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.     

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.     

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.     

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.     

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.     

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.     

Polytitanium sulfate (PTS): Coagulation application and Ti species detection

Interest in the development of inorganic polymerized coagulants is growing; however, there are only limited studies on the synthesis of polytitanium coagulants, which are expected to exhibit improved coagulation efficiency with better floc properties. This study presents the synthesis of polytitanium sulfate (PTS) for potential application in water purification, followed by characterization of PTS flocs and titanium species detection. Stable PTS solutions were successfully synthesized and standard jar tests were conducted to evaluate their coagulation efficiency. Electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) speciation analysis revealed that a variety of mononuclear and polynuclear complexes were formed in PTS solution, indicating the polymeric nature of the synthesized coagulant. Floc characteristics were studied through on-line monitoring of floc size using a laser diffraction particle size analyzer. Results showed that PTS had a comparable or in some cases even higher organic matter and particulate removal efficiency than Ti(SO₄)₂. The effluent pH after PTS coagulation significantly improved toward desirable values closer to neutral pH. Properties of flocs formed by PTS were significantly improved in terms of floc size, growth rate and structure. This study showed that PTS could be an efficient and promising coagulant for water purification, with the additional benefit that its coagulated sludge can be used to recover valuable TiO₂ nanoparticles for various commercial applications.     

生活垃圾焚烧厂渗滤液生化出水的混凝机理研究

分别采用Al₂(SO₄)₃、FeCl₃、PAC、PAFC对垃圾焚烧厂渗滤液生化出水进行混凝研究,并建立混凝处理模型.结果表明,在pH值为6时,单独投加500 mg/L的Al₂(SO₄)₃、FeCl₃、PAC、PAFC时,COD去除率分别为20％、17％、30％、40％.焚烧厂渗滤液生化出水中有机物主要是由相对分子质量小于2 000的可溶性物质组成;通过透射电镜扫描技术(TEM)和Zeta电位分析,发现中和及网捕桥联是渗滤液混凝处理的主要作用机理;相比无机盐混凝剂,聚合物混凝剂具有较强的电中和以及网捕架桥功能.     

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 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.     

新生态型聚硅酸铁锰处理染料废水的优化

为了提高混凝剂对染料废水的净化效率,本文利用硅酸钠、硫酸亚铁和高锰酸钾为原料合成了新型复配混凝剂聚硅酸铁锰(PSFM),分别以直接大红、分散蓝和活性黄染料废水为处理对象进行混凝模拟实验,研究了碱度和浊度等因素对PSFM混凝去除染料性能影响.结果表明,PSFM对直接大红和分散蓝染料废水具有较好的混凝净化效能,其色度和TOC去除率分别可达99.2%、95.4%和98.5%、93.8%,效果优于聚硅酸铁(PSF)、Al2(SO4)3和Fe Cl3等常规混凝剂,PSFM对活性黄染料废水色度和TOC去除率分别为56.3%和51.3%.浊度对PSFM混凝效能无明显影响.在碱度分别为50、0和75 mg·L~(-1)时,PSFM对直接大红、分散蓝和活性黄去除率分别达到最高.此外,利用扫描电子显微镜(SEM)、傅里叶红外(FTIR)和X射线衍射仪(XRD)等高级表征手段对PSFM进行了表征,对混凝过程中的混合液和絮体分别进行Zeta电位和絮体粒径在线监测,探索得PSFM混凝主要机制为Fe+与Mn+水解产生的带正电的多核配合物和聚硅的桥联聚合,同时还包括新生态水合二氧化锰和羟基氧化铁的吸附助凝作用.     

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.     

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.      

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.     

颗粒物对混凝过程及超滤膜污染的影响

以nm-SiO₂和μm-SiO₂体系为研究对象,使用3种不同Al形态的混凝剂（AlCl₃、Al₁₃和Al₃₀）进行混凝-超滤实验,考察不同pH值下SiO₂去除率、出水余Al及混凝预处理对膜通量的影响,借助马尔文激光粒度仪、SEM、BET和AFM表征絮体性质及在超滤膜表面的分布和作用力.结果表明,nm-SiO₂体系中SiO₂去除率均低于μm-SiO₂体系,在纳米颗粒物体系中投加混凝剂后膜通量从0.68分别提升至0.96（AlCl₃）、0.86（Al₁₃）和0.87（Al₃₀）,微米颗粒物体系中投加3种混凝剂后膜通量从0.79提升至0.80~0.84.微米级颗粒物是颗粒间的碰撞,纳米级颗粒物主要以团聚态的形式碰撞.低聚态铝（Al_a）和颗粒物形成絮体的粒径均大于150μm,体系zeta电位为负与膜表面产生斥力;在中性条件下Al₁₃与颗粒物形成絮体的强度因子远高于AlCl₃和Al₃₀,中聚态铝（Al_b）将膜孔内部较小颗粒物堵塞形成的不可逆膜污染转移成膜孔表面的可逆膜污染;高聚态铝（Al_c）具有较强吸附架桥和网捕卷扫能力,无定形、不规则的团聚态小颗粒在这一过程中形成较大絮体缓解膜污染.     

聚合硫酸铁(PFS)混凝腐殖酸(HA)的过程中典型操作因素的影响研究

针对聚合硫酸铁（PFS）混凝-沉淀去除腐殖酸（HA）水样的过程,通过测定典型操作因素（PFS投加量、原水pH和搅拌方式）下微絮体的zeta电位、上清液的浊度、UV254、pH值及电导率和絮体沉降体积变化,探讨了这些因素对该过程的影响.结果表明：在原水pH=6.00时,PFS混凝HA的主要机制为电中和作用,搅拌方式对PFS的最佳投加范围没有明显的影响,但单一搅拌方式下HA的去除效果更好;在原水pH=8.00时,吸附络合-卷扫絮凝成为主要的混凝机制,复合搅拌方式下PFS的最佳投加量范围大于单一搅拌方式,且前者的HA去除效果更好.整体而言,几种混凝条件下PFS最佳投药量对应的微絮体zeta电位均在-12.00mV左右;原水pH=6.00时PFS混凝-沉淀去除HA的效果比原水pH=8.00时的好,且前者形成的PFS-HA沉淀絮体体积较小,但单一搅拌方式下絮体结构的重组过程并不是影响絮体体积的主要因素.复合搅拌方式中开始阶段的高强度搅拌有助于PFS组分在HA水样中的分散而有利于其电中和作用的发挥,但对PFS的水解过程影响不大.     

复合生物絮凝剂CBF-1的絮凝作用机理研究

采取PAC+絮凝剂的复配方式开展高岭土悬浊液烧杯实验,考察了复合生物絮凝剂CBF-1、CBF-1溶解物及微生物絮凝剂MBF8的絮凝特性,并借助iPDA仪分析和扫描电镜、光学显微镜观察等手段,比较分析了絮凝过程及絮体特性的差异.结果表明,各复配絮凝的浊度去除效果排序为CBF-1＞ CBF-1溶解物＞MBF8,CBF-1投加量1 mg·L-1时,浊度去除率可达到97.5％;絮体强度排序为CBF-1＞ CBF-1溶解物＞MBF8,絮体恢复因子排序为MBF8＞CBF-1溶解物＞CBF-1,絮体大小排序为CBF-1＞ CBF-1溶解物＞MBF8.单独投加PAC或投加PAC+MBF8的情况下,形成的絮体形态相对规整、密实;投加PAC+ CBF-1溶解物或投加PAC+ CBF-1形成的絮体则相对无序、疏松,CBF-1作用下絮体大、沉降快.CBF-1中高电荷MBF8组分及大分子羧甲基纤维素、羧甲基多聚糖等组分具有强的电荷中和与桥联协同增效作用;CBF-1还含有纤维素、木质素等大分子量且带多种官能团的不溶性组分,在桥联和吸附过程中也起着重要作用.     

Purification and characterization of Al13 species in coagulant polyaluminum chloride

Nano-Al₁₃ was separated and purified by four methods to investigate its characteristic, and was analyzed by Al-Ferron timed complexation spectrophotometer,²⁷ Al-NMR (nuclear magnetic resonance), and transmission electron microscopy (TEM). Coagulation efficiency of nano-Al₁₃, polyaluminum chloride (PAC), and AlCl₃ in synthetic water were also investigated by jar test. The dynamic process and aggregation state of kaolin suspensions coagulating with nano-Al₁₃, PAC, and AlCl₃ were also investigated. The experimental results indicated that the efficiency of gel column chromatography method was the highest for separating PAC solution with low Al concentration. Ethanol and acetone method was simple and could separated PAC solution with different Al concentrations, while silicon alkylation white block column chromatography method could separate PAC solution only with low Al concentration. The SO₄²−/Ba²⁺ displacement method could separate PAC solution with high Al concentration, but extra inorganic cation and anion could be introduced into the solution during the separation. The coagulation efficiency and dynamic experimental results showed that nano- Al₁₃ with a high positive-charged species was the main species of electric neutralization in coagulation process, and it could reduce the turbidity and increase the effective particles collision rate efficiently in coagulation process. Its coagulation speed and the particle size of coagulant formed were of greatest value in this study.     

Two-dimensional correlation spectroscopic analysis on the interaction between humic acids and aluminum coagulant

In this study, two-dimensional correlation spectroscopy integrated with synchronous fluorescence and infrared absorption spectroscopy was employed to investigate the interaction between humic acids and aluminum coagulant at slightly acidic and neutral p H. Higher fluorescence quenching was produced for fulvic-like and humic-like fractions at p H 5. At p H 5, the humic-like fractions originating from the carboxylic acid, carboxyl and polysaccharide compounds were bound to aluminum first, followed by the fulvic-like fractions originating from the carboxyl and polysaccharide compounds. This finding also demonstrated that the activated functional groups of HA were involved in forming the Al-HA complex, which was accompanied by the removal of other groups by co-precipitation.Meanwhile, at p H 7, almost no fluorescence quenching occurred, and surface complexation was observed to occur, in which the activated functional groups were absorbed on the amorphous Al(OH)3. Two-dimensional FT-IR correlation spectroscopy indicated the sequence of HA structural change during coagulation with aluminum, with IR bands affected in the order of COOH COO-NH deformation of amide Ⅱ aliphatic hydroxyl C\OH at p H 5, and COO-aliphatic hydroxyl C\OH at p H 7. This study provides a promising pathway for analysis and insight into the priority of functional groups in the interaction between organic matters and metal coagulants.