polymer have significant influences on the coagulation-flocculation behaviors of PACl. Both cationic and anionic polymers can improve the turbidity removal performancc of PACl but the mechanisms arc much different： cationic organic polymer mainly increases the charge neutralization ability, but anionic polymer mainly enhances the bridging function.     

Hydrolyzed Al(Ⅲ) clusters: Speciation stability of nano-Al13

Pure nano-Al13 and aggregates at various concentrations were prepared to examine the particle size effect of coagulation with inorganic polymer fiocculant. The property and stability of various species formed were characterized using Infrared, 27Al-NMR,photo correlation spectroscopy (PCS), and Ferron assay. Results showed that concentration and temperature exhibited different roles on the stability of Al13. The quantity of Alb species analyzed by ferron assay in the initial aging period corresponded well with that of Al13, which has been confirmed in a dimension range of 1-2 nm by PCS. Al13 solutions at high concentrations (0.5-2.11 mol/L)were observed to undergo further aggregation with aging. The aggregates with a wide particle size distribution would contribute to the disappeared/decreased Al13 basis on the 27Al-NMR spectrum, whereas a part of Al13 would still remain as Alb. At low concentrations,Al13 solution was quite stable at normal temperature, but lost its stability quickly when heating to 90°C.     

Hydrolyzed AI（Ⅲ） clusters： Speciation stability of nano-All3

Pure nano-Al13 and aggregates at various concentrations were prepared to examine the particle size e ect of coagulation with inorganic polymer flocculant. The property and stability of various species formed were characterized using Infrared, 27Al-NMR, photo correlation spectroscopy (PCS), and Ferron assay. Results showed that concentration and temperature exhibited di erent roles on the stability of Al13. The quantity of Alb species analyzed by ferron assay in the initial aging period corresponded well with that of Al13, which has been confirmed in a dimension range of 1–2 nm by PCS. Al13 solutions at high concentrations (0.5–2.11 mol/L) were observed to undergo further aggregation with aging. The aggregates with a wide particle size distribution would contribute to the disappeared/decreased Al13 basis on the 27Al-NMR spectrum, whereas a part of Al13 would still remain as Alb. At low concentrations, Al13 solution was quite stable at normal temperature, but lost its stability quickly when heating to 90°C.     

聚合氯化铝镁钛的制备及结构表征

为提高铝基复合混凝剂的混凝效果,以AlCl₃、MgCl₂、TiCl₄为原料,通过共聚反应制备出无机复合高分子混凝剂PCAMT（聚合氯化铝镁钛）,并探究其混凝机理.采用Ferron（高铁试剂）逐时络合比色法、红外光谱、X-射线衍射谱图、扫描电镜与能谱分析（SEM-EDS）、Zeta电位对产物的Al形态、结构形貌、组成及混凝机理进行分析.结果表明:①采用单因素试验法获得最佳合成条件,即反应温度为60 ℃,Mg/Al（摩尔比,下同）为0.5,Ti/Al（摩尔比,下同）为0.5,OH/（Al+Mg+Ti）（摩尔比,下同）为0.6.②形态分析表明,反应温度、Mg/Al、Ti/Al,OH/（Al+Mg+Ti）对Al的形态分布均存在影响.随着反应温度的升高,n（Ala）（Ala在Al的水解聚合形态中所占摩尔分数,下同）先减后增,n（Alb）（Alb在Al的水解聚合形态中所占摩尔分数,下同）先增后减,n（Alc）（Alc在Al的水解聚合形态中所占摩尔分数,下同）逐渐减小;随着Mg/Al的增大,n（Ala）先减后增,n（Alb）、n（Alc）为先增后减的趋势;随着Ti/Al的增大,n（Ala）逐渐增加,n（Alb）逐渐减少,n（Alc）先增后减;随着OH/（Al+Mg+Ti）的增大,n（Ala）逐渐减少,n（Alb）、n（Alc）逐渐增加.③通过红外光谱、X-射线衍射,确定了PCAMT的结构组成,表明PCAMT是一种—OH桥联的铝镁钛复杂无定型聚合物,含有Al—OH—Mg与Ti—O—Ti新基团以及形成了Mg_1.5Ti_1.25O₄、Mg_1.2Ti_1.8O₅、Al₃Ti₅O₂等共聚物.④扫描电镜与能谱结果表明,PCAMT呈紧凑的空间立体网状形貌结构,利于发挥吸附架桥、网捕卷扫作用.⑤由PCAMT投加量对Zeta电位的影响分析可知,低投药量的混凝过程中起主导作用的是电中和作用,高投药量PCAMT处理原水的混凝机制以吸附架桥和网捕卷扫作用为主.研究显示,AlCl₃、MgCl₂和TiCl₄通过共聚反应,可生成具有更高聚合度的无定型共聚物PCAMT,利于电中和、吸附架桥和网捕卷扫,具有较好的混凝效果.      

新型絮凝剂聚合氯化铝钙中铝形态表征及钙含量测定

以Al2O3和CaCO3为原料经高温焙烧酸溶制备工艺合成新型高效絮凝剂——聚合氯化铝钙。采用Al-Ferron逐时络和比色法研究产品中的铝形态;络合滴定法研究钙含量。结果表明:焙烧工艺对钙含量的影响较大,酸溶工艺对钙含量的影响较小。在最佳配比条件下,生成的Alb为最佳;焙烧温度提高Ala、Alc含量减小,Alb含量增大;增长酸溶反应时间Alb含量减少;增加酸用量,Ala、Alc含量减少,Alb含量增大。     

Preferential binding between intracellular organic matters and Al13 polymer to enhance coagulation performance

Coagulation is the best available method for removing intracellular organic matter (IOM), which is released from algae cells and is an important precursor to disinfection by-products in drinking water treatment. To gain insight into the best strategy to optimize IOM removal, the coagulation performance of two Al salts, i.e., aluminum chloride (AlCl₃) and polyaluminum chloride (PACl, containing 81.2% Al₁₃), was investigated to illuminate the effect of Al species distribution on IOM removal. PACl showed better removal efficiency than AlCl₃ with regard to the removal of turbidity and dissolved organic carbon (DOC), owing to the higher charge neutralization effect and greater stability of pre-formed Al₁₃ species. High pressure size exclusion chromatography analysis indicated that the superiority of PACl in DOC removal could be ascribed to the higher binding affinity between Al₁₃ polymer and the low and medium molecular weight (MW) fractions of IOM. The results of differential log-transformed absorbance at 254 and 350?nm indicated more significant formation of complexes between AlCl₃ and IOM, which benefits the removal of tryptophan-like proteins thereafter. Additionally, PACl showed more significant superiority compared to AlCl₃ in the removal of < 5?kDa and hydrophilic fractions, which are widely viewed as the most difficult to remove by coagulation. This study provides insight into the interactions between Al species and IOM, and advances the optimization of coagulation for the removal of IOM in eutrophic water.     

颗粒物悬浮体系中聚合铝凝聚絮凝形态表征 (Ⅰ):Al-Feron法的应用研究

应用Ａｌ－Ｆｅｒｒｏｎ法于悬浮体系中聚合铝的形态分布表征，对其中的主要影响因素进行探讨，就不同碱化度聚合铝的形态分析进行实例研究．结果表明，混合方式对Ａｌ－Ｆｅｒｏｎ法的应用具有一定的影响作用．比色管混合测得Ａｌａ为２１．５４％，低于磁力搅拌方式结果（２４．５２％，２５．２２％，２５．０６％）．应用磁力搅拌方式可以获取较好的重复性与更多初期反应信息．颗粒物的存在对反应的影响主要取决于其浓度与粒度分布，成一定线性关系，可以从中加以扣除．在本实验范围内因其溶解所产生的影响可以忽略不计．对多个碱化度聚合铝的实例研究表明，Ａｌ－Ｆｅｒｏｎ法完全适用于颗粒物悬浮体系中的形态分布表征     

颗粒物悬浮体系中聚合铝凝聚絮凝形态表征 (Ⅰ):Al-Feron法的应用研究

应用Ａｌ－Ｆｅｒｒｏｎ法于悬浮体系中聚合铝的形态分布表征,对其中的主要影响因素进行探讨,就不同碱化度聚合铝的形态分析进行实例研究。结果表明,混合方式对Ａｌ－Ｆｅｒｒｏｎ法的应用具有一定的影响作用。比色管混合测得Ａｌａ为２１．５４％,低于磁力搅拌方式结果（２４．５２％,２５．２２％,２５．０６％）。应用磁力搅拌方式可以获取较好的重复性与更多初期反应信息。颗粒物的存在对反应的影响主要取决于其浓度与粒度     

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.     

PACl-Al30絮凝剂研究现状和展望

具30个铝原子的Al30是继Al13之后新发现的一种高铝聚合形态,与Al13类似,具Keggin结构,也被认为是聚合氯化铝(PACl)中的新型优势混凝形态。文章从PACl发展的视角,对Al30形态的合成、鉴定以及混凝作用进行了综述,并就高Al30的合成、新型Al30复合硅絮凝剂的开发以及其表征和混凝机理研究等三个方面作出了有关展望。     

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