聚磷氯化铝溶液形态分布及转化规律

聚磷氯化铝是一种新型高效混凝剂，采用逐时络合比色法和酸中和速度法研究了聚磷氯化铝溶液的形态分布。结果表明，聚磷氯化铝的聚合形态为聚合铝形态与磷酸根作用新形态之和，其形态分布取决于羟比值和磷铝比值等因素，在一定的羟铝比值和磷铝比值时，聚磷氯化铝溶液可划分为５类形态，描绘出了聚磷氯化铝的形态转化规律。     

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.     

聚合铝的凝聚絮凝特征及作用机理

采用不同碱化度B(OH/Al)值的聚合铝和AlCl_3对高岭土悬浊液进行凝聚絮凝实验,同时测定电泳度及表面吸附特征,结合不同铝盐的化学形态分布,探讨聚合铝的高效凝聚作用原理.并求得表面吸附覆盖率,电位变化与形态分布间的定量关系,绘出聚合铝的凝聚区域图,对阐明聚合铝的作用机理提供了实验依据.     

环境化学

X13 9502639水解聚合铝溶液中形态分布的定量模拟研究/栗兆坤…(中科院生态环境研究中心)//环境科学学报/中科院环委会一1995,一s(一),一39~47 环信X一9 通过Al一Ferron逐时络合比色法和2了AI核磁共振(NMR)法,并应用“MINEQL”化学平衡模式计算法,对采用不同反应途径制得的聚合铝(PAC)溶液中的化学形态分布规律进行了定量模拟研究和对比。模式计算结果与两种实验定量分析结果都较为吻合。结果表明,在水解聚合铝溶液中较稳定的化学形态主要有五种:一种单体形态〔Ala〕,即A13+,Al(OH)2+;AI(OH对;3种聚合形态〔AI‘〕,即Al:(OH砖+…     

聚合氯化铝的27Al NMR研究

聚合氯化铝(PAC)是一种水处理混凝剂,七十年代以来已在我国、日本及其它一些画家得到应用。这种混凝剂是铝离子的水解聚合产物,有较高的铝含量及较大的羟铝比。我们用~(27)Al NMR(核磁共振)法对PAC及其水稀释物中铝的形态进行初步研究,以了解稀释对PAC组成变化的影响。     

Al(Ⅲ)盐水解聚合过程中聚合铝含量的定量计算

依据Al(Ⅲ)盐强制水解聚合过程的电位滴定实验结果,利用铝盐水解聚合电位滴定曲线上的3个临界特征点,同时利用Origin软件自备的Boltzmann方程对滴定曲线拟合,给出了通过电位滴定实验计算聚合铝含量的定量公式。此公式能方便地计算出铝盐强制水解聚合溶液中的聚合铝含量。模式计算结果与Al-Ferron逐时络合比色法的测试结果线性拟合较好。     

聚硅氯化铝PASC的制备及混凝效果研究

采用共聚法制备出不同c(OH)/c(Al)和c(Si)/c(Al)的聚硅氯化铝(PASC)混凝剂,并对其进行了铝形态表征.讨论了c(OH)/c(Al)与c(Si)/c(Al)对铝形态分布的影响.比较了不同聚合时间、聚合酸碱条件下PASC的稳定性.通过混凝实验确定了最佳c(Si)/c(Al)为1:7,最佳投加量质量浓度为80 mg/L,并就混凝效果与PAC进行了对比.结果表明PASC要优于PAC.     

聚合氯化铝与有机高分子复合絮凝剂的形态分布研究--Al-Ferron和27Al-NMR相结合

主要研究了Al Ferron逐时络合比色法和2 7Al NMR法应用于聚合铝与有机高分子复合絮凝剂形态分布的测定 .结果表明 ,两种方法分别测定的Alb 和Al13 的结果具有一定的相关性 ;聚合铝与有机高分子复合后其形态分布发生了一定的变化 ,Alb(或Al13 )的含量有所降低 ,但仍是优势形态 ,Ala(或Al单)的含量基本保持不变 .     

混凝过程中铝与聚合铝水解形态的动力学转化及其稳定性

采用Ｆｅｒｒｏｎ逐时络合比色法，并结合电泳测定研究了混凝过程中氯化铝和聚合氯化铝的水解形态动力学转化及稳定性。结果表明，ＡＣ在混凝过程中所形成的水解形态完全不同于ＰＡＣ的预制水解聚合形态，其电荷及分子量均明显低于聚合铝且不稳定，ＡＣ随混凝条件如投加浓度、ＰＨ和混合时间而变，而ＰＡＣ－２５水解聚合形态不随混凝条件变化，始终保持稳定状态，ＡＣ水解沉淀规律与理论计算相符并形成无定形Ａｌ（ＯＨ）３絮体颗粒     

环境化学

X 13 9700041AI Ferr(in逐时络合比色法研究PACS中铝的水解聚合形态/高宝玉…(山东大学环境工程系)沼环境化学/中科院生态环境研究中心一1996,15(3)一234一238环信X一87 制备了碱化度(B)及不同A13+/S()牙一摩尔比的系列P八CS,用八1一Ferron逐时络合比色法研究了铝的形态分布,考察了碱化度(B)、A13十/S()芍卒尔比、稀释作用及pH值对铝的形态分布的衫响。实验结果表明,A13十/S(滩一摩尔比及溶液的Pll位对铝的形态分布有较大的影响,稀释作J手J对铝的形态分布影响较小。A13+/S()军一摩尔比愈小,pH位愈高,铝的水解聚合大分子及胶体粒…     

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     

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.     

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.     

固态聚合氯化铝的27Al NMR研究

聚合氯化铝(PAC)是一种水处理混凝剂,可为液态(PAC-L),也可浓缩成固体(PAC-S)、PAC-L在水中稀释时铝的形态的变化已用~(27)Al核磁共振法(NMR)进行了研究。本工作试图用~(27)Al NMR法对PAC-S及其在水中溶解稀释物中铝的形态进行研究,以探讨固化对PAC及其在水中铝的形态的影响。     

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.     

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.     

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.     

Effects of low temperature on aluminum(Ⅲ) hydrolysis: theoretical and experimental studies

In this study, the effects of low temperature on aluminum(III) (Al) hydrolysis were examined both theoretically and experimentally by constructing a solubility diagram for amorphous aluminum hydroxide (Al(OH)3(am)) and a distribution diagram of hydrolyzed Al species. Firstly, thermodynamic data of Al species at 4℃ were calculated from that at 25℃. A well confirmed polymeric Al species, AlO4Al12(OH)247 (Al13), was involved in building the diagrams and, correspondingly, the non-linear simultaneous equations with 13 degrees were resolved. Secondly, polarized Zeeman atomic absorption spectrophotometry (AAS), 27Al nuclear magnetic resonance (NMR) spectroscopy, and ferron-based spectrophotometry were applied for constructing the practical diagrams. The results show that a decrease of temperature from 25 to 4℃ caused the Al(OH)3(am) boundary on the solubility diagram to shift toward the alkaline side by about 1.0 pH unit and the minimum solubility of Al(OH)3(am) to reduce by 1.0 log unit. The distribution diagram indicates that the monomeric Al, Al13, and solid-phase Al(OH)3 were alternately the predominant species with the increase of pH value during Al hydrolysis. At 25℃, Al13 was the dominant species in a pH range of 4.0 to 4.5, whereas at 4℃, Al13 was the leading species in a pH range spaced from 4.5 to 6.3. The predominant species changed from the monomeric Al to the solid-phase Al(OH)3 over the range of 1.8 pH units at 4℃ in comparison with the range of 0.5 pH unit at 25℃.     

A novel method to synthesize polyaluminum chloride with a membrane reactor

Al13 or Alb is usually regarded as the most efficient species of polyaluminum chloride(PAC), the performance flocculant for water treatment. This paper was intended to report a new method to synthesize PAC with high content Alb, by using the membrane reactor. NaOH solutions were managed to permeate slowly through the micropores of ultrafiltration membrane into AlCl3 solutions under the suitable transmembrane pressure(TMP). Meanwhile NaOH drops size was limited to nano-scale, resulting in dramatical reduction of the characteristic diffusion time and great increment of contact interface between the strong base and AI ions in solution to favor the formation of Al(OH)4^-, the precursor of AI,3, so few precipitates and much Alb are produced. When the initial concentration of AlCl3/NaOH is 0.40/2.0 (mol/L), MWCO = 10000, TMP = 0.0085 MPa, T= 305 K and B(molar ratio of OH^-/Al^3 ) = 2.25, the quantity of Alb attains about 80%. The results of ^27Al-NMR determination showed that the Al13 content is equal to Alb content. And our PAC product has shown better flocculation effects than the commercial product.     

Effects of low temperature on aluminum(III) hydrolysis: Theoretical and experimental studies

In this study, the effects of low temperature on aluminum(III) (Al) hydrolysis were examined both theoretically and experimentally by constructing a solubility diagram for amorphous aluminum hydroxide (Al(OH)3(am)) and a distribution diagram of hydrolyzed Al species. First, thermodynamic data of Al species at 4 degrees C were calculated from that at 25 degrees C. A well confirmed polymeric Al species, AlO4Al12(OH)24(7+)(Al13), was involved in building the diagrams and, correspondingly, the non-linear simultaneous equations with 13 degrees were resolved. Secondly, polarized Zeeman atomic absorption spectrophotometry (AAS), 27Al nuclear magnetic resonance (NMR) spectroscopy, and ferron-based spectrophotometry were applied for constructing the practical diagrams. The results show that a decrease of temperature from 25 to 4 degrees C caused the Al(OH)3(am) boundary on the solubility diagram to shift toward the alkaline side by about 1.0 pH unit and the minimum solubility of Al(OH)3(am) to reduce by 1.0 log unit. The distribution diagram indicates that the monomeric Al, Al13, and solid-phase Al(OH)3 were alternately the predominant species with the increase of pH value during Al hydrolysis. At 25 degrees C, Al13 was the dominant species in a pH range of 4.0 to 4.5, whereas at 4 degrees C, All3 was the leading species in a pH range spaced from 4.5 to 6.3. The predominant species changed from the monomeric Al to the solid-phase Al(OH)3 over the range of 1.8 pH units at 4 degrees C in comparison with the range of 0.5 pH unit at 25 degrees C.