Effects of alkalinity on interaction between EPS and hydroxy-aluminum with different speciation in wastewater sludge conditioning with aluminum based inorganic polymer flocculant

Extracellular polymeric substances (EPS) form a stable gel-like structure to combine with water molecules through steric hindrance, making the mechanical dewatering of wastewater sludge considerably difficult. Coagulation/flocculation has been widely applied in improving the sludge dewatering performance, while sludge properties (organic fraction and solution chemistry conditions) are highly changeable and have important effects on sludge flocculation process. In this work, the alkalinity effects on sludge conditioning with hydroxy-aluminum were comprehensively investigated, and the interaction mechanisms between EPS and hydroxy-aluminum with different speciation were unraveled. The results showed that the effectiveness of hydroxy-aluminum conditioning gradually deteriorated with increase in alkalinity. Meanwhile, the polymeric hydroxy-aluminum (Al₁₃) and highly polymerized hydroxy-aluminum (Al₃₀) were hydrolysed and converted into amorphous aluminum hydroxide (Al(OH)₃), which changed the flocculation mechanism from charge neutralization and complexing adsorption to hydrogen bond interaction. Additionally, both Al₁₃ and Al₃₀ showed higher binding capacity for proteins and polysaccharides in EPS than monomeric aluminum and Al(OH)₃. Al₁₃ and Al₃₀ coagulation changed the secondary structure of proteins in EPS, which caused a gelation reaction to increase molecular hydrophobicity of proteins and consequently sludge dewaterability. This study provided a guidance for optimizing the hydroxy-aluminum flocculation conditioning of sludge with high solution alkalinity.     

3类金属离子对活性污泥吸附水体腐殖酸的影响

研究了3类金属离子对活性污泥吸附水体腐殖酸效果的影响.结果表明,盐类金属离子(Na )、硬度金属离子(Ca2 、Mg2 )和水解金属离子(Al3 、Fe3 )均能在一定程度上提高吸附效率.作为活性污泥助凝剂,以大于10-2mol/L硬度离子的促进效果为好.加入10-2mol/L Ca2 、Mg2 48 h后溶液中的腐殖酸浓度分别为(0.64±0.17)mg/L和(2.32±0.40)mg/L,其去除率分别为98.4%和94.2%;当加入10-1mol/L Ca2 、Mg2 48 h后,其去除率均接近100%,而且Ca2 离子促进作用要优于Mg2 .盐类金属离子、硬度金属离子、水解金属离子提高活性污泥吸附腐殖酸的主要作用机理可能分别是压缩双电层、架桥作用、吸附共沉淀.同时,投加金属离子也可能使活性污泥上的吸附位性质改变或失效,对腐殖酸的吸附有一定的负面影响.     

Al3+对序批式生物膜反应器(SBBR)中污泥脱氢酶活性(DHA)和胞外聚合物(EPS)的影响

通过向序批式生物膜反应器(SBBR)中投加氯化铝,研究了化学协同生物除磷过程中Al~(3+)对污泥脱氢酶活性(DHA)、胞外聚合物(EPS)及系统处理效果的影响.结果表明,氯化铝投加量少于0.1 mmol·L~(-1)时,Al~(3+)对微生物的活性有促进作用,多于0.1 mmol·L~(-1)的Al~(3+)对其活性有明显的抑制作用.氯化铝投加量少于0.1 mmol·L~(-1)时,Al~(3+)能够促进EPS中多糖(PS)和蛋白质(PN)的分泌,多于0.1 mmol·L~(-1)的Al~(3+)则只促进多糖的分泌,但对EPS的分泌总量没有影响.Al~(3+)会使污泥的SVI值显著降低,大大改善其沉降性能.MLSS、MLVSS基本上是随着Al~(3+)投加量的增加而增大,MLVSS/MLSS随着投药量的增加先减小后增大再减小.Al~(3+)对COD和TN的去除具有轻微抑制作用,但对TP的去除具有显著的改善作用.当Al~(3+)的投加为0.5 mmol·L~(-1)时,TP的去除效果最好,出水浓度仅为0.44 mg·L~(-1),满足一级A排放标准.此时,TP的去除率为92.7%,比不加药时提升了10.2%.     

高碳氮负荷下同时脱氮除碳好氧颗粒污泥研究

在4 L反应器中,以补加葡萄糖和硫酸铵的猪场废水为基质,不接种活性污泥,加入粉末状活性炭对废水土著微生物进行预固定.通过批次进水并控制运行条件（逐渐提高COD、NH 4＋-N负荷、缩短沉降时间、提高曝气量）培养同时脱氮除碳好氧颗粒污泥,研究了该好氧颗粒污泥的脱氮除碳功能及对高碳氮负荷冲击的响应.结果表明,成熟好氧颗粒污泥为土黄色不规则球状,粒径为0.5～3.5 mm.COD和NH 4＋-N负荷分别在4.80～12.6 kg.（m3.d）-1和0.217～0.503 kg.（m3.d）-1时,好氧颗粒污泥对COD的去除率〉94%,对NH 4＋-N的去除率〉98%.当COD和NH 4＋-N负荷分别提高至15.70 kg.（m3.d）-1和0.723kg.（m3.d）-1并运行4 d后,反应器内絮体激增,颗粒沉降变差并开始破碎,NH 4＋-N去除率下降至81.6%.排出部分污泥并降低负荷继续运行,颗粒污泥的NH 4＋-N去除率可迅速恢复至98%以上.本研究培养的好氧颗粒污泥具有良好的同时脱氮除碳功能,可以耐受高COD和NH 4＋-N负荷的双重冲击.     

Magnetically recoverable Fe3O4@polydopamine nanocomposite as an excellent co-catalyst for Fe3+ reduction in advanced oxidation processes

Advanced oxidation processes are widely applied to removal of persistent toxic substances from wastewater by hydroxyl radicals(·OH),which is generated from hydrogen peroxide(H_2O_2) decomposition.However,their practical applications have been hampered by many strict conditions,such as iron sludge,rigid pH condition,large doses of hydrogen peroxide and Fe~(2+),etc.Herein,a magnetically recyclable Fe_3O_4@polydopamine(Fe_3O_4@PDA) coreshell nanocomposite was fabricated.As an excellent reducing agent,it can convert Fe~(3+)to Fe~(2+).Combined with the coordination of polydopamine and ferric ions,the production of iron sludge is inhibited.The minimum concentration of hydrogen peroxide(0.2 mmol/L and Fe~(2+)(0.18 mmol/L)) is 150-fold and 100-fold lower than that of previous reports,respectively.It also exhibits excellent degradation performance over a wide pH range from 3.0 to 9.0.Even after the tenth recycling,it still achieves over 99% degradation efficiency with the total organic carbon degradation rate of 80%,which is environmentally benign and has a large economic advantage.This discovery paves a way for extensive practical application of advanced oxidation processes,especially in environmental remediation.     

氯化铁用于反硝化同步化学生物絮凝工艺研究

通过小试考察了氯化铁用于反硝化同步化学生物絮凝工艺的可行性.结果表明,在氯化铁投加量（以铁计）为20mg.L-1的条件下,反硝化污泥通过14 d的驯化,可以适应氯化铁的投加,反硝化速率、COD和NO3--N去除效果与空白反应器无明显差异,同时具有较好的TP去除效果,去除率高于80%.氯化铁的投加虽然提高了污泥浓度,但由于污泥中无机物比例增加、密度增大,同时污泥粒径变小,使污泥的沉淀性能与空白反应器中的污泥无明显差异,且SV30值仅为22%左右,小于空白反应器中污泥的27%.投加氯化铁后的污泥比阻平均为1.5×1012m.kg-1,远低于空白反应器中污泥的40.2×1012m.kg-1,浓缩后污泥的体积减少和比阻的降低有利于污泥的后续处理.     

Effect of AlCl3 concentration on nanoparticle removal by coagulation

In recent years, engineered nanoparticles, as a new group of contaminants emerging in natural water, have been given more attention. In order to understand the behavior of nanoparticles in the conventional water treatment process, three kinds of nanoparticle suspensions, namely multi-walled carbon nanotube-humic acid (MWCNT-HA), multi-walled carbon nanotube-N,N-dimethylformamide (MWCNT-DMF) and nanoTiO₂-humic acid (TiO₂-HA) were employed to investigate their coagulation removal efficiencies with varying aluminum chloride (AlCl₃) concentrations. Results showed that nanoparticle removal rate curves had a reverse “U” shape with increasing concentration of aluminum ion (Al^3 +). More than 90% of nanoparticles could be effectively removed by an appropriate Al^3 + concentration. At higher Al^3 + concentration, nanoparticles would be restabilized. The hydrodynamic particle size of nanoparticles was found to be the crucial factor influencing the effective concentration range (ECR) of Al^3 + for nanoparticle removal. The ECR of Al^3 + followed the order MWCNT-DMF > MWCNT-HA > TiO₂-HA, which is the reverse of the nanoparticle size trend. At a given concentration, smaller nanoparticles carry more surface charges, and thus consume more coagulants for neutralization. Therefore, over-saturation occurred at relatively higher Al^3 + concentration and a wider ECR was obtained. The ECR became broader with increasing pH because of the smaller hydrodynamic particle size of nanoparticles at higher pH values. A high ionic strength of NaCl can also widen the ECR due to its strong potential to compress the electric double layer. It was concluded that it is important to adjust the dose of Al^3 + in the ECR for nanoparticle removal in water treatment.     

Effectiveness of Poliovirus Concentration and Recovery from Treated Wastewater by Two Electropositive Filter Methods

Enteric viruses are often present in low numbers in various water matrices. Virus sampling therefore involves multiple concentration steps to condense large samples down to small volumes for detection by cell culture or molecular assays. The NanoCeram^® Virus Sampler has been demonstrated to be effective for the recovery of viruses from tap water, surface waters, and seawater. The goal of this study was to evaluate a new method using NanoCeram^® filters for the recovery of poliovirus 1 (PV-1) from treated wastewater. Activated sludge effluent samples were spiked with PV-1 and concentrated in side-by-side tests by two methods: (1) NanoCeram^® filtration, elution with sodium polyphosphate buffer, secondary concentration via centrifugal ultrafiltration; and (2) 1MDS filtration, elution with beef extract, secondary concentration via organic flocculation. The virus retention and elution efficiencies did not differ significantly between the two methods. In contrast, the secondary concentrate volume was smaller for the NanoCeram^® method (8.4 vs. 30 mL) and the secondary concentration efficiencies were different between the two methods with 98 % for centrifugal ultrafiltration (NanoCeram^®) and 45 % for organic flocculation (1MDS). The overall method efficiencies were significantly different (P ≤ 0.05) with the NanoCeram^® method yielding a 57 % and the 1MDS a 23 % virus recovery. In addition, there appeared to be less interference with viral detection via polymerase chain reaction with the NanoCeram^® concentrates. This NanoCeram^® method therefore is able to efficiently recover PV-1 from large volumes of wastewater and may serve as an inexpensive alternative to the standard 1MDS filter method for such applications.     

好氧/厌氧潜流湿地结构工艺优化

前期研究表明在人工潜流湿地(SFCWs)中设置好氧段和厌氧段可显著提高SFCWs对COD、NH4+-N的去除率.然而曝气产生的富氧环境不利于NO3--N和NO2--N的去除,一定程度上抑制了反硝化反应的进行.反硝化程度较低是实验中仍需进一步解决的问题.本研究在前期研究的基础上,对好氧/厌氧多级串联潜流人工湿地结构及工艺进行了改进优化,采用多点进水的措施来强化反硝化过程,并设计相应的区段去除该部分污染物.结果表明,水力负荷约为0.06m3.(m2.d)-1时,进一步优化结构和比例的好氧-缓冲-厌氧-缺氧-好氧曝气多点进水湿地对COD、NH4+-N和TN的去除率可达到91.6%、100%和87.7%.在补充进水之后的区段,COD/N迅速升高到10以上,做到了补充碳源的同时最大限度地利用湿地去除污染物.改良后的湿地达到了净化工艺优化的目的,为提高人工湿地总氮去除效率提供了理论依据及应用基础.     

Biological nutrient removal by internal circulation upflow sludge blanket reactor after landfill leachate pretreatment

The removal of biological nutrient from mature landfill leachate with a high nitrogen load by an internal circulation upflow sludge blanket （ICUSB） reactor was studied. The reactor is a set of anaerobic-anoxic-aerobic （A^2/O） bioreactors, developed on the basis of an expended granular sludge blanket （EGSB）, granular sequencing batch reactor （GSBR） and intermittent cycle extended aeration system （ICEAS）. Leachate was subjected to stripping by agitation process and poly ferric sulfate coagulation as a pretreatment process, in order to reduce both ammonia toxicity to microorganisms and the organic contents. The reactor was operated under three different operating systems, consisting of recycling sludge with air （A^2/O）, recycling sludge without air （low oxygen） and a combination of both （A^2/O and low oxygen）. The lowest effluent nutrient levels were realised by the combined system of A^2/O and low oxygen, which resulted in effluent of chemical oxygen demand （COD）, NH3-N and biological oxygen demand （BOD5） concentrations of 98.20, 13.50 and 22.50 mg/L. The optimal operating conditions for the efficient removal of biological nutrient using the ICUSB reactor were examined to evaluate the influence of the parameters on its performance. The results showed that average removal efflciencies of COD and NH3- N of 96.49% and 99.39%, respectively were achieved under the condition of a hydraulic retention time of 12 hr, including 4 hr of pumping air into the reactor, with dissolved oxygen at an rate of 4 mg/L and an upflow velocity 2 m/hr. These combined processes were successfully employed and effectively decreased pollutant loading.     

厌氧氨氧化微生物颗粒化及其脱氮性能的研究

利用厌氧颗粒污泥作为种泥,启动SBR反应器,旨在培养厌氧氨氧化颗粒污泥以及研究其脱氮性能.结果表明,水力停留时间(HRT)是富集厌氧氨氧化微生物的1个重要控制因素,以HRT为30 d,第58 d时,SBR反应器就出现厌氧氨氧化现象,与此同时,颗粒污泥由灰黑色变为棕褐色,粒径减小.到第90 d时,成功培养出厌氧氨氧化颗粒污泥,NH⁺₄-N和NO^-₂-N同时被去除,最大去除速率分别达到14.6 g/(m³·d)和6.67 g/(m³·d).从第110　d开始,逐步降低HRT,以提高基质负荷促进厌氧氨氧化菌生长.到目前t＝156　d,HRT降到5　d,氨氮和亚硝酸氮的去除率分别达到60.6%和62.5%,亚硝酸氮/氨氮的比率为1.12.污泥也由棕褐色变为红棕色,形成红棕色的具有高厌氧氨氧化活性颗粒污泥,总氮负荷达到34.3 g/(m³·d).     

高氮渗滤液短程深度脱氮及反硝化动力学

采用单级UASB-SBR生化系统处理实际高氮晚期渗滤液,重点研究了系统的有机物和氮去除特性,同时考察了SBR短程生物脱氮系统内微生物的反硝化动力学特性.试验结果表明,该生化系统能够高效、深度去除渗滤液内高浓度有机物和氮.UASB反应器的平均COD负荷为6.5 kg/(m3.d),去除速率为5.3 kg/(m3.d).在进水COD平均为6 537 mg.L-1,NH+4-N为2 021mg.L-1的条件下,出水分别为354 mg.L-1和2.8 mg.L-1以下,去除率分别为94.6%和99.8%,尤其是该系统获得了99.2%的TN去除率,出水TN20 mg.L-1,实现了深度脱氮的目的.SBR反应器实现并维持了稳定的短程硝化,通过90%以上的亚硝化率实现高效的氨氮去除,同时SBR系统内微生物的反硝化特性符合Monod动力学方程.     

PACS中铝的形态分布及其经验公式

利用AlCl₃·6H₂O,Na₂SO₄和NaOH为原料制备了一系列具有不同Al3+/SO2₄-摩尔比及碱化度的PACS样品,利用Al-Ferron逐时络合比色法就Al3+/SO2_４-摩尔比及碱化度对PACS中铝的形态分布影响进行了实验研究,得到了一系列实验结果,建立了PACS中铝的水解形态分布与Al3+/SO2₄-摩尔比和碱化度之间的数学模型,数据拟合结果与实验结果比较,证明二者基本吻合。      

Flocculating characteristic of activated sludge flocs: Interaction between Al3+ and extracellular polymeric substances

Aluminum flocculant can enhance the flocculating performance of activated sludge.However,the binding mechanism of aluminum ion(Al 3+) and extracellular polymeric substances(EPS) in activated sludge is unclear due to the complexity of EPS.In this work,threedimensional excitation emission matrix fluorescence spectroscopy(3DEEM),fluorescence quenching titration and Fourier transform infrared spectroscopy(FT-IR) were used to explore the binding behavior and mechanism between Al 3+ and EPS.The results showed that two fluorescence peaks of tyrosineand tryptophan-like substances were identified in the loosely bound-extracellular polymeric substances(LB-EPS),and three peaks of tyrosine-,tryptophanand humic-like substances were identified in the tightly boundextracellular polymeric substances(TB-EPS).It was found that these fluorescence peaks could be quenched with Al 3+ at the dosage of 3.0 mg/L,which demonstrated that strong interactions took place between the EPS and Al 3+.The conditional stability constants for Al 3+ and EPS were determined by the Stern-Volmer equation.As to the binding mechanism,the-OH,N-H,C=O,C-N groups and the sulfurand phosphorus-containing groups showed complexation action,although the groups in the LB-EPS and TB-EPS showed different behavior.The TB-EPS have stronger binding ability to Al 3+ than the LB-EPS,and TB-EPS play an important role in the interaction with Al 3+.     

DPR-SNED系统处理低C/N城市污水与硝酸盐废水的运行特性

为实现低C/N城市污水与含硝酸盐废水的同步处理,采用SBR接种活性污泥,通过合理控制厌氧/缺氧/低氧时间和溶解氧(DO)浓度,实现了反硝化除磷耦合同步硝化内源反硝化(DPR-SNED)系统的启动,并对启动过程中系统的脱氮除磷特性进行了研究.结果表明采用厌氧/低氧的运行方式,控制厌氧时间为3 h,好氧段DO浓度为0. 5～1. 0 mg·L-1,60 d可实现同步硝化内源反硝化除磷(SNEDPR)系统的启动,出水PO_4~(3-)-P浓度0. 5 mg·L-1,系统氮磷去除率维持在90%以上,COD的去除率维持在80%以上,系统SNED率和CODins率分别维持在70%和95%左右;随后改变运行方式,采用厌氧/缺氧/低氧的方式运行,缺氧段前进含硝酸盐废水,45 d可实现DPR-SNED系统的启动,缺氧末PO_4~(3-)-P浓度1. 1 mg·L-1,出水PO_4~(3-)-P浓度0. 5 mg·L-1,系统磷、COD去除率均维持在90%以上,氮去除率维持在88%以上,系统SNED率和CODins率分别维持在62%和90%左右. DPR-SNED系统的成功启动后,厌氧段聚糖菌和聚磷菌对城市污水有限碳源的充分利用和强化储存,可为后续缺氧段及好氧段的脱氮除磷提供充足的内碳源.此外,DPR-SNED系统缺氧段内源短程反硝化的进行保障了系统在低C/N(4)条件下的高效脱氮.     

Simultaneous removal of SO2 and NO using a spray dryer absorption (SDA) method combined with O3 oxidation for sintering/pelleting flue gas

Based on the demand of sintering/pelleting flue gas ultra-low emission, a semi-dry method using a spray dryer absorber (SDA) combined with O₃ oxidation was proposed for simultaneous removal of SO₂ and NO. Effects of O₃ injection site, O₃/NO molar ratio, and spray tower temperature on the removal efficiencies were investigated. It was revealed that both desulfurization and denitrification efficiencies could reach to 85% under the conditions of setting O₃ injection site inside of tower, O₃/NO molar ratio 1.8, spray tower temperature 85°C, Ca/(S + 2 N) molar ratio 2.5 and slurry flow rate 300 mL/hr. CaSO₃/Ca(OH)₂ mixture slurry was used as absorbent to simulate operating conditions in iron and steel industry. The result shows that the addition of CaSO₃ weakens both removal efficiencies. In addition, the reaction mechanism of simultaneous removal of SO₂ and NO using SDA combined with O₃ oxidation was proposed.     

Taylor-Couette流场数值模拟及絮凝效果研究

通过流体力学中的Fluent软件模拟了Taylor-Couette反应器的速度矢量分布、湍动动能分布和有效能耗分布,同时实验研究了TaylorCouette反应器不同内筒转速下三氯化铁对高岭土悬浊液的絮凝效能.结果表明,内外筒环隙间存在亚微尺度的涡旋,当转速为30～60 r·min-时,涡旋形状闭合完整,相互分离,涡旋内部速度梯度较小,湍动动能k在0.00010 ～0.00023 m2·s-2的范围内,有效能耗ε在0.00057 ～0.00189 m2·s-3的范围内,絮凝效能达到最大(80％以上),湍动动能和有效能耗过大或过小均不利于形成完整闭合的涡旋,絮凝效能较差.     

聚合铝铁对A2/O系统 EPS及生物絮凝性能的影响

通过向实验室构建的A2/O模型好氧池末端投加聚合铝铁(PAFC)来强化系统的生物除磷,使得出水总磷达到《城市污水处理厂污染物排放标准GB 18918-2002》中的一级A标准,并重点分析投加的PAFC对A2/O系统中活性污泥胞外聚合物(EPS)和活性污泥生物絮凝性能的影响.结果表明,随着PAFC投药量的增加,A2/O系统活性污泥EPS总量变化不大,但EPS组分中蛋白/多糖含量的比值逐渐降低,由投药前的3.30降低至投药后的2.30;EPS中金属离子含量逐渐增加,在厌氧-缺氧-好氧的运行周期内,各处理单元污泥的EPS中金属铝离子含量增加.投加PAFC后,活性污泥颗粒变大,二沉池出水的Zeta电位明显降低,由投药前-15.83 mV降低至-21.20 mV,污泥产量增加.因此,适量投加PAFC后,生物絮凝性能得到改善,出水中悬浊颗粒减少,出水水质变好.     

Nitrogen and phosphorus removal in an airlift intermittent circulation membrane bioreactor

A new airlift intermittent circulation integrated bioreactor was developed for simultaneous nitrogen and phosphorus removal of wastewater, in which, circulation of mixed liquid between mixing zone and aeration zone was realized by aeration power, alternately anaerobic/anoxic bio-environment in mixing zone was realized by intermittent circulation and simultaneous nitrogen and phosphorus removal was obtained through strengthened denitrifying phosphorus removal process. Removal performance of the reactor was investigated and pollutant removal and transfer mechanism in one operation circle was analyzed. The experiment results indicated that under the influent condition of chemical oxygen demand (COD) concentration of 642.1 mg/L, total nitrogen (TN) of 87.4 mg/L and PO₄^3?-P of 12.1 mg/L, average removal efficiencies of COD, TN and PO₄^3?-P reached 96.4%, 83.2% and 90.5%, respectively, with the hydraulic residence time of 22 hr and operation circle time of 185 min. Track studies indicated that the separation of aeration and mixing zones and intermittent circulation of mixed liquid between the two zones provided distinct biological environments spatially and temporally, which ensured the occurrence of multifunctional microbial reactions.     

Nitrogen and phosphorus removal in an airlift intermittent circulation membrane bioreactor

A new airlift intermittent circulation integrated bioreactor was developed for simultaneous nitrogen and phosphorus removal of wastewater, in which, circulation of mixed liquid between mixing zone and aeration zone was realized by aeration power, alternately anaerobic/anoxic bio-environment in mixing zone was realized by intermittent circulation and simultaneous nitrogen and phosphorus removal was obtained through strengthened denitrifying phosphorus removal process. Removal performance of the reactor was investigated and pollutant removal and transfer mechanism in one operation circle was analyzed. The experiment results indicated that under the influent condition of chemical oxygen demand (COD) concentration of 642.1 mg/L, total nitrogen (TN) of 87.4 mg/L and PO₄^3--P of 12.1 mg/L, average removal efficiencies of COD, TN and PO₄^3--P reached 96.4%, 83.2% and 90.5%, respectively, with the hydraulic residence time of 22 hr and operation circle time of 185 min. Track studies indicated that the separation of aeration and mixing zones and intermittent circulation of mixed liquid between the two zones provided distinct biological environments spatially and temporally, which ensured the occurrence of multifunctional microbial reactions.