蒸发壁式超临界水氧化反应器处理分散红和活性红染料废水的比较

采用蒸发壁式超临界水氧化反应器对染料分散红C.I.60和活性艳红M-2B配制的模拟废水进行降解实验.实验结果表明,2种染料的COD和TN去除率随着反应温度、氧化剂过量比(r)的升高而上升.COD去除率活性红要高于分散红,而TN去除率则相反.根据GC-MS分析和陶瓷膜SEM图像,分析测得2种染料主要反应中间产物均含有苯酚和苯甲酸,2种染料的反应对陶瓷膜均有轻微的腐蚀.     

还原铁粉/紫外光体系对活性艳红X-3B溶液的脱色

研究了在紫外杀菌灯（λmax=253．7nm,30W）照射下,添加还原铁粉的活性艳红X－3B水溶液的脱色作用。当pH=3．5,铁粉投加量为2．0g／L时,20mg／L活性艳红X－3B溶液在光照180min后的脱色率为79％。脱色为动力学零级反应。染料溶液的pH、铁粉投加量、活性艳红初始浓度对脱色有影响。初步探讨了脱色反应的机理。     

Adsorption behavior of reactive dye in aqueous solution on chemical cross-linked chitosan beads

A batch system was applied to study the adsorption of reactive dye (reactive red 189) from aqueous solutions by cross-linked chitosan beads. The ionic cross-linking reagent sodium tripolyphosphate was used to obtain more rigid chitosan beads. To stabilize chitosan in acid solutions, chemical cross-linking reagent epichlorohydrin (ECH), glutaraldehyde and ethylene glycol diglycidyl ether was used and ECH shows a higher adsorption capacity. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms at different particle sizes and isotherm constants were determined. The Langmuir model agrees very well with experimental data and its calculated maximum monolayer adsorption capacity has very large value of 1802-1840 (g/kg) at pH 3.0, 30 degrees C. The kinetics of the adsorption with respect to the initial dye concentration, temperature, pH, ionic strength, and wet/dry beads were investigated. The pseudo-first-order, second-order kinetic models and intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The dynamical data fit well with the second-order kinetic model, except for the dry beads fitting better with the first-order model. The adsorption capacity increases largely with decreasing solution pH or with increasing initial dye concentration. Thermodynamic parameters such as change in free energy (deltaG(0)), enthalpy (deltaH(0)), entropy (deltaS(0)) and activation energy were also determined. The adsorption mechanism is shown to be the electrostatic interactions between the dye and chitosan beads. The desorption data shows that the removal percent of dye RR 189 from the cross-linked chitosan beads is 63% in NaOH solutions at pH 10.0, 30 degrees C. The desorbed chitosan beads can be reused to adsorb the dye and to reach the same capacity as that before desorption.     

混合添加剂对PVDF平板疏水膜结构及性能的影响

以不同添加剂采用浸没沉淀相转换法制备基于无纺布支撑的聚偏氟乙烯(PVDF)平板疏水膜,考察了不同添加剂的加入对膜性能与结构的影响;并利用扫描电子显微镜(SEM)、原子力学显微镜(AFM)、红外光谱(FTIR)、接触角测量及膜蒸馏实验等对疏水膜的结构及性能进行表征。结果表明,引入混合型添加剂制备的膜具有较高通量和盐截留率,其疏水性最强,而添加剂对聚合物的晶型影响较小。以35 g/L的NaCl盐溶液为进料液对制备的平板膜进行直接接触式膜蒸馏实验,在热侧进水温度为50℃、冷侧温度为20℃的条件下,所制备的疏水膜通量最高可达12.45 kg/(m2.h),截留率为99.99%。     

平板膜生物反应器中临界通量问题研究

通过小试试验,探讨了平板膜生物反应器中临界通量问题。在试验中发现,平板膜生物反应器运行过程中,存在临界通量值,本试验中污泥质量浓度为10 g/L,临界通量值为4.86×10-6m/s;在该通量值以下运行时,膜污染速度比较缓慢,在该通量值以上运行时,膜污染比较迅速。通过对膜运行过程阻力的分析发现,随着通量的提高,内部污染阻力增加速度大于膜泥饼污染阻力增加速度。膜片在恒流下运行一段时间后,压力会突然上升,其主要原因是由于膜面泥饼的聚集。     

Functional group influences on the reactive azo dye decolorization performance by electrochemical oxidation and electro-Fenton technologies

Electrochemical water treatment technologies are highly promising to achieve complete decolorization of dyebath effluents, as demonstrated by several studies reported in the literature. However, these works are focused on the treatment of one model pollutant and generalize the performances of the processes which are not transposable since they depend on the pollutant treated. Thus, in the present study, we evaluate, for the first time, the influence of different functional groups that modify the dye structure on the electrochemical process decolorization performance. The textile azo dyes Reactive Orange 16, Reactive Violet 4, Reactive Red 228, and Reactive Black 5 have been selected because they present the same molecular basis structure with different functional groups. The results demonstrate that the functional groups that reduce the nucleophilicity of the pollutant hinder the electrophilic attack of electrogenerated hydroxyl radical. Thereby, the overall decolorization efficiency is consequently reduced as well as the decolorization rate. Moreover, the presence of an additional chromophore azo bond in the molecule enhances the recalcitrant character of the azo dyes as pollutants. The formation of a larger and more stable conjugated π system increases the activation energy required for the electrophyilic attack of ^?OH, affecting the performance of electrochemical technologies on effluent decolorization.     

中水回用中平板膜的污染机理分析

采用间歇式生物反应器,对模拟小区生活污水的人工配水进行了生物处理;然后,在操作压力为0.1 MPa,搅拌速度为300 r/min条件下,选用膜生物反应器中常用的聚醚砜(PES,切割分子量分别为2万、1万和5千)、聚丙烯腈(PAN,切割分子量为20万)、聚偏氟乙烯(PVDF,切割分子量为20万)超滤平板膜和聚醚砜(PES,孔径为0.1μm)、聚丙烯腈(PAN,孔径为0.1μm)、聚偏氟乙烯(PVDF,孔径为0.1μm)微滤平板膜在实验室用死端超滤器上分别对活性污泥悬浮液进行了过滤并探讨了和间歇式生物反应器组合在一起用于中水回用的效果,结果表明:每种组合处理后的出水水质为COD＜50 mg/L,NH3-N＜10 mg/L,SS为0 mg/L,浊度为0 NTU,都达到了中水回用的水质标准(CJ25.1-89),其中生物反应器分别与PES超滤膜(5千、1万、2万)和PAN(20万、0.1μm)膜组合时,对COD的去除率较高,但所有组合对NH3-N、TOC去除率及膜的渗透通量都相差不大.此外,根据恒压堵塞过滤定律对膜的污染机理进行的研究证实:对于微滤膜和PAN(20万)超滤膜而言,由滤饼过滤过渡到完全(标准)堵塞,再到滤饼过滤;但对于PVDF(20万)和PES(2万)超滤膜,则由标准堵塞过渡到完全堵塞,再到滤饼过滤;PES(5千、1万)超滤膜的污染机理相对简单,整个过程以滤饼过滤为主.     

中水回用中平板膜的污染机理分析

采用间歇式生物反应器，对模拟小区生活污水的人工配水进行了生物处理；然后，在操作压力为0．1MPa，搅拌速度为300r／min条件下，选用膜生物反应器中常用的聚醚砜（PES，切割分子量分别为2万、1万和5千）、聚丙烯腈（PAN，切割分子量为20万）、聚偏氟乙烯（PVDF，切割分子量为20万）超滤平板膜和聚醚砜（PES，孔径为0．1μm）、聚丙烯腈（PAN，孔径为0．1μm）、聚偏氟乙烯（PVDF，孔径为0．1μm）微滤平板膜在实验室用死端超滤器上分别对活性污泥悬浮液进行了过滤并探讨了和间歇式生物反应器组合在一起用于中水回用的效果，结果表明：每种组合处理后的出水水质为COD〈50mg／L，NH3-N〈10mg／L，SS为0mg／L，浊度为0NTU，都达到了中水回用的水质标准（CJ25．1．89），其中生物反应器分别与PES超滤膜（5千、1万、2万）和PAN（20万、0．1μm）膜组合时，对COD的去除率较高，但所有组合对NH3-N、TOC去除率及膜的渗透通量都相差不大。此外，根据恒压堵塞过滤定律对膜的污染机理进行的研究证实：对于微滤膜和PAN（20万）超滤膜而言，由滤饼过滤过渡到完全（标准）堵塞，再到滤饼过滤；但对于PVDF（20万）和PES（2万）超滤膜，则由标准堵塞过渡到完全堵塞，再到滤饼过滤；PES（5千、1万）超滤膜的污染机理相对简单，整个过程以滤饼过滤为主。     

Comparative performance evaluation of Aspergillus lentulus for dye removal through bioaccumulation and biosorption

Dyes used in various industries are discharged into the environment and pose major environmental concern. In the present study, fungal isolate Aspergillus lentulus was utilized for the treatment of various dyes, dye mixtures and dye containing effluent in dual modes, bioaccumulation (employing growing biomass) and biosorption (employing pre-cultivated biomass). The effect of dye toxicity on the growth of the fungal isolate was studied through phase contrast and scanning electron microscopy. Dye biosorption was studied using first and second-order kinetic models. Effects of factors influencing adsorption and isotherm studies were also conducted. During bioaccumulation, good removal was obtained for anionic dyes (100 mg/l), viz. Acid Navy Blue, Fast Red A and Orange-HF dye (99.4 %, 98.8 % and 98.7 %, respectively) in 48 h. Cationic dyes (10 mg/l), viz. Rhodamine B and Methylene Blue, had low removal efficiency (80.3 % [48 h] and 92.7 % [144 h], respectively) as compared to anionic dyes. In addition to this, fungal isolate showed toxicity response towards Methylene Blue by producing larger aggregates of fungal pellets. To overcome the limitations of bioaccumulation, dye removal in biosorption mode was studied. In this mode, significant removal was observed for anionic (96.7–94.3 %) and cationic (35.4–90.9 %) dyes in 24 h. The removal of three anionic dyes and Rhodamine B followed first-order kinetic model whereas removal of Methylene Blue followed second-order kinetic model. Overall, fungal isolate could remove more than 90 % dye from different dye mixtures in bioaccumulation mode and more than 70 % dye in biosorption mode. Moreover, significant color removal from handmade paper unit effluent in bioaccumulation mode (86.4 %) as well as in biosorption mode (77.1 %) was obtained within 24 h. This study validates the potential of fungal isolate, A. lentulus, to be used as the primary organism for treating dye containing wastewater.     

双分离层复合纳滤膜的制备及其性能

以改性后的聚丙烯腈(PAN)超滤膜为基膜,依次采用层层自组装(LBL)和界面聚合的方法制备了具有双层分离层的复合纳滤膜。以间苯二胺(MPD)为水相单体,均苯三甲酰氯(TMC)为有机相单体,聚乙烯亚胺(PEI)为阳离子聚电解质,聚(4-苯乙烯磺酸钠)(PSS)为阴离子聚电解质,探索了LBL条件对双分离层复合纳滤膜性能的影响,考察了通过不同制备方法获得的纳滤膜对硫酸镁(MgSO4)的分离性能,得到了最佳的LBL制备条件：PEI溶液的浓度为1.00 g·L-1,pH为7;PSS溶液的浓度为1.00 g·L-1,pH为10,支撑电解质氯化钠(NaCl)浓度为1.00 mol·L-1,单一聚电解质(PEI或PSS)的沉积时间为20 min。与仅通过界面聚合法制得的聚酰胺纳滤膜相比,在界面聚合反应之前,先通过LBL沉积1.5层的聚电解质层时得到的复合纳滤膜分离性能优异稳定,在0.80 MPa的压力下,过滤2.00 g·L-1 MgSO4溶液时的通量为18.6 L·(m2·h)-1,截留率达到99.07%。     

Two stage biological treatment of a diazo reactive textile dye and the fate of the dye metabolites

A two stage anaerobic/aerobic bacterial process was used to decolorize and partially mineralize a reactive vinyl sulfone diazo dye C.I. Reactive Black 5 (RB5) in a synthetic wastewater. Since the anchor group of reactive dyes reacts during the dyeing process, the effect the degree of hydrolysis of the vinyl sulfone dye had on decolorization, mineralization and toxicity in each stage was investigated. An overall color removal of approximately 65% was found for both the fully and partially hydrolyzed dye. Partial mineralization of the fully hydrolyzed RB5 was achieved in the two stage rotating disc reactors. While the anchor group metabolite p-aminobenzene-2-hydroxyethylsulfonic acid (p-ABHES) was mineralized, an oxidized form of the center metabolite (1,2-ketimino-7-amino-8-hydroxynaphthalene-3,6-disulfonic acid) remained in the aerobic stage effluent, causing the effluent to be colored although no RB5 was present. Partially hydrolyzed dye in the influent with vinyl forms of the anchor group caused cessation of biogas production and a reduction in decolorization efficiency in the anaerobic stage. No evidence for mineralization of the partially hydrolyzed dye or its metabolites was found. A method for evaluating dye mineralization using lumped parameters is presented.     

UASB反应器降解活性染料废水的特性

中温（35±1）℃条件下,采用上流式厌氧污泥床（upflowanaerobicsludgebed,简称UASB）反应器处理了含蒽醌类-活性艳蓝（c．I．ReactiveBlue5,简称K—GR）或偶氮类-活性艳红（C．I．ReactiveRed20,简称KD-8B;C．I．ReactiveRed2,简称X-3B）模拟染料废水,重点研究了回流比对染料脱色率和COD去除率的影响,在最佳回流比的条件下,探讨HRT（hydraulicretentiontime）对脱色的影响和不同结构染料的脱色效果,并初步分析了脱色机理。结果表明,适宜的回流比有利于提高系统的脱色率;控制回流比和HRT分别为2和24h,当模拟废水中染料的浓度为100mg／L时,COD去除率和脱色率分别为90％～96％和85％～92％;蒽醌和偶氮类染料的脱色是通过偶氮键和葸醌共轭结构的断裂来实现的。     

微通道湍流促进器强化平板MBR的CFD数值模拟

采用CFD中的Standard k-ε湍流模型模拟微通道湍流促进器在平板膜生物反应器中的5种不同放置位置及其6种不同形状对膜生物反应器流体动力学性能的影响,通过定性和定量分析附加微通道湍流促进器后平板膜生物反应器中的流体速度、静压、湍流动能、湍流耗散率和剪切力性能指标的变化。从模拟结果可得出,附加微通道湍流促进器的平板膜生物反应器的流体动力学性能要优于无湍流促进器的流体动力学性能,且梯形微通道湍流促进器双面平行放置于平板膜生物反应器时增加流体速度、湍流动能和剪切力且湍流耗散率和静压增加幅度较小,并在微通道湍流促进器附近有涡的产生,从而有效抑制膜表面滤饼层的形成,减缓浓差极化和减轻膜污染。     

The effect of pre-ozonation on the biocompatibility of reactive dye hydrolysates

Pre-ozonation of 14 different reactive dyestuff hydrolysates at alkaline pH was investigated to assess possible relationships between ozone transfer efficiency, first order decolourization kinetics, release of initially complexed heavy metals and relative changes in the biodegradability of the partially oxidized dye waste samples. Biocompatibility of the raw (untreated) and ozonated dye hydrolysates was comparatively tracked through specific oxygen uptake rate measurements from which the respirometric inhibition of biological activated sludge imparted by raw and ozonated reactive dye wastewater with respect to synthetic domestic wastewater was determined. It could be demonstrated that preliminary ozonation of reactive azo dyes increases their biological compatibility more significantly than formazan copper complex, copper complex azo and phythalocyanine dyes as a consequence of heavy metal release associated with the cleavage of associated chromophoric groupings right at the initial stages of pre-ozonation.     

Wet air oxidation of a reactive dye solution using CoAlPO(4)-5 and CeO(2) catalysts

Wet air oxidation of a prepared reactive dye solution was performed to assess the efficacy of CoAlPO(4)-5 and CeO(2) as catalysts in the reaction. Via adsorption and oxidation of dye, CoAlPO(4)-5 effectively decreased American Dye Manufacturers Institute and chemical oxygen demand (COD) values in the dye solution. At a reaction temperature of 135 degrees C and an applied pressure of 1.0 MPa, color and COD removal were as high as 95% and 90%, respectively, after 2 h. Active sites on the outer surface of CoAlPO(4)-5 are responsible for adsorption and decomposition of dye while active sites in the pores dominate further destruction and oxidation of intermediate products. Since the outer surface only represents a minor part of the total surface, the color removal does not increase appreciably with loading of CoAlPO(4)-5. The CeO(2) catalyst, calcined from cerium chloride under high thermal impact (type A CeO(2)) was very effective in removing color and COD from the solution. This catalyst demonstrated near 100% color removal at temperatures above 135 degrees C and the COD removal could be above 95% at 165 degrees C. With both CoAlPO(4)-5 and CeO(2) catalysts, COD rose and then fell back during the reaction, a feature typical of a consecutive reaction. In contrast to prepared CeO(2), a commercial CeO(2) did not exhibit any catalytic ability for the removal of color and COD. The durability of both CoAlPO(4)-5 and prepared CeO(2) is considered to be fair.     

MBR平板膜中气泡运动的水力特征的数值分析

膜污染是膜生物反应器系统在污水和废水处理应用中最主要的问题之一。针对这一问题,通过计算流体动力学(CFD)仿真模拟,研究了单个气泡以及气泡群在平板膜中的水力学特征,包括气泡速度和膜表面剪切应力等,以达到优化膜组件几何特征和运行条件的目的。模拟结果表明,对于单个气泡而言,随着气泡尺寸的增加,气泡上升速度开始随着直径的增加而升高,在气泡直径为4 mm时,其可达到最大值,随后随着直径的增加反而降低。此外,对于直径为4 mm的气泡,随着膜间隙距离的增加,气泡上升速度明显呈升高的趋势,而剪切应力呈现下降趋势。考虑到实际运行中的膜堵塞问题,建议在平板膜组件中使用7 mm的膜间距,以适当增强膜表面剪切应力。气泡群的模拟结果表明,当膜间液相上升流速较大时,气相和液相所产生的剪切应力相当。而当膜间液相上升流速较小时,气相产生的剪切应力占主导。以上研究结果可为膜生物反应器的设计及运行提供参考。     

丙酮酸钠光解引发染料水溶液的脱色

对丙酮酸钠紫外光解所引发的染料橙黄Ⅱ的脱色进行了研究,讨论了pH值、丙酮酸钠初始浓度、染料初始浓度及外加Fe(Ⅲ)对橙黄Ⅱ光致脱色的影响,比较了4种染料的脱色效果,并对反应机理进行了初步探讨.实验表明,丙酮酸盐对染料有较高的光降解脱色效率;pH为3.0～8.0的范围内,橙黄Ⅱ都有很高的脱色率;丙酮酸盐的初始浓度越大,橙黄Ⅱ脱色率和反应初始速率越大;橙黄Ⅱ浓度越大,其脱色率越低,但反应初始速率变化不大;外加Fe(Ⅲ)会抑制橙黄Ⅱ脱色;Fe(Ⅲ)-丙酮酸在水体中也能产生·OH;橙黄Ⅱ的脱色是由丙酮酸钠光解产生的活性自由基等所致,但不是·OH.     

Characterization of tannery sludge activated carbon and its utilization in the removal of azo reactive dye

Introduction  

The removal of azo Reactive Red 31(RR31) from synthetic dye solution using tannery sludge-developed activated carbon (TSC) was investigated.     

载钴催化剂的制备及对染料降解

以氧化石墨和六水合硝酸钴为前驱体用水热法制备出了不同的催化剂。通过透射电镜、红外光谱、热重以及X射线衍射等测试方法对制得的催化剂进行了表征与分析,并通过对酸性橙Ⅱ的催化降解实验确定催化剂的催化性能。通过实验发现,催化剂制备条件为:六水合硝酸钴与氧化石墨质量比为1: 1,肼的质量为氧化石墨的7/10,加热时间为4 h时,降解染料所用的时间最短。在此条件下制出的催化剂可催化单过硫酸氢钾在10 min内将染料色度基本去除。     

Semiconductor-assisted photocatalytic degradation of reactive dyes in aqueous solution

This work reports the semiconductor-assisted photochemical degradation of reactive dyes. In an oxygenated-UV-ZnO system almost total decolorization of Remazol Brilliant Blue R, Remazol Black B, Reactive Blue 221 and Reactive Blue 222 was observed in reaction times of about 60 min. Extending the photochemical treatment up to 120 min, mineralization higher than 80% for all the dyes was observed. During the same period, the residual acute toxicity was significantly reduced only for Remazol Black B. A systematic optimization study carried out by factorial design showed that for the reactive dyes tested, the ZnO semiconductor exhibits a better efficiency than that observed with anatase TiO2. A synergistic effect in the coupled TiO2-ZnO system was not observed.