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.     

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.     

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.     

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.     

铜绿微囊藻对混凝除氟的促进作用及机理分析

以铜绿微囊藻、氯化铝（AlCl₃·6H₂O）为研究对象,通过三维荧光、场发射扫描电镜等表征,探究了藻类对氟化物混凝去除机制的影响.结果表明,在pH值为7.0,8.0,9.0,Al投加量在20.0~80.0mg/L的条件下,铜绿微囊藻对混凝除氟有明显的促进作用,其促进作用主要在于藻絮体对氟的表面吸附.铜绿微囊藻与氯化铝水解产物通过吸附架桥和网捕卷扫作用,聚集成较大较多的絮体.絮体粒径越大,除氟率越高.pH值为7.0,Al投加量为40.0mg/L时,絮体粒径达到最大值500μm,此时氟去除率最高,为77.37%;当Al投加量为80.0mg/L时,藻细胞破损严重,有机物过多释放,对混凝除氟起阻碍作用.絮体破碎吸附实验结果表明,对絮体进行一定强度破碎可以增加吸附位点,从而提高氟的去除率;但破碎强度过大,絮体粒径过小,对氟的吸附效率亦会降低.     

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.     

Influential factors of formation kinetics of flocs produced by water treatment coagulants

The growth rate and size of floc formation is of great importance in water treatment especially in coagulation process.The floc formation kinetics and the coagulation efficiency of synthetic water were investigated by using an on-line continuous optical photometric dispersion analyze and the analysis of water quality.Experimental conditions such as alum dosage,pH value for coagulation,stirring intensity and initial turbidity were extensively examined.The photometric dispersion analyze results showed that coagulation of kaolin suspensions with two coagulants(alum and polyaluminium chloride) could be taken as a two-phase process:slow and rapid growth periods.Operating conditions with higher coagulant doses,appropriate pH and average shear rate might be particularly advantageous.The rate of overall floc growth was mainly determined by a combination of hydraulic and water quality conditions such as pH and turbidity.The measurement of zeta potential indicates that polyaluminium chloride exhibited higher charge-neutralizing ability than alum and achieved lower turbidities than alum for equivalent Al dosages.Under the same operating conditions,the alum showed a higher grow rate,but with smaller floc size.     

引入分形维数的混凝动力学方程数值求解

运用Smoluchowskj基本原理,建立了引入絮凝体分形维数的混凝动力学模型.该模型在絮凝过程中考虑了不同时刻形成的絮凝体中引入的初始颗粒数目和空隙率,并以此来推求不同时刻形成的絮凝体所对应的分形维数.采用有限差分法对建立的混凝动力学模型进行了数值计算.结果表明,初始颗粒的结构特征和碰撞效率是影响絮凝体粒径分布的主要因素.初始颗粒的分形维数和碰撞效率越大,絮凝体粒径分布越宽泛,大尺寸的颗粒所占的份额越多.同时计算结果表明,絮凝体的分形维数有随其粒径增大而逐渐降低的趋势,其原因是絮凝体的成长粒径与絮凝体中所包含的初始颗粒增长速度不成比例.以腐殖酸为混凝对象,采用硫酸铝作为混凝剂进行混凝实验,并以其初始絮凝条件作为数值计算初始条件,研究表明数值计算分析结果和模拟结果吻合较好.     

腐殖酸絮凝体形成过程中初期搅拌条件对其形态结构的影响

以腐殖酸为研究对象,采用硫酸铝为混凝剂进行混凝杯罐实验,借助PDA在线监测系统、图像解析法及粒子图像测速技术分析评价絮凝体的构造特征,着重探讨了混凝过程中初期快速搅拌条件对絮凝体形态结构的影响.结果表明,快速搅拌条件对腐殖酸絮凝体的形成过程及形态结构有着显著影响.最佳快速搅拌条件为:搅拌历时l min,搅拌强度300 r·min-,此时形成的絮凝体结构密实,抗剪切能力强,整体性能最优,絮凝体分形维数、强度及平均粒径分别为1.8842、0.164 N·m-2、0.43 mm.腐殖酸絮凝体的形成包括不溶性微粒的产生及初期颗粒的形成与结合等过程,其中,不溶性微粒的形成及初期颗粒的致密化过程是决定最终絮凝体形态构造的重要环节,而快速搅拌条件影响着混凝剂扩散混合效果和初期颗粒的形成速率与致密化程度,这也是初期快速搅拌条件对于腐殖酸混凝过程有显著影响的一个重要因素.     

低温条件下絮体破碎再絮凝去除水中颗粒的研究

为了了解低温条件下絮体的形成/破碎/再絮凝过程在适当条件下对絮凝去除水中颗粒物的强化效果,采用PDA2000透光率脉动检测仪对絮凝破碎再絮凝过程进行了在线监测.研究结果表明,当电中和机理占主导作用时(混凝剂投加量小于0.1 mmol·L-1),絮体破碎后能重新絮凝,絮体大小能恢复到破碎之前;而当网捕卷扫机理占主导作用时(混凝剂投加量大于0.2 mmol·L-1),絮体的恢复情况不如电中和条件,再絮凝能力降低.投加适量的腐殖酸会增加絮体破碎前后的分形维数,但过量的腐殖酸则会降低破碎前后絮体的分形维数.絮体破碎再絮凝后其分形维数比破碎前高.腐殖酸的投加量并不会明显影响絮凝和破碎后再絮凝的FI指数.电中和絮体破碎前初始絮凝时间越长破碎后沉后水浊度越低,破碎后其浊度会比破碎前显著减小.较低投量的铝盐就能使得沉后水浊度降到很低,因此可以降低混凝剂投量而达到更好的水处理效果.     

聚硅酸硫酸铁强化混凝去除微污染水源水中天然有机污染物

应用强化混凝技术,降低原水中有机物含量,是控制消毒副产物生成的有效途径之一。通过混凝搅拌试验,评价了聚硅酸硫酸铁混凝剂对原水中有机污染物的去除效果,考察了混凝剂投加量、pH值等对去除效果的影响。结果表明：聚硅酸硫酸铁去除有机物和除浊能力明显优于硫酸铁、聚合硫酸铁,其适宜的投药量范围和pH值范围宽;聚硅酸硫酸铁在混凝过程中形成的矾花较大,沉降速度快,因而可缩短处理水在构筑物中的停留时间,提高系统的处理能力;此外,通过正交实验确定了聚硅酸硫酸铁混凝剂的最佳水力条件。     

二氧化氯预氧化对藻类絮体形态的影响

针对高含藻高含盐杨埕水库原水藻类特征,采用聚合氯化铝(PAC)、硫酸铝(AS)、聚合硫酸铁(PFS)和氯化铁(FC)4种混凝剂进行混凝除藻试验,用图像法对藻类絮体的分形维数进行测定,分析混凝剂种类及投量、二氧化氯投加量等因素对混凝除藻效果及藻类絮体形态的影响。结果表明,杨埕水库夏季藻类种属相对较为单一,以小型色球藻、微小平裂藻、不整齐蓝纤维藻为优势藻类;4种混凝剂的除藻性能优劣依次为:AS>PAC>PFS>AC。在AS最佳投加量(以Al2SO4计)70 mg/L下,藻类的去除率为85.3%。此时,杨埕水库夏季藻类以藻类絮体分形维数值为1.54,形成的絮体密实且沉降性好。以AS为混凝剂,投加量为70 mg/L下,二氧化氯投加量为0.8 mg/L时助凝效果最好,藻类的去除率比单独投加AS时提高了6.3%,藻类絮体分形维数值为1.71,形成的藻类絮体更加密实。二氧化氯过量投加无益于藻类去除。     

Nano-TiO2回收过程中SO42-对不同混凝剂混凝过程的影响

为了降低纳米TiO₂使用成本,采用不同混凝剂对纳米TiO₂悬浊液进行固液分离.通过考察浊度去除率、出水pH值的变化情况,并结合X射线光电子能谱（XPS）、傅里叶红外光谱（FTIR）、固体核磁（NMR）、扫描电镜（SEM）及能谱分析（EDS）表征,探究了纳米TiO₂回收过程中SO₄^2-对不同混凝剂混凝过程的影响.结果表明,当使用AlCl₃作混凝剂时（0.1mmol/L）,SO₄^2-浓度从0.0mmol/L增加到20.0mmol/L,浊度去除率降低了0.80%,絮体粒径从450μm下降到215 μm,而强度因子无明显变化.低聚合态的Al_a不与SO₄^2-结合,混凝过程中通过吸附架桥和网捕卷扫的作用形成大量无定形的Al （OH）₃.当使用Al₁₃作混凝剂时,再生长后絮体的粒径随着SO₄^2-浓度的增加而下降,S-O峰的红移证明有新的含S聚合物产生,Al 2p的峰均向较高的结合能移动证明生成的絮体不是Al （OH）₃.     

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.     

聚合氯化铝及聚合氯化铝铁处理微污染地表水效果

选用两种无机高分子混凝剂聚合氯化铝(PAC)和聚合氯化铝铁(PAFC),与传统混凝剂Al2(SO4)3处理微污染地表水。以浊度和CODMn去除率为主要指标,考察投药量和pH对混凝效果的影响。通过考察沉淀时间对浊度去除效果的影响,结合实验现象,讨论三种混凝剂生成矾花的大小和沉降性能。结果发现,PAC和PAFC在5mg/L的投药量下可以取得较好的混凝效果,出水符合GB 5749-2006《生活饮用水卫生标准》。三种混凝剂的最佳pH为6,PAFC受pH影响较小,当pH为5～8时可取得较好的CODMn去除效果。PAFC生成的矾花体积较大,沉降性能较好,在实际应用中可缩短沉淀池的水力停留时间。     

On-line optical determination of floc size of Fe(Ⅲ) coagulants

This study investigated the floc aggregation, average floc size, floc size variance and floc growth velocity when ferric chloride （FeCl3） and polyferric chloride （PFC） were used to treat the simulated water samples. The factors including coagulant dose, ionic strength and solution pH, which affect the floc aggregation, were studied. Experiments were carried out in a bench-scale reactor using photometric dispersion analyzer （ PDA）. Results showed that there were great differences between the floc aggregation of PFC and FeCl3. The average floc size and fioc growth velocity of PFC were much larger than those of FeCl3. Compared with FeCl3, PFC gave a better coagulation performance in wider range of pH, dosage and ionic strength. It was also found that the coagulation efficiency of PFC did not depend on average floc size but on floc growth velocity.     

On-line optical determination of floc size of Fe( Ⅲ ) coagulants

This study investigated the floc aggregation, average floc size, floc size variance and floc growth velocity when ferric chloride (FeCl3) and polyferric chloride (PFC) were used to treat the simulated water samples. The factors including coagulant dose, ionic strength and solution pH, which affect the floc aggregation, were studied. Experiments were carried out in a bench-scale reactor using photometric dispersion analyzer (PDA). Results showed that there were great differences between the floc aggregation of PFC and FeCl3.The average floc size and floc growth velocity of PFC were much larger than those of FeCl3. Compared with FeCl3, PFC gave a better coagulation performance in wider range of pH, dosage and ionic strength. It was also found that the coagulation efficiency of PFC did not depend on average floc size but on floc growth velocity.     

腐殖酸铝盐絮凝体的动态特性

通过显微摄影分析研究了腐殖酸铝盐絮凝体成长的动态过程以及在混凝过程中絮凝体构造(分形维数)的变化规律.结果表明,在腐殖酸混凝过程中,随搅拌历时延长,絮凝体粒径不断成长变大,最终达到平衡状态.随着絮凝体的成长,其构造呈现由密实逐渐向疏松过渡的过程,空隙率变大,二维分形维数由初期的1.8左右下降到1.4左右.絮凝体分形维数D_f和粒径d_f之间具有D_f=Ad_f^-     

水泥混凝处理模拟染料废水及其循环再生利用的研究

以常见的CA-70铝酸盐水泥、32.5R硅酸盐水泥、白水泥作为混凝剂,处理活性艳蓝X-BR模拟染料废水。在测定模拟废水在混凝过程中有机物含量以及pH值变化的基础上,探讨了以水泥替代传统混凝剂的可行性。依据水泥水化产物的性质,采用高温煅烧方法使混凝剂再生,实现了其循环使用的目的。研究结果表明:水泥作为混凝剂,在水化过程中能形成具有良好混凝性能的形态,对模拟染料废水中活性艳蓝X-BR去除率达90%以上,且通过高温再生后,可重复使用10次以上,出水均达到纺织染整工业水污染物排放标准。混凝污泥的沉淀性能良好,便于稳定化处理。     

絮体老化与调节对回流进水及混凝的影响机制

为探索絮体老化与pH值调节对回流进水颗粒组成及混凝的影响,采用激光粒度仪进行了絮体粒径分析并通过Al （OH）₃胶体（Al-gel）的老化实验探究了老化与pH值调节对絮体形态及性质的内在影响机制.结果表明,原水颗粒物粒径呈现单峰分布,絮体回流进水颗粒物粒径呈现双峰分布,并且回流进水颗粒d₅₀随着絮体老化时间的增加而减小;由于絮体回流提高了颗粒物与混凝剂接触机率和碰撞效率,因此加快了絮体的生长;絮体在pH=5的环境下老化12h后进行回流混凝的絮体粒径生长速率最高（1.16 μm/s）并且生成的絮体具有较大的分形维数（2.35）.Al-gel的老化实验结果表明,絮体老化过程会涉及羟桥反应和结晶反应并导致絮体的表面活性基团数量减少,从而不利于与原水颗粒物的相互作用.pH值调节对絮体产生不同的影响,pH=5的条件下进行老化会加速絮体的羟桥反应和结晶反应,而pH=9的条件下进行老化则会涉及溶解-沉淀-结晶反应.