聚合铝水解聚合形态分布的影响因素研究

聚合铝的水解聚合形态有Ala、Alb、Alc,其中最佳絮凝形态Alb的含量是衡量聚合铝絮凝活性的主要指标。采用一次加碱法制备聚合铝时,水解聚合形态分布的主要影响因素依次为碱化度,加热温度,氯化铝浓度,碱浓度。实验确定的优化工艺条件为碱化度2.2,加热温度72℃,氯化铝浓度0.5mol/L,碱浓度0.7～1.0mol/L。检测结果表明在优化工艺条件下,制备的聚合铝中Alb含量为80.26%。应用实验表明在同等加药量的条件下,高Alb含量聚合铝对生活污水絮凝效果明显优于工业聚合铝和氯化铝     

不同聚合铝对水中有机物的去除研究

强化混凝是去除水中消毒副产物的最佳方法之一。文章针对强化混凝技术,从去除水中有机物的角度出发,对不同聚合铝的处理效果进行了研究。结果表明,酸性条件、加大投药量有利于水中TOC及UV254的去除,且酸性条件更为有利。在pH=6.3,工业PAC投药量为1.5×10-4mo(l有效铝)时去除效果最佳,水中总有机碳(TOC)及紫外吸光度(UV25)4的去除率分别可达到46%及57%,实验室制备的聚合铝碱化度越高越有利于水中有机物的去除。     

聚合铝水解聚合形态分布的影响因素研究

聚合铝的水解聚合形态有Ala、Alb、Alc，其中最佳絮凝形态Alb的含量是衡量聚合铝絮凝活性的主要指标。采用一次加碱法制备聚合铝时，水解聚合形态分布的主要影响因素依次为：碱化度，加热温度，氯化铝浓度，碱浓度。实验确定的优化工艺条件为：碱化度2．2，加热温度72℃，氯化铝浓度0．5mol／L，碱浓度0．7～1．0mol／L。检测结果表明：在优化工艺条件下，制备的聚合铝中Alb含量为80．26％。应用实验表明：在同等加药量的条件下，高Alb含量聚合铝对生活污水絮凝效果明显优于工业聚合铝和氯化铝。     

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.     

混凝-吸附处理黄河水及对氯消毒中氯衰减的影响

选用2种无机高分子混凝剂聚合氯化铁(PFC)和聚合氯化铝(PAC)处理黄河水,考察了混凝剂的投加量对浊度、UV254、DOC和高锰酸盐指数的去除效果,并结合混凝出水的Zeta电位分析其混凝机制.选择粉末活性炭与混凝联用,研究了混凝剂和吸附剂投加量以及二者的投加顺序对有机物去除效果的影响,并对混凝吸附后出水进行加氯消毒,考察水中残余氯随时间的变化.结果表明,2种混凝剂均有较高的浊度去除率(﹥90%).PAC对UV254、高锰酸盐指数和DOC的去除率分别为29.2%、26.1%和27.9%;PFC对三者的去除率分别为32.3%、23.3%和32.9%.PAC在混凝过程中,电中和作用占主导地位;PFC在混凝过程中,吸附架桥和电中和同时发挥作用.混凝-吸附联用处理黄河水样时,有机物的去除率随混凝剂和吸附剂投加量的增加而升高.先混凝后吸附工艺对UV254和DOC的去除效果优于先吸附后混凝工艺.先使用PAC混凝后吸附对UV254和DOC的去除率分别为95.2%和99.9%;对于PFC,先混凝后吸附对UV254和DOC的去除率分别为90.1%和99.9%.但是先投加粉末活性炭能提高矾花的沉降性能,且处理出水在保持持续消毒效果方面优于前者.     

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.     

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.     

纳微米塑料的聚合铝铁强化混凝去除及铝残余特征

微纳塑料作为一种典型新污染物,广泛存在于水环境中,具有较强的生物毒性效应.混凝作为胶体和悬浮颗粒物去除的关键技术,主流铝铁絮凝剂对于微纳米塑料的去除效率相对较低,症结是对相关机制仍不明晰.为此,本研究通过预水解制备多种聚合铝铁絮凝剂,研究铁含量和预水解过程对微纳塑料去除效果的影响,解析微纳塑料絮体形成机制和混凝机理.结果表明,絮凝剂铁含量的增加对微米塑料的去除有促进作用,但对纳米塑料的去除有抑制作用.铝铁物质的量的比为9∶4的聚合絮凝剂对微纳塑料均具有较高的去除效率.微米塑料的去除以网捕卷扫为主,而纳米塑料的去除以电中和为主.预水解过程可以增强双金属絮凝剂对纳米塑料的吸附电中和能力,同时有效抑制铝残留.本研究从絮凝剂优化角度解析了微纳塑料的混凝去除机制,可为强化混凝高效去除微纳塑料同时控制铝残留提供参考.     

新生态铁的混凝作用探索

利用双氧水和亚铁瞬时反应制备新生态铁作为混凝剂,采用杯罐试验确定了最优制备条件老化时间、酸的添加量、n(H2O2)/n(Fe),并且通过对比新生态铁、硫酸铁、聚合硫酸铁分别对浊度、UV254吸光度的去除效果、沉后水Zeta电位来衡量新生态铁的混凝效果并推测其可能的反应机制.结果表明,老化时间对新生态铁的除浊效果影响极小,可忽略不计;添加酸浓度为[H+]=0.1 mol.L-1时制备出的新生态铁混凝效能最佳;提高n(H2O2)/n(Fe)可显著增强新生态铁的混凝效果,最为经济有效的摩尔比值为0.55.新生态铁对浊度的去除效果与硫酸铁、聚合硫酸铁相近;对UV254吸光度有机物的去除率比Fe2(SO4)3高20%～44%;沉后水Zeta电位随新生态铁投量增加逐渐趋近于0 mV,电中和作用较强.新生态铁是一种具有开发价值的新型混凝剂,老化时间极短,过程简化,原料价格低廉,对浊度、UV254吸光度去除效果较好.     

基于新生态铁的复合混凝剂的净化效能研究

在以H2O2氧化Fe(Ⅱ)制得新生态铁的基础上,通过加入一定量的铝盐或聚合季铵盐进行复合改性,得到基于新生态铁的复合混凝剂。利用杯罐实验考察了不同复配比的新生态复配铁铝混凝剂和聚合季铵盐-新生态铁复合混凝剂对松花江水的浊度、色度以及TOC的去除效果,并在不同的混凝剂剂量下与单纯新生态铁或聚合氯化铝的混凝效果对比。实验结果表明:在不同的混凝剂剂量下新生态复配铁铝均可提高新生态铁对浊度、色度的去除效果,且在较低混凝剂剂量下,复配铝含量越高,对浊度和色度的去除效果越好;在剂量小于0.20 mmol/L时,新生态铁及新生态复配铁铝对浊度的去除效果均低于聚合氯化铝,但当剂量达到0.20 mmol/L及以上时,各混凝剂对浊度的去除效果相当;新生态铁对TOC的去除效果要优于新生态复配铁铝;在剂量低于0.10 mmol/L时,各新生态复配铁铝对TOC的去除效果次于聚合氯化铝,但当剂量在0.10 mmol/L以上时,随着剂量的增大,其去除效果逐渐赶超聚合氯化铝,且混凝沉后水残余铝含量低于聚合氯化铝。聚合季铵盐-复合新生态铁也可提高新生态铁对浊度、色度的去除效果,还可使混凝后残余铁含量大幅降低。聚合季铵盐-新生态铁在剂量6 mg/L时,沉后水浊度即可达到5 NTU以下,而单纯新生态铁在12 mg/L时,沉后水浊度才达到5 NTU以下。基于新生态铁的复合混凝剂与单纯新生态铁或聚合氯化铝相比,可以提高对浊度、色度或有机物的去除效果并降低沉后残余金属含量,因此是一种较有研究价值和开发前景的混凝剂。     

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.     

Preparation of high concentration polyaluminum chloride by chemical synthesis-membrane distillation method with self-made hollow fiber membrane

A method of direct contact membrane distillation (DCMD) with a self-made hollow polyvinylidene fluoride membrane was applied to prepare high concentration polyaluminum chloride (PACl) with high Al_b content based on chemical synthesis. The permeate flux and Al species distribution were investigated. The experimental results showed that the permeate flux decreased from 14 to 6 kg/(m²·hr) at the end of the DCMD process, which can be mainly attributed to the formation of NaCl deposits on the membrane surface. The Al_b content decreased slightly, only from 86.3% to 84.4%, when the DCMD experiment finished, correspondingly the Al_c content increased slightly from 7.2% to 8.5%, and the Al_a content remained at 7% during the whole DCMD process. A PACl with Al_b content of 84% at total aluminum concentration 2.2 mol/L was successfully prepared by the chemical synthesis-DCMD method.     

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.     

Purification, characterization and application of dual coagulants containing chitosan and different Al species in coagulation and ultrafiltration process

The objective of this study was to investigate the effect of different Al species and chitosan (CS) dosages on coagulation performance, floc characteristics (floc sizes, strength and regrowth ability and fractal dimension) and membrane resistance in a coagulation–ultrafiltration hybrid process. Results showed that different Al species combined with humic acid in diverse ways. Al_a had better removal efficiency, as determined by UV₂₅₄ and dissolved organic carbon, which could be further improved by the addition of CS. In addition, the optimal dosage of different Al species was determined to be 4.0 mg/L with the CS concentration of 1.0 mg/L, by orthogonal coagulation experiments. Combining Al_a/Al_b/Al_c with CS resulted in larger flocs, higher recovery, and higher fractal dimension values corresponding to denser flocs; in particular, the floc size at the steady state stage was four times larger than that obtained with Al species coagulants alone. The results of ultrafiltration experiments indicated that the external fouling percentage was significantly higher than that of internal fouling, at around 85% and 15%, respectively. In addition, the total membrane resistance was significantly decreased due to CS addition.     

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.     

臭氧对有机物混凝的影响

采用PDA(Photometric Disperse Analysis)和有机物表观分子量分级、有机物化学极性分级技术从絮体形成过程、絮体表现、有机物分子水平变化等方面研究了臭氧预氧化对混凝过程的影响;并对比了不同混凝剂在预臭氧条件下的混凝过程和效率.结果表明:臭氧预氧化对混凝过程有复杂的影响,其剂量和水体有机物特征决定了其对混凝的整体影响效果.有机物分级显示,臭氧化对有机物结构有重要影响,导致有机物极性、亲水性组分含量大幅提高(36.7%),小分子量组分(<10×10³)大幅增高(100%左右);但总的DOC去除率不高(3.28%).对PACl而言,在中、低剂量(O₃/TOC<0.7)下,臭氧对絮体形成过程影响较小,但对絮体沉降性和浊度去除已经有阻碍作用.在中、高剂量下(O₃/TOC>0.7),对絮体形成有显著滞后,浊度、有机物去除效率下降.AlCl₃对臭氧化作用反应敏感,臭氧化在试验剂量条件下,对絮体形成和浊度、有机物去除都有明显的阻碍作用.     

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.     

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.