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 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.     

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.     

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.      

柠檬酸对不同混凝剂混凝效果的影响

通过对不同混凝剂(Al2(SO4)3、Fe2(SO4)3、PACl25)混凝过程中絮体粒径大小的测定,研究了在不同pH条件下柠檬酸浓度对3种混凝剂混凝效果的影响.结果发现,随着柠檬酸浓度的增加,3种混凝剂混凝过程中生成絮体的速率和粒径大小都在逐渐降低,但3种混凝剂受到抑制的程度不同:对于硫酸铝,当n(柠檬酸)/n(Al) =0.1时,混凝20 min内没有絮体生成;对于硫酸铁,仅当n(柠檬酸)/n(Fe)=0.05时,絮体就不再生成;而当n(柠檬酸)/n(Al) =0.5时,PACl25絮体仍能很快地形成.不同的pH值下柠檬酸对混凝效果的抑制程度也不同:对于硫酸铝,pH =6时生成絮体最大,pH =8时没有絮体生成;对于硫酸铁,pH =5时产生絮体的情况和pH =6时相似,而pH =7时絮体消失;而对于PACl25,絮体大小随着pH值的升高而增大(pH在7～9之间).另外,通过对Zeta电位的测定可知,随着柠檬酸浓度的增加,3种混凝剂的Zeta电位都在降低,但降低的速率不同:硫酸铁＞硫酸铝＞ PACl25,这与絮体粒径大小的变化规律一致.     

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.     

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.     

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.     

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.     

高浓度聚合氯化铝的合成及其形态分布与转化规律

以CaO为碱化剂采用一次加碱法合成了高浓度聚合氯化铝(PAC),研究了其反应特性及产品的铝形态分布与转化规律.结果表明,CaO特殊的水化反应可使PAC达到较高浓度和较高B值,PAC最高浓度可达2.1mol/L,B值为2.1.合成过程中无论高铝浓度体系还是低铝浓度体系,均存在一最佳B值,此B值下产品的Al_b含量最高.最佳B值和最高Al_b含量均随总铝浓度的升高而降低.B值小于最佳B值时,总反应主要表现为生成Al_b;B值大于最佳B值时,总反应表现为生成Al_c.     

Effects of fluoride on the removal of cadmium and phosphate by aluminum coagulation

This study focuses on the effects of pH and fluoride at different molar ratios of fluoride to Al (R_F:Al) on the removal of cadmium (Cd²⁺) and phosphate by Al coagulation. Fluoride at R_F:Al ≥ 3:1 inhibits the removal of Cd over wide Al dose ranges from 5 to 10 mg/L as Al. The removal of phosphate decreases significantly at high R_F:Al of 10:1 whereas at lowered R_F:Al (i.e., ≤ 6:1), an adverse effect is observed only at insufficient Al doses below 2 mg/L. Fluoride shows inhibitive effects towards the removal of Cd at pH 7 and 8 and that of phosphate at pH 6. Fluoride decreases the ζ-potential in both systems, and the decreasing extent is positively correlated to the elevated R_F:Al. The Al fluoride interactions include the formation of Al–F complexes and the adsorption of fluoride onto Al(OH)₃ precipitates, i.e., the formation of Al(OH)_nF_m. Al–F complex formation inhibits Al hydrolysis and increases residual Al levels, and a more significant increase was observed at lower pH. Al–F complexes at high R_F:Al complicate the coagulation behavior of Al towards both negative and positive ionic species. Moreover, fluoride at low R_F:Al shows little effect on Al coagulation behavior towards Cd^2 + and phosphate, and the spent defluoridation adsorbent, i.e., aluminum (Al) hydro(oxide) with adsorbed fluoride at R_F:Al of below 0.1:1, may be reclaimed as a coagulant after being dissolved.     

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。     

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.     

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.     

信号分子强化改性挂膜沸石持续抑制沉积物中氨氮释放

为寻找一种长期有效的底泥修复方式,对沸石进行了改性并挂膜的实验.考察了4种铝盐[AlCl₃、 Al（NO₃）₃、 Al₂（SO₄）₃和KAl（SO₄）₂]改性挂膜沸石对上覆水中氨氮的去除情况.结果表明,AlCl₃改性挂膜沸石效果最佳,且最佳改性浓度为0.8 mol·L^-1.进一步分析添加信号分子OHHL后,AlCl₃改性挂膜、 NaCl改性挂膜和天然挂膜沸石抑制河流底泥中氮释放的持续性.其中AlCl₃改性挂膜沸石上附着的细菌量多,反硝化菌数量占比高（初始82.1%; 30 d后61.1%）,因此,生物再生率高（64.9%）,从而使得该沸石使用寿命长达8.5个月.可见,AlCl₃改性挂膜沸石能对底泥释放的氮负荷达到有效持续地抑制.     

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.     

藻形态及混凝剂组成对混凝-超滤过程的影响

为了保证藻类暴发阶段优质的饮用水供应,提高藻类的去除率,缓解藻类对水处理过程的影响,本研究以铜绿微囊藻(蓝藻)、小球藻(绿藻)和小环藻(硅藻)这3种不同形态藻细胞为研究对象,使用了3种具有不同铝形态分布的混凝剂[Al_2(SO_4)_3(AS)、Al_(13)、Al_(30)]进行混凝-超滤实验.在分离胞外有机物(EOM)的情况下,考察混凝过程中絮体的特性(粒径,强度因子,恢复因子)以及不同条件下形成的絮体对膜通量的影响.结果表明Al_(13)与Al_(30)的混凝作用以静电簇作用为主导,AS主要是以电中和作用为主导.对于铜绿微囊藻与小球藻体系,由于藻颗粒表面存在一定的凹陷,当Al_(13)与Al_(30)做混凝剂时,在投加量较低的情况下,吸附在颗粒表面凹陷处的混凝剂“失活”,其他部位由于仍带有一定的负电荷而造成絮体形成不明显,而AS做混凝剂时,混凝机制主要是电中和作用,可以明显降低颗粒之间的排斥力,在较低投加量下即可形成絮体.对于小环藻体系,由于其藻细胞呈现光滑的表面,Al_(13)与Al_(30)可有效发挥其静电簇作用机制,絮体在较低投加量下即可有效形成.膜通量与絮体粒径有明显的相关性,絮体粒径越大,超滤过程中形成的沉积层越疏松,膜比通量越大.     

Effects of Al3+ on the microstructure and bioflocculation of anoxic sludge

The aluminum ions generated from mining aluminum,electrolytic aluminum and the industrial production of aluminum-based coagulants(such as AlCl_3 and Al_2(SO_4)_3) enter sewage treatment plants and interact with activated sludges.An anaerobic/anoxic/oxic(A~2 O) process was used to reveal the effects of Al~(3+) on the pollutant removal efficiencies,bioflocculation and the micro structure of sludge.The results showed that a low concentration of Al~(3+) improved the pollutant removal efficiencies and increased the sludge particle size.However,a high concentration of Al~(3+) hindered microbial flocculation and reduced the pollutant removal efficiencies.With a 10 mg/L Al~(3+) addition,the chemical oxygen demand(COD),total nitrogen(TN) and NH_4~+-N increased by 3%,16% and 27%,and reached as high as 68%,60% and 87%,respectively.At the same time,the dehydrogenase activity,flocculation ability(FA) and contact angle of the sludge reached their maximum levels at 41.3 mg/L/hr,45% and 79.63°,respectively.The specific surface area of the sludge decreased to 7.084 m2/g and the sludge pore size distribution shifted to concentrate in the me soporous range.Most of Al~(3+) was adsorbed on the surface of sludge,changing the physicochemical properties and physical structure of the sludge.     

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.