MB(A2/O)处理城市污水富磷上清液的化学除磷研究

为开发新型除磷脱氮工艺,研制了将MBR和A²/O工艺相结合的新型MB(A²/O)反应器。研究了MB(A²/O)反应器处理城市污水厌氧富磷上清液的化学除磷,并分析了过程机理及特性。结果表明：对于TP在30～45 mg/L的富磷上清液,采用含20% Ca(OH)₂的工业石灰与P的最佳投加质量比为22.5;纯Ca(OH)₂与P的最佳投加质量比为5.6（摩尔比为2.5）;FeSO₄·7H₂O与P的最佳投加质量比为10.7（Fe^2＋与P的摩尔比为1.3）;Al₂(SO₄)₃·12H₂O与P的最佳投加质量比为12（Al^3＋与P的摩尔比为1.3）时,均可使出水TP稳定在0.3 mg/L以下;以石灰、NaOH的联合投加方式可大幅减少石灰投加量。     

新型絮凝剂含硼聚硅铝铁的制备和性能研究

向聚硅酸中引入Al³⁺、Fe³⁺、B,制得稳定性更好的高效絮凝剂含硼聚硅铝铁（PFASB）。通过实验得到其最佳配比为：n_(B)/n_(Si)=0.16、n_(Fe)/n_(Al)=0.5 、n_(Al+Fe)/n_(Si)=1。对造纸废水和焦化废水进行混凝实验表明,PFASB的除浊、除COD的能力均优于聚合铝、聚合铝铁和聚硅铝铁,而且矾花产生迅速,矾花粗大密实,是一种性能优异的新型高分子絮凝剂。实验还考察了絮凝剂的形貌和结构,结果表明B、铝及其水解产物、铁及其水解产物和聚硅酸等多种组分之间有相互作用,形成了尺度更大的聚集单元。PFASB的这种特殊结构是其具有良好稳定性和混凝性能的根本原因。     

几种阴阳离子对磷钨酸光催化降解甲基橙的影响

以磷钨酸为光催化剂,在紫外灯照射下,对甲基橙溶液进行光催化降解,考察了几种阴阳离子对磷钨酸光催化降解甲基橙溶液的影响。结果表明：Mg²⁺、Ca²⁺、NO^-₃、SO^2-₄和CO^2-₃均对催化活性有促进作用,其中Mg²⁺和Ca²⁺仅有微弱的促进作用;NO^-₃和SO^2-₄随着浓度的增加促进作用也有所增加;CO^2-₃则随着浓度的增加促进作用呈下降趋势;Mn²⁺、Al³⁺和Cl^-对光解反应存在较强的抑制作用,且Al³⁺和Cl^-随着其浓度的增加,抑制作用增强。     

混凝工艺去除合流污水中有机物及营养元素

通过系列杯罐试验混凝处理合流污水,采用硫酸铝（Al₂(SO₄)₃）、硫酸铁（Fe₂(SO₄)₃）、聚合氯化铝（PAC）和聚合氯化铝铁（PAFC）4种混凝剂均能有效去除污水中的 TP、PO^3-₄-P、SS和COD。聚合金属盐（PAC和PAFC）混凝处理效果优于金属盐（Al₂(SO₄)₃和Fe₂(SO₄)₃）,达到相同的处理效果的投加量明显低于后者。助凝剂采用聚丙烯酰胺（PAM）、聚乙烯醇（PVA）、自制的高分子聚合物（AN）和活化硅酸（AS）,在保持较低混凝剂投加量的条件下可明显提高污水处理效果;添加助凝剂对强化PO^3-₄-P的去除作用不明显,PO^3-₄-P的去除仅与混凝剂的投加量相关。混凝剂和助凝剂对污水中NH₃-N的去除作用相对不显著。SS去除率随混凝剂投加量的变化趋势说明混凝的机理较为复杂,可能存在多种混凝机理共同作用。     

4种固定化藻类对污水中氮的净化能力研究

取培养至对数末期的藻,采用海藻酸钙凝胶包埋固定,对人工污水进行静态模拟净化试验,研究了蛋白核小球藻、鱼腥藻、双对栅藻和突变衣藻4种藻在固定和悬浮状态下,对污水中的氨氮和硝酸氮的净化效率以及藻类的生长特性。结果表明：固定化藻细胞比悬浮态藻细胞具有生长更趋于稳定、藻类的活性保持时间更长的优势。4种藻类中,小球藻和鱼腥藻在污水中的生长状况更好,较适宜采用海藻酸钙凝胶包埋固定化技术。实验第5 d时,固定化小球藻、鱼腥藻、双对栅藻和衣藻对NH₃-N去除率分别为91.9%、84.8%、68.3%和51.2%;对NO^-₃-N的去除率分别为85.1%、100%、96.9%和65.9%。固定化小球藻对NH₃-N的去除效果最好,而固定化鱼腥藻对NO^-₃-N的去除效果最好。因此,小球藻和鱼腥藻更适用于去除污水中的氮,具有很好的应用前景。     

固载型TiO2光催化反应器对富营养水体杀藻作用研究

以泡沫镍作为载体，利用电沉积技术将纳米TiO₂负载在泡沫镍上，制成固载型TiO₂光催化反应器。研究表明，经过光催化反应器处理的富营养水体，30 h内叶绿素a由96.2 mg/m³降至2.2mg/m³，下降率达97.6％，而未负载纳米TiO₂普通泡沫镍材料，在同样光强的紫外灯照射下，叶绿素a下降率为74.3％，表明紫外光照射虽然也具有一定的杀藻功能，但是光催化反应才是藻类被杀灭的主要原因。利用9.54 m³景观喷水池进行杀藻中试，光催化反应器也同样表现出优异的杀藻性能，12 d内叶绿素a由18.7 mg/m³降至1.9mg/m³，下降率达到89.8％，水体由浓绿变为清澈见底，这表明光催化反应器具有很强的杀藻能力，通过有效杀灭富营养水体中藻类、控制藻类基数，对应急处理城市景观水、湖泊等富营养水体和突发性藻华，提高生物-生态法处理效率，改善城市水环境具有十分重要的意义。     

共存物质对重金属絮凝剂 MCC 除镉性能的影响简

为进一步拓展天然高分子絮凝剂壳聚糖的应用范围,以壳聚糖、L-半胱氨酸为原料,通过酰胺化反应制备一种具有重金属捕集功能的高分子重金属絮凝剂-2-氨基-3-巯基丙酰壳聚糖（MCC）,研究了水体中常见的阴阳离子、有机配位剂及浊度对MCC除镉性能的影响,探讨了絮体形貌与絮体分形维数及絮凝除镉效果间的关系。结果表明,Na⁺、Cl^-、NO₃^-、F^-、SO₄^2-的存在对MCC除Cd²⁺均有促进作用,Ca²⁺表现为明显的抑制作用;低浓度的EDTA对除镉有促进作用,随着EDTA浓度的增大,逐渐转为抑制作用;低浓度的腐殖酸对MCC去除Cd²⁺有显著的促进作用;在一定范围内,浊度可促进 MCC对Cd²⁺的去除;絮体间空隙越多,絮体分形维数越小,除镉效果越好。     

原位柱撑改性膨润土在微污染饮用水除磷中的应用研究

利用Al3+离子较易水解聚合的性质,微波辅助合成了keggin Al₁₃原位柱撑改性膨润土(PMCs),并探究了其对微污染饮用水中磷元素的去除作用,研究表明,PMCs对磷的混凝和去除作用优于原土、工业 PAC和传统的柱撑改性膨润土(CPMCs);影响除磷效果的主要因素有：搅拌时间、搅拌速度、水样的pH值以及初始浓度等,其最佳除磷条件是：在500 mL 10 mg/L含磷水样中加入1.5 g改性膨润土,搅拌速度为180 r/min,搅拌时间为5 h,水样pH为6～8。     

原位水解生成的羟基氧化铁凝聚吸附除磷效能与机制简

将不同摩尔比Fe³⁺与OH^-（[Fe³⁺]：[OH^-]=1：0、1：1、1：2和1：3）反应获得原位水解生成的羟基氧化铁（in situ FeO_xH_y）,研究了具有不同水解程度的羟基氧化铁对凝聚吸附除磷效能与机制。研究显示,In situ FeO_xH_y对磷的去除率随铁投量增大而升高,且均在中性pH范围内具有最佳除磷效果;在相同铁投量条件下,磷去除率随着[OH^-]：[Fe³⁺]的升高而降低;当体系碱度较低时（pH<6）,引入OH^-可促进Fe³⁺水解而提高除磷效果。4种羟基氧化铁均可在15 s内可快速吸附磷,且吸附过程符合准二级动力学模型;Freundlich模型均可很好地描述磷在4种羟基氧化铁表面的吸附行为。磷酸盐吸附后,In situ FeO_xH_y表面Zeta电位明显降低,且[Fe³⁺]：[OH^-]为1：0的羟基氧化铁降低最为显著。结合MINITEQ计算软件磷酸盐、铁盐形态分析结果显示,对于碱度较低的体系,通过投加一定量OH^-可促进Fe³⁺水解,进而使得其更易与水中H₂PO₄^-与HPO₄^2-结合,生成具有多核羟基的磷酸铁络合物,进而提高除磷效果。     

复配混凝剂理化特性及性能

用聚二甲基二烯丙基氯化铵（PDM）、聚合氯化铝（PAC）按照质量比1%制备了复配混凝剂,研究了其理化特性及原水污染物去除效果。利用Al-Ferron逐时络合比色法研究了复配混凝剂的铝（Ⅲ）形态分布,结果表明,Al_a、Al_b和Al_c分别占12.62%、16.02%和71.36%。复配混凝剂Zeta电位平均值为41.6 mV。红外吸收光谱分析表明复配混凝剂的羟基缔合程度比PAC要高。扫描电镜结果表明,固体复配混凝剂表面较为粗糙、结构疏松。相同投加量时,复配混凝剂对江河水、水库水的浊度、COD_Mn、UV₂₅₄的去除效率均优于PAC。实验利用针杆藻人工模拟高藻原水,当投加PDM：PAC质量比10%的复配混凝剂10 mg/L时,复配混凝剂对藻类的去除率为80.5%。     

铁氧化物复合氧化铝催化臭氧化过程中溴酸盐的生成控制简

以市售活性炭、硅藻土和氧化铝小球为载体,考察了负载铁基活性组分对催化臭氧化过程中溴酸盐的控制情况,其中,铁基复合氧化铝小球体现出更好的溴酸盐还原特性和催化剂稳定性,证实催化剂中铁氧化物是溴酸盐得到有效控制的主要活性组分。进一步考察了铁基复合氧化铝小球催化臭氧化处理实际原水过程中对溴酸盐的生成控制,以及反应过程中溶解性有机碳（DOC）的去除情况。结果表明,与单独臭氧化相比,该催化剂既能有效去除水中的溶解性有机物,又能明显抑制溴酸盐的生成,反应50 h,其活性并没有明显下降。催化剂失活主要归因于吸附位点数量的下降,可以通过负载铁氧化物来实现催化剂的再生。     

Single and combined effects of aluminum (Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) and zinc (ZnO) oxide nanoparticles in a freshwater fish, <Emphasis Type="Italic">Carassius auratus</Emphasis>

The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al₂O₃.L^?1, 10 μg ZnO.L^?1, 10 μg Al₂O₃.L^?1 plus 10 μg ZnO.L^?1, 100 μg Al₂O₃.L^?1, 100 μg ZnO.L^?1, and 100 μg Al₂O₃.L^?1 plus 100 μg ZnO.L^?1). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L^?1 of both single ZnO and Al₂O₃ NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L^?1 Al₂O₃ NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al₂O₃ (except for 10 μg Al₂O₃.L^?1), and after 14 days of exposure to ZnO (10 and 100 μg.L^?1) and Al₂O₃ (100 μg.L^?1)_. The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.     

Toxicity of nanoparticulate and bulk ZnO, Al2O3 and TiO2 to the nematode Caenorhabditis elegans

Limited information is available on the environmental behavior and associated potential risk of manufactured oxide nanoparticles (NPs). In this research, toxicity of nanoparticulate and bulk ZnO, Al₂O₃ and TiO₂ were examined to the nematode Caenorhabditis elegans with Escherichia coli as a food source. Parallel experiments with dissolved metal ions from NPs were also conducted. The 24-h median lethal concentration (LC₅₀) and sublethal endpoints were assessed. Both NPs and their bulk counterparts were toxic, inhibiting growth and especially the reproductive capability of the nematode. The 24-h LC₅₀ for ZnO NPs (2.3 mg L⁻¹) and bulk ZnO was not significantly different, but significantly different between Al₂O₃ NPs (82 mg L⁻¹) and bulk Al₂O₃ (153 mg L⁻¹), and between TiO₂ NPs (80 mg L⁻¹) and bulk TiO₂ (136 mg L⁻¹). Oxide solubility influenced the toxicity of ZnO and Al₂O₃ NPs, but nanoparticle-dependent toxicity was indeed observed for the investigated NPs.     

层状氢氧化镁铝对直接冻黄的脱色性能研究

采用共沉淀法合成出一系列镁铝摩尔比不同的磷酸二氢根型层状氢氧化镁铝,考察了层状氢氧化镁铝及其焙烧产物对直接冻黄染料模拟废水的脱色效果。实验结果表明：以镁铝摩尔比为3制得的层状氢氧化镁铝对直接冻黄溶液的脱色效果最好;在最佳处理条件下,层状氢氧化镁铝及其焙烧产物的脱色率可分别达到99.68%和99.87%;处理直接冻黄染料模拟废水时在较宽的pH值范围内,二者均具有良好的脱色效果;焙烧态的层状氢氧化镁铝在脱色时用量更少,脱色反应更迅速,脱色性能更好。     

Effects of the Basicity on the Comelting Conditions of Municipal Solid Waste Incinerator Fly Ash and Sewage Sludge Ash

Abstract

In this study, the effects of the basicity on the pouring point of the municipal solid waste incinerator fly ash-sewage sludge ash mixture is investigated. Four kinds of sewage sludge ash, which were collected from several primary and secondary sewage treatment plants and were produced by different processes and sludge conditioning alternatives, were used as modifiers. The results indicate that the pouring point of the mixture increased with increasing basicity, within the range of 0.65–1.90. The pouring point is affected by the contents of the mixtures (CaO, SiO₂, Al₂O₃, and the flux). It is suggested that an increase in the CaO content tends to raise the pouring point, whereas an increase in the SiO₂ and/or the Al₂O₃ contents cause as adverse reaction. The prediction equation, obtained by multilinear regression (significant level is 0.05), is as follows: pouring temperature =1189.6 + 4.19CaO-0.96 SiO₂-4.33 Al₂O₃ (R² = 0.91). In general, the pouring point decreased when the basicity was <1. The pouring point apparently increased when the basicity was>1.2. The regression squares for the different basicities were between 0.84 and 0.91. From these relationships, we note that a basicity index of 5 gave the best R² (0.91). From the results of this study, it can be concluded that the modification of the basicity of the fly ash by the addition of sewage sludge ash to lower the pouring point is feasible and leads to a more energy-efficient melting process. In addition, these synthetic slags have a good pozzolanic reactive activity.     

Hydrolysis of di-n-butyl phthalate, butylbenzyl phthalate and di(2-ethylhexyl) phthalate in human liver microsomes

Diester phthalates are industrial chemicals used primarily as plasticizers to import flexibility to polyvinylchloride plastics. In this study, we examined the hydrolysis of di-n-butyl phthalate (DBP), butylbenzyl phthalate (BBzP) and di(2-ethylhexyl) phthalate (DEHP) in human liver microsomes. These diester phthalates were hydrolyzed to monoester phthalates (mono-n-butyl phthalate (MBP) from DBP, mono-n-butyl phthalate (MBP) and monobenzyl phthalate (MBzP) from BBzP, and mono(2-ethylhexyl) phthalate (MEHP)) by human liver microsomes. DBP, BBzP and DEHP hydrolysis showed sigmoidal kinetics in V-[S] plots, and the Hill coefficient (n) ranged 1.37-1.96. The S₅₀, V_max and CL_max values for DBP hydrolysis to MBP were 99.7 μM, 17.2 nmol min⁻¹ mg⁻¹ protein and 85.6 μL min⁻¹ mg⁻¹ protein, respectively. In BBzP hydrolysis, the values of S₅₀ (71.7 μM), V_max (13.0 nmol min⁻¹ mg⁻¹ protein) and CL_max (91.3 μL min⁻¹ mg⁻¹ protein) for MBzP formation were comparable to those of DBP hydrolysis. Although the S₅₀ value for MBP formation was comparable to that of MBzP formation, the V_max and CL_max values were markedly lower (<3%) than those for MBzP formation. The S₅₀, V_max and CL_max values for DEHP hydrolysis were 8.40 μM, 0.43 nmol min⁻¹ mg⁻¹ protein and 27.5 μL min⁻¹ mg⁻¹ protein, respectively. The S₅₀ value was about 10% of DBP and BBzP hydrolysis, and the V_max value was also markedly lower (<3%) than those for DBP hydrolysis and MBzP formation for BBzP hydrolysis. The ranking order of CL_max values for monoester phthalate formation in DBP, BBzP and DEHP hydrolysis was BBzP to MBzP ? DBP to MBP > DEHP to MEHP > BBzP to MBP. These findings suggest that the hydrolysis activities of diester phthalates by human liver microsomes depend on the chemical structure, and that the metabolism profile may relate to diester phthalate toxicities, such as hormone disruption and reproductive effects.     

粉煤灰制备混凝剂及其对黄河水的处理效果

以粉煤灰和铁泥为原料、加入一定量NaCl作助溶剂室温下制备粉煤灰混凝剂,考察酸灰比与酸浓度对Fe3+、Al3+溶出率及混凝剂对黄河水处理效果的影响。结果表明,Fe3+、Al3+的最佳溶出条件为酸灰比3 mL/g、HCl浓度4 mol/L,此时Fe3+溶出率为28.1%,浓度为11.81 g/L;Al3+溶出率为5.2%,浓度为1.86 g/L。粉煤灰混凝剂对黄河水的处理效果在投加量2.38 mL/L、沉降时间30 min、pH 6.2～7.5时最佳,对浊度、SS和CODMn平均去除率分别为89.7%、83.6%和62.3%,优于传统市售混凝剂PAC和FC,Fe3+、Al3+同时存在有利于各自优势的发挥从而提高混凝效果。     

Kinetics of the Homogeneous Gas Phase Hydrolysis of CCl3COCl,CCl2HCOCl,CH2CICOCl and COCl2

The homogeneous gas phase hydrolysis kinetics of the above compounds has been investigated in the 470° to 620°K temperature range. The following biomolecular rate constants were obtained: k(CCl₃COCl) = 2.54 × 10⁶ exp (?18,350 ± 1750)/RT, k(CClH₂COCl) = 1.14 × 10⁸ exp (?22,630 ± 780)/RT, and fr(COCl₂) = 9192 exp (?14,200 ± 2100)/RT liter mole^?1 sec^?1. Experimental difficulties prevented data being obtained for CHCl₂COCl. The half lives of these species with respect to homogeneous gas phase hydrolysis in the atmosphere have been estimated and it is concluded that this is not an efficient conversion process. Heterogeneous hydrolysis by water droplets may be a more efficient atmospheric scavenging process for these compounds.     

富含活性氯与Al_(13)水处理药剂对铜氰络合物去除效能

含重金属铜离子与氰离子(CN)的络合物广泛存在于电镀、冶金等工业废水中,是一种较难处理的污染物。富含活性氯和Al13聚合体的水处理药剂(PACC)兼具氧化和絮凝效能,在处理含重金属氰络合物([Cu(CN)3]2-)废水方面具有良好的应用前景。研究PACC与[Cu(CN)3]2-的反应计量学、动力学,考察了pH、反应时间和投药量等影响因素,确定PACC的最佳工作参数。结果表明,PACC可同时实现对CN的氧化和对Cu2+的絮凝,有效去除水中[Cu(CN)3]2-。使用PACC对[Cu(CN)3]2-的无害化处置过程分为2个阶段:CN-首先被氧化成氰酸根(OCN-);然后OCN-被进一步氧化并生成碳酸氢根和氮气,同时所释放的游离态铜离子被絮凝去除。这2个阶段反应的最佳pH分别为11和8,去除1 mol[Cu(CN)3]2-的最佳投药量为9.35 mol Cl2的PACC;在此条件下反应43 min后,其出水中CN-和Cu2+的浓度均达到排放标准(GB21900-2008)要求。