Effect of Pre-ozonation on Optimized Coagulation of a Typical North-China Source Water

Although ozone is widely used as a pre-oxidant before coagulation in water treatment, the effect of pre-ozonation on optimized coagulation for removal of particle and natural organic matter (NOM) is still not fully understood. In this paper, pilot-scale investigation was conducted to examine the impact of pre-ozonation on coagulation for particle and NOM removal. Changes in the particle and NOM distributions were characterized by various methods, including laser light granularity system, particle counter, ultrafiltration, and resin absorbent fractionation. A novel composite flocculant–HPAC was compared with the traditional ferric chloride coagulant in terms of coagulation efficiency under the influence of pre-ozonation. Typical micro-polluted North China surface water was used for pilot coagulation tests. The results show that the effect of pre-ozonation on coagulation is associated with the dosage of ozone, coagulant type, and water contamination characteristics. For FeCl₃, pre-ozonation acts as a coagulation aid at low dosage (1.0 mg L⁻¹ O₃) for turbidity and UV₂₅₄ removal; while at higher dosage (2.0 mg L⁻¹ O₃), pre-ozonation is detrimental to UV₂₅₄ removal although it is still beneficial for turbidity removal. In the case of composite flocculant–HPAC, pre-ozonation demonstrates negligible influence on both turbidity and UV₂₅₄ removal. Ozone can simultaneously aggregate fine particles and break down large ones, making them more mineralized and easier to remove. NOM with intermediate molecular weight and hydrophobic neutral property increases at lower ozone dosage, favoring removal by coagulation. At higher ozone dosages, NOM becomes more hydrophilic and its molecular weight becomes smaller, decreasing NOM removal.     

优化混凝处理低温低浊黄河水及对余铝的控制

考察了4种混凝剂,高效聚合氯化铝（HPAC）,聚合氯化铝（PACl）,硫酸铝（Al2（SO4）3）,混合PACl和氯化铁（FeCl3）,对低温低浊黄河原水的混凝效果与沉后水残留铝含量的关系。结果表明,当采用Al2（SO4）3或PACl做混凝剂时,在取得较好浊度去除的投药量下,水中余铝浓度会超过国家标准（0．2131g／L）。而采用HPAC或FeCl3和PACl复配药剂,在取得与Al2（SO4）3或PACl类似的浊度去除效果的同时,也能较好地控制水中的余铝含量。当HPAC投加量为21mg／L时,沉后水浊度降至1．3NTU,残留铝含量为0．147mg／L。复配投加PACl 15mg／L和FeCl3 12mg／L后,沉后水浊度为1．18NTU,残留铝含量为0．074mg／L。PACl和氯化铁的复配比例需要精确的调控,否则容易导致出水余铁余铝含量增加。而HPAC投加量小于21mtg／L时出水余铝浓度均低于国家标准。因此,在这4种混凝剂中,就混凝效果及余铝控制而言,HPAC更适合充当低温低浊水源水的混凝处理药剂。     

不同混凝剂处理低温低浊水

针对低温低浊水处理难度大的问题进行了一系列的混凝实验,实验结果表明,随着混凝剂投加量的增加,剩余浊度呈现先降低后升高的趋势,单独使用HPAC时,剩余浊度在投加量为14 mg/L时达到最低(2.39 NTU)。pH值对余铝含量具有重要的影响,3种铝系混凝剂均在pH=7.0时余铝含量达到最低。AlCl3对水中有机物的去除率较其他3种混凝剂低。絮体形成与破碎受搅拌强度的影响很大,当破碎强度增加到50 r/min,使用PACl、HPAC、FeCl3作混凝剂时絮体粒径下降不明显,当破碎强度增加到100 r/min时,絮体粒径有明显的下降。破碎结束后,絮体粒径有所恢复,但是并不能增长到破碎前的粒径。PACl、HPAC以及FeCl3形成的絮体的沉降性较好,上覆水浊度下降较快,经过3 h的沉降后,剩余浊度分别达到1.82、1.44和0.97 NTU。     

响应面法优化混凝处理西北农村水窖水

针对西北地区水窖水低温低浊且微污染的水质特点,采用混凝工艺实现水质提升。通过研究混凝剂投量、助凝剂投量、pH等单因素对浊度、高锰酸盐指数、UV₂₅₄、氨氮去除率的影响,并利用Design-Expert软件对实验数据进行处理,得到二次响应曲面模型各因素间相互作用对响应值的影响,以及其最佳水平。结果表明：采用PAC+PAM的组合处理窖水时,最佳工艺参数PAC投加量为52.08 mg·L⁻¹,PAM投加量为0.32 mg·L⁻¹,pH为8.03时,微污染窖水浊度、高锰酸盐指数、氨氮去除率分别为95.8%、81.1%、48.6%。且在浊度、高锰酸盐指数、氨氮模型中,各因变量的影响程度依次为：pH>助凝剂投加量>混凝剂投加量;助凝剂投加量>混凝剂投加量>pH;混凝剂投加量>pH>助凝剂投加量。通过模型可信度分析证明：响应曲面法用于优化混凝工艺处理水窖水的可行性和有效性,同时也为雨雪水等非常规水源水质的净化提供了技术参考。     

Enhanced coagulation with polyaluminum chlorides: role of pH/alkalinity and speciation

Enhanced coagulation is considered to be among the best available techniques (BAT) for disinfection by-product (DBP) precursor removal in water treatment. Improving existing understanding requires further consideration of nuances of chemical speciation relative to source water chemistry. In this paper, the effect of alkalinity/pH and speciation on inorganic polymer flocculants, polyaluminum chlorides (PACls) for enhanced particle and natural organic matter (NOM) removal was investigated. Three kinds of well-characterized typical source waters in China with low, moderate, and high alkalinity were selected. Performance of coagulants is controlled not only by preformed species but also by those formed in situ. At neutral and basic pH values, PACls with higher basicity (ratio of OH(-)/Al), which have more stable preformed Alb (the rapid reacted species as in ferron assay), are more efficient for turbidity and NOM removal. At slightly acidic pH, PACls with lower basicity are more efficient since more Alb can be formed in situ. Optimal NOM removal was achieved at pH 5.5-6.5 for all PACls. Basicity, speciation, and dosage of coagulant should be optimized based on raw water alkalinity to enhance the removal efficiency of NOM.     

高效聚合氯化铝对超滤膜污染影响的中试研究

针对某水厂以超滤为核心的短流程水处理工艺,在通过聚氯乙烯(PVC)超滤膜之前选择不同投加量(5、10、15和20 mg/L)的高效聚合氯化铝(HPAC)对长江下游原水进行混凝处理。通过跨膜压差(TMP)增长趋势、CODMn的去除率以及混凝后的水质,可知HPAC的最优投加量为15 mg/L。在此投加量下,运用体积排阻色谱法分析原水、膜前水、膜后水中各相对分子质量有机物的变化,可以发现混凝去除有机物的效果要优于超滤截留的。继而将HPAC与另外4种常用混凝剂:硫酸铝(分析纯)、氯化铁(化学纯)、聚合氯化铝(PAC)、聚合硫酸铁进行对比,结果表明,在它们各自最优投加量下,HPAC能够更有效地减缓超滤膜TMP的增长率,从而降低膜污染。因此,认为HPAC是与PVC超滤合金膜契合效果最佳的混凝剂。     

不同混凝剂处理松花江低温水

东北松花江地区冬季有将近6个月的冰封期,低温季节水源水处理难度大。为了保证东北地区冬季饮用水供应,研究几种混凝剂在处理冬季松花江低温水时的混凝效果。实验结果表明,NPAC1和NPAC2水解产物中具有较高的Alb和Alc成分,拥有较高的电中和、吸附和网捕卷扫性能,高效聚铝铁(PAF)水解产物Fe(OH)3具有比表面积大、吸附架桥作用较强的优点。这3种混凝剂无论是在控制出水浊度还是在对水体有机物去除能力方面均优于目前水厂所使用的PAC和聚合氯化铝铁(水厂PAF);NPAC2的投加量达到50 mg/L时,出水浊度达到最优;当混凝剂投加量达到50 mg/L时,NPAC1的浊度去除率逐渐超过NPAC2,剩余浊度低于3.0 NTU;NPAC1、NPAC2和PAF 3种混凝剂对有机物的去除能力大致相当,当混凝剂投加量为50 mg/L时,这3种混凝剂处理后的水的UV254的值均低于0.06,而水厂使用的2种混凝剂处理后的水的UV254仍高于0.1;结合其对浊度去除的情况,可以判断55 mg/L的投药量为NPAC1的最优投药点,PAF的最佳投药量为65 mg/L;投加适量的粉末活性碳可以有效地提高氨氮的去除率,当粉末活性炭的投加量为30 mg/L时,氨氮的去除率基本达到最大(51.27%)。表面负荷对混凝效果具有重要的影响,合理降低沉淀池的表面负荷对于提高出水水质具有重要作用。     

Removal of humic acid using TiO2 photocatalytic process--fractionation and molecular weight characterisation studies

The photocatalytic removal of humic acid (HA) using TiO₂ under UVA irradiation was examined by monitoring changes in the UV₂₅₄ absorbance, dissolved organic carbon (DOC) concentration, apparent molecular weight distribution, and trihalomethane formation potentials (THMFPs) over treatment time. A resin fractionation technique in which the samples were fractionated into four components: very hydrophobic acids (VHA), slightly hydrophobic acids, hydrophilic charged (CHA) and hydrophilic neutral (NEU) was also employed to elucidate the changes in the chemical nature of the HA components during treatment. The UVA/TiO₂ process was found to be effective in removing more than 80% DOC and 90% UV₂₅₄ absorbance. The THMFPs of samples were decreased to below 20 μg l⁻¹ after treatments, which demonstrate the potential to meet increasingly stringent regulatory level of trihalomethanes in water. Resin fractionation analysis showed that the VHA fraction was decreased considerably as a result of photocatalytic treatments, forming CHA intermediates which were further degraded with increased irradiation time. The NEU fraction, which comprised of non-UV-absorbing low molecular weight compounds, was found to be the most persistent component.     

基于微滤技术供水厂的臭氧预氧化前置工艺中臭氧投加量的优化

通过臭氧预氧化降解水体中溶解性有机物(DOM)对DOM的氧化效果以及微滤(MF)膜污染的缓和效应进行了研究,并分析了臭氧氧化过程中光谱参数变化的规律,进而提出一种通过多目标优化模型确定最佳臭氧投加量的方法。结果表明,臭氧预氧化技术能够将中等分子质量的芳香类DOM转化为低分子质量的有机化合物,对应的UV₂₅₄去除率最高可达90.34%,从而显著改变了MF进水的光谱特性。此外,臭氧预氧化还显著缓解了DOM造成的膜污染,膜污染指数(FI)最多可降低51.49%。根据上述结果可建立多目标优化模型,并用于确定臭氧预氧化-膜过滤工艺最佳臭氧投加量。根据层次分析法,对SUVA₂₅₄、FI和臭氧利用率3个客观指标分配不同的权重,以满足不同饮用水厂的需求。此外,模型分析中可用光谱斜率作为SUVA₂₅₄的替代参数,特别是S_275~295 (R²=0.979 7),用UV₂₅₄作为FI的替代参数(R²=0.879 9),进而简化模型系数的获取。以上研究结果可为水厂在实际应用中优化臭氧投加量、综合提高水处理效果、缓解膜污染并降低运行成本提供参考。     

混凝剂中的铝形态对黄河水源水中出水余铝的影响

铝系混凝剂是应用最广泛的无机混凝剂,改善混凝剂中的铝形态可有效提高混凝效果,但其在净水过程中产生的余铝对人体健康及输水过程具有显著的影响。本文研究了氯化铝(AlCl₃)和高聚十三铝(Al₁₃) 2种混凝剂在处理黄河上游水源水时的混凝过程,结合出水中的溶解态及不同分子质量余铝含量、有机物紫外吸光度(UV₂₅₄)、pH、浊度、有机物种类及含量和絮体特性的变化趋势,探究混凝剂中的铝形态对混凝过程的影响。结果表明,在实验投加量范围内,当Al₁₃做混凝剂时,出水余铝质量浓度均低于0.2 mg·L⁻¹。Al₁₃具有较高的形态稳定性,在混凝过程中对出水pH影响较小。絮体粒度随混凝剂投加量的增加而增加,Al₁₃投加量达到0.08 mmol·L⁻¹时絮体粒度下降(强度因子由于静电排斥作用而下降)。在不同投加量下,使用AlCl₃做混凝剂时出水余铝均高于Al₁₃体系,且在不同投加量下AlCl₃体系出水余铝中小于1 000 Da的余铝占比最大。Al₁₃对富里酸和腐殖酸的去除效果优于AlCl₃,且AlCl₃在较高投加量下才能实现水中有机物的有效去除。     

粉末吸附材料协同HPAM强化混凝消除微污染水中OCPs

以阴离子型聚丙烯酰胺(HPAM)为絮凝剂,采用强化混凝的处理方法,对微污染水中有机氯农药(OCPs)的消除进行了研究。考察了HAPM投加量、pH值、原水浊度、粉末活性炭及改性凹凸棒土助凝剂等因素对OCPs消除效果的影响。结果表明,HPAM投加量为0.05~0.1 mg/L时,OCPs不同异构体的去除率可达57.00%~74.56%;浊度去除率与OCPs去除率之间显著相关(p<0.05),较高的原水浊度有利于HPAM对OCPs的去除;HPAM混凝消除OCPs的最佳pH值为5~6;改性凹凸棒土作为助凝剂复配HPAM可有效提高OCPs的去除率,粉末活性炭复配效果不明显,所以凹凸棒土比粉末活性炭更加适合作为助凝剂在强化混凝中去除OCPs。     

纳米SiO2对Pb2+污染水源水混凝过程的影响

随着纳米材料的广泛应用,越来越多的纳米材料会泄露到水环境中,但目前关于纳米材料对混凝过程的影响还缺乏充分的研究。针对不同浊度,不同纳米SiO2浓度,不同pH以及腐殖酸对混凝去除Pb2+的影响进行了一系列的研究。结果表明,在低投加量(40 mg/L) 条件下,Pb2+的去除率受浊度影响较大,然而在高投加量(80 mg/L) 条件下,Pb2+的去除率受浊度的影响反而较小,且随着浊度从15.0 NTU增加到90.0 NTU,Pb2+的去除率从70.172%下降到63.925%。当浊度为45.0 NTU,投加量为40 mg/L时,铅离子的去除率在 SiO2投加量达到0.8 mg/L时达到最高(92.34%)。由于在低浊度条件下絮体形成不充分,以至于生成的絮体对SiO2的吸附去除率较低,所以吸附在SiO2表面的Pb2+会悬浮在溶液体系中,造成Pb2+去除率的下降。随着pH的升高,Pb2+去除率呈先升高后降低的趋势,且在偏碱性条件下达到最高。pH对Pb2+去除率的影响主要体现在其对纳米SiO2表面电荷的影响,SiO2表面负电荷增多可有效提高Pb2+的去除率,说明纳米SiO2的吸附作用在去除Pb2+的过程中起重要的作用。在高混凝剂投加量(80.0 mg/L)下腐殖酸对Pb2+的去除有促进作用,且当腐殖酸存在时,SiO2的含量对Pb2+的去除率无明显影响。     

Effect of copper(II) on natural organic matter removal during drinking water coagulation using aluminum-based coagulants.

Coagulation has been proposed as a best available technology for controlling natural organic matter (NOM) during drinking water treatment. The presence of heavy metals such as copper(II) in source water, which may form copper-NOM complexes and/or interact with a coagulant, may pose a potential challenge on the coagulation of NOM. In this work, the effect of copper(II) on NOM removal by coagulation using alum or PAX-18 (a commercial polymerized aluminum chloride from Kemiron Inc., Bartow, Florida) was examined. The results show that the presence of 1 to 10 mg/L of copper(H) in the simulated waters improved the total organic carbon (TOC) removal by up to 25% for alum coagulation and by up to 22% for PAX-18 coagulation. The increased NOM removal with the presence of copper(II) in the waters can most likely be ascribed to the formation copper-NOM complexes that may be more adsorbable on aluminum precipitates and to the formation of copper(II) co-precipitates that may also adsorb NOM. The presence of 1 to 5 mg/L of copper(I) in the waters containing 3 mg/L NOM as carbon was reduced below the maximum contaminant level goal (1.3 mg/L as copper) using either coagulant. The results suggest that the presence of copper(H) in source water may not adversely affect the NOM removal by coagulation. A good linear correlation was observed between the TOC removal efficiency and the log-total moles of the precipitated metals, which include the metal ion from a coagulant and the divalent metal ion(s) in source water.     

聚硅酸阳离子絮凝剂处理印染废水

以工业废弃物为主要原料,经过同时聚合制备聚硅酸阳离子絮凝剂(PSiC)。实现硅酸缩合自聚、铁铝离子羟化聚合以及硅与铁铝离子聚合同步交互进行。利用PSiC处理印染废水,研究PSiC去除浊度、色度和和UV254的性能,分析其除污染机理。结果表明,PSiC处理印染废水时最佳投放量为80 mg/L,此时浊度和色度去除率分别达到50%和90%。废水pH为7、PSiC投加量80 mg/L时对印染废水UV254的去除率为65%。pH和投加量过大或过小都会降低PSiC去除UV254的效果。在混凝搅拌初期UV254迅速下降,停止搅拌后又略有所上升。沉淀初期UV254稍有波动,沉降10 min后基本趋于稳定。     

不同有机物对含藻水体混凝效果和絮体特性的影响

为了解不同有机物对含藻水体混凝过程的影响,以含铜绿微囊藻水体作为实验对象,考察牛血清蛋白(BSA)和腐殖酸(HA)2种有机物及其质量浓度对含藻水体浊度、藻类有机物的去除效果以及絮体形成、破碎、再絮凝的影响。结果表明,少量的BSA对混凝反应起促进作用,当BSA的投加量超过1 mg·L⁻¹转为抑制作用,因为投加量升高时,BSA抢占混凝剂活性位点,抑制混凝反应。HA不利于混凝反应的进行,因为HA中的官能团优先与混凝剂结合,从而导致混凝效果变差。提高混凝药剂投加量可缓解有机物质量浓度增加对混凝效果的影响。当BSA投加量为5 mg·L⁻¹,PACl投加量为0.06 mmol·L⁻¹时,能达到出水浊度小于1 NTU,藻细胞去除率大于90 %的混凝效果,HA添加量为5 mg·L⁻¹,PACl投加量为0.12 mmol·L⁻¹时,也能达到相同的混凝效果。混凝更容易去除分子质量较大的BSA和HA,而对小分子亲水性有机物的去处效果较差,如藻类有机物或HA中小分子有机物。少量的BSA和HA增加了混凝絮体的生成速率和初始粒径。本研究结果可为天然水体混凝除藻工艺优化运行提供参考。     

应用加载磁混凝处理微污染河水

实验对比考察了常规混凝和加载磁混凝工艺对微污染河水中COD、浊度和TP等污染物的去除效果,系统研究了混凝剂用量、磁种加载量、搅拌条件和药剂投加顺序等因素对加载磁混凝效果的影响。实验结果表明,加载磁种后沉淀颗粒的体积平均粒径为从常规混凝工艺的50.1 μm显著增加到68.6 μm;污染物去除效果明显优于常规混凝工艺,尤其对浊度和总磷的去除效果得到了显著的提升;在实验最优条件下COD、浊度和TP的去除率分别达到54.17%、99.28%和75.82%;并且加载磁种后可减少50%以上的混凝剂投加量,同时大大缩短沉淀时间。     

UV-H2O2 based AOP and its integration with biological activated carbon treatment for DBP reduction in drinking water

The presence of disinfection byproducts (DBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs) in drinking water is of great concern due to their adverse effects on human health. Emerging regulation limiting the concentration of DBPs in drinking water has increased demands for technologies and processes which reduce the formation of DBPs in drinking water. In this study, UV-H₂O₂ based advance oxidation process (AOP) was used to treat raw surface water. Experiments were conducted using low pressure mercury vapor UV lamps in collimated beam and flow-through annular photoreactors. The effect of UV fluence (0–3500 mJ cm⁻²) and hydrogen peroxide concentration (0–23 mg l⁻¹) in reducing the concentration of THMs and HAAs was examined. The UV-H₂O₂ AOP was then coupled with a downstream biological activated carbon (BAC) treatment to assess the synergetic benefits of combining the two treatments. It was observed that UV-H₂O₂ AOP was only effective at reducing DBPs at UV fluences of more than 1000 mJ cm⁻²and initial H₂O₂ concentrations of about or greater than 23 mg l⁻¹. However, the combined AOP–BAC treatment showed significant reductions of 43%, 52%, and 59% relative to untreated raw water for DBPs, TOC, and UV₂₅₄, respectively.     

Oxidative treatment of simulated dyehouse effluent by uv and near-UV light assisted Fenton's reagent

UV/Fenton, near-UV-visible/Fenton, dark Fenton, and H₂O₂/UV reactions have been used to treat simulated dyehouse effluents representing wastewater from the textile dyeing and rinsing process. Experiments were carried out in a lab - scale photochemical reactor using concentrations of 0.5–25 mM H₂O₂, 0.04-0.5 mM Fe²⁺-ion and different dilutions of textile wastewater. To assess the extent of mineralization, decolourization kinetics and the effect of different fight sources on treatment efficiency, DOC, optical density at 254 nm and 600 nm wavelength and residual H₂O₂ concentrations were measured during the course of the advanced oxidation reactions. Comparative evaluation of the obtained results revealed that the decolourization rate increased with applied H₂O₂ and Fe²⁺-ion dose as well as the strength of the synthetic textile wastewater. The best results were obtained by the near - UV/visible/Fenton process with a decolourization rate constant of 1.57 min⁻¹, a UV_254nm reduction of 97% and a DOC removal of 41% at relatively low doses of the H₂O₂ oxidant and Fe²⁺-ion catalyst within 60 min treatment time.     

陶瓷印花废水处理的混凝剂及工艺条件

采用混凝剂聚合氯化铝（PAC）、聚丙烯酰胺（PAM）、聚合硫酸铁（PFS）对陶瓷印花废水进行混凝沉降处理,监测水样的吸光度、浊度、悬浮物,以脱色率、浊度去除率、悬浮物去除率评价混凝处理的效果。结果表明：PAC是陶瓷印花废水沉降处理的理想混凝剂;水样的吸光度、浊度、悬浮物随混凝剂用量增大和沉降时间延长而呈降低趋势,而脱色率、浊度去除率、悬浮物去除率随混凝剂和沉降时间的增大呈增大的趋势;PAC投加量为20mg／L,沉降时间约为24h,水样脱色率达到90．0％,而当PAC投加量达到100mg／L,沉降时间约为4h,陶瓷印花水的脱色率可达到96．0％。证明了药剂用量的增加与沉降时间的延长对混凝过程具有增效作用。     

氢氧化镁混凝过程絮体形成研究

以不同浊度高岭土水样为研究对象,运用激光光散射法对氢氧化镁混凝剂絮体开始形成时间和氯化镁最小投加量进行测定,探讨了氯化镁投加量对沉后出水浊度和Zeta电位的影响.结果表明:(1)氢氧化镁混凝剂絮体开始形成时间随着氯化镁投加量的增大而缩短;pH增大及浊度增大时,絮体开始形成时间总体缩短,pH=11.5、氯化镁投加量为25...