铁促双电极电化学氧化处理丙烯腈生产废水的研究

采用钛基二氧化锡(Ti/SnO₂)和金属铁构成组合阳极,并以石墨为阴极,研究了铁促双电极电化学氧化处理丙烯腈生产废水的效果及反应过程的相关规律.结果表明,与传统电化学氧化相比,采用组合阳极的双电极氧化过程获得了更高的有机物去除率并提高了电流效率.在相同电压下,当不外加H₂O₂时,COD去除率比采用传统电化学氧化提高11.0%～13.8%,电流效率提高8.0%～15.0%,而当外加H₂O₂浓度为2 200　mg·L^-1,且电压为4.0V时,COD去除率达74.6%, TOC去除率达67.9%.随着外加H₂O₂浓度的增加,COD和TOC去除率增加.反应初始阶段H₂O₂浓度较高而Fe²⁺浓度很低,随反应时间延长H₂O₂浓度迅速下降而Fe²⁺浓度则逐渐升高.反应过程中H₂O₂与Fe²⁺浓度变化速率与电压密切相关. H₂O₂初始浓度一定的情况下,阳极通电时间对电流效率影响显著.双电极电化学氧化对丙烯腈生产废水色度也具有良好的去除作用.铁促双电极电化学氧化为有机废水的处理提供了一个新的选择.     

活性炭-Fenton组合法去除水中PAEs的研究

采用活性炭-Fenton组合方法催化氧化去除水中的邻苯二甲酸酯(PAEs),研究了H₂O₂、Fe^2+-、H₂O₂/Fe^2+-及活性炭的用量、pH值、反应时间以及PAEs的初始浓度等对水中PAEs去除率的影响.结果表明,在Fenton试剂与活性炭的协同作用下,对PAEs具有较好的去除效果.PAEs水溶液(DMP、DEP、DBP、DOP各为12　mg·L^-1),经活性炭-Fenton法处理15　h后,PAEs的平均去除率可达到99.1%.     

Fenton试剂处理废水中各影响因子的作用机制

以洗胶废水为研究对象初步研究了 Fenton试剂处理有毒有机废水时各影响因子的作用机制 ,通过正交实验确定了 Fen-ton反应各种影响因子的最佳操作条件为 :[H₂O₂]=0.2 mol· L^-1、[Fe²⁺]=40 mmol· L^-1、反应温度 85℃ ,反应时间 60 min、反应体系的 pH值为3左右 .此条件下废水 COD的去除率普遍大于 80% .试验发现紫外光和配体络合物可提高 Fenton试剂对有机物的降解能力 .在各影响因子与 COD去除率的关系曲线基础上 ,分析了混合废水中各影响因子的作用机理和综合反应机理的关键及控制步骤 ,提出了改进的思路 .     

新鲜渗滤液与长填埋龄渗滤液的Fenton处理过程特征

以新鲜渗滤液和长填埋龄渗滤液为对象,采用Fenton法对其进行处理,通过相对分子质量（M_r）分布、COD、总有机碳（TOC）、COD/TOC等表征手段,比较分析渗滤液性质对Fenton处理效果的影响.结果表明,长填埋龄渗滤液的有机物平均M_r高于新鲜渗滤液,其M_r>105的组分占到了总量的64%,但在Fenton法作用下其更易转化为可溶性小分子有机质（M_r<10³）;新鲜渗滤液的COD去除率(61%～84%)高于长填埋龄渗滤液(31%～60%),而长填埋龄渗滤液的TOC去除率(85%～91%)高于新鲜渗滤液(52%～80%);无论是处理新鲜渗滤液还是难降解的长填埋龄渗滤液,Fenton法的氧化作用对COD去除的贡献均大于絮凝作用.絮凝作用的COD（COD_coag）去除率受氧化作用的COD（COD_oxid）去除率影响,COD_oxid去除率越大,COD_coag去除率越低;物料平衡结果显示,长填埋龄渗滤液的TOC_oxid去除量大于COD_oxid去除量,而新鲜渗滤液的的TOC_oxid去除量小于COD_oxid去除量;长填埋龄渗滤液和新鲜渗滤液的初始COD/TOC分别为1.17和1.58,在Fenton处理的氧化作用下,COD/TOC分别变为1.96和0.68,表明长填埋龄渗滤液发生的是完全氧化,而新鲜渗滤液同时发生了部分氧化和完全氧化;2种渗滤液的COD_coag和TOC_coag变化说明,长填埋龄渗滤液中受絮凝作用去除的有机物的氧化态明显低于新鲜渗滤液.     

光电芬顿氧化反应降解染料罗丹明B

以有机染料罗丹明B为目标污染物,利用光电芬顿方法对其进行降解研究。研究汇总考察了芬顿试剂（二价铁盐、双氧水）的用量及比例、初始pH值、电流强度等对罗丹明B降解效果的影响。实验结果表明：芬顿试剂H₂O₂?/?Fe²⁺的最佳物质的量比为1∶1,Fe²⁺浓度降低或H₂O₂浓度升高,罗丹明B降解效果增强;罗丹明B在pH＝3.0的酸性体系中降解效果最好;电流强度为0.005 A时,罗丹明B降解效果好且耗能最低。在H₂O₂?/?Fe²⁺物质的量比为1∶1、电流为0.005 A、初始pH＝3.0、H₂O₂初始浓度为1.0 mM条件下,以350 nm紫外光照射的光电芬顿反应降解初始浓度为0.1 mM的罗丹明B溶液,处理10 min后罗丹明B去除效率可达99%以上。     

铁促电解深度处理填埋场渗滤液的研究

采用箱式电化学反应器（具有氧化物涂层的钛基阳极）进行填埋场渗滤液的深度处理,考察了FeSO₄浓度、初始pH值、电压（电流）对污染物去除的影响,对比了铁促电解过程使用Fe²⁺和Fe³⁺的污染物去除效果.结果表明,与传统有机物电化学氧化相比,铁促电解显著提高了有机物的去除效率.FeSO₄浓度增大,有机物去除效果提高,当FeSO₄浓度大于1　250　mg·L^-1,有机物去除率提高幅度减小;污染物去除速率在30　min内较快,然后逐渐递减;合理的初始pH值范围为3～4;若有效去除COD和NH⁺₄-N,则电解电压须大于3.3 V,电流大于4.8 A;Fe³⁺促进电解去除有机物的效果略低于Fe²⁺;提出了铁盐循环利用和将酸洗废水应用于铁促电解过程的设想.     

Fenton氧化/混凝协同处理焦化废水生物出水的研究

对Fenton氧化/混凝协同处理焦化废水生物出水的方法进行了研究,在综合考虑经济性和去除效果的前提下,提出了反应的最佳条件:H₂O₂投加量为220 mg/L,Fe²⁺投加量为180 mg/L,聚丙烯酰胺投加量为4.5 mg/L,反应时间为0.5h,pH=7.最终COD去除率可达44.5%,色度可以降为35倍,出水符合国家污水排放二级标准.同时,通过分析分子量分布和小分子有机物组成,揭示了Fenton氧化/混凝协同处理焦化废水生物出水的污染物变化规律.结果表明焦化废水经过Fenton氧化/混凝协同处理后,其出水可达到国家二级排放标准,并且处理成本相对较低,具有实际应用的前景.     

Fe2+-H2O2法处理DSD酸生产氧化母液的研究

为改善DSD酸氧化母液的可生化降解性,将废液先用有机絮凝剂TS-1(一种季胺盐)处理,TS-1的投加量为3g/L,其后用Fe²⁺-H₂O₂法氧化,Fe²⁺和H₂O₂的量分别为150mg/L,7g/L,废液COD和色度的去除率分别可达64%和62%。经处理后的废水,其BOD₅/COD≈0.3,可以认为已达到生化处理的要求。当H₂O₂的投量为2g/L,经Fe²⁺-H₂O₂氧化处理后的废液,再用FeCl₃进行两级混凝处理(FeCl₃的投加量分别为5g/L和2g/L),则COD和色度的去除率可达90%和95%。     

Photochemical degradation of nonylphenol in aqueous solution：The impact of pH and hydroxyl radical promoters

The degradation of nonylphenol (NP) in aqueous solution with UV, H₂O₂/UV, and Fenton/photo-Fenton processes was studied. The efficacy of direct and hydrogen peroxide photolysis proved to be dependent on the pH value. The addition of H₂O₂ to UV treatment improved NP degradation. The application of UV photolysis and the H₂O₂/UV system at pH 7 resulted in low pseudo first-order rate constants at 10^-4 sec^-1. In the experiments at elevated pH values the pseudo-first order rate constants increased to 10^-3 sec^-1. The efficacy of the Fenton process was lower in comparison with UV and hydrogen peroxide photolysis. The addition of UV irradiation to the H₂O₂/Fe²⁺ system substantially improved NP degradation efficacy. In terms of performance, the photo-Fenton process was similar to the H₂O₂/UV process. The most favourable process for complete nonylphenol degradation considering both operational cost and treatment efficacy was H₂O₂/UV at pH 11 and 250 mol/L H₂O₂.     

Fe3+或Fe2+均相催化H2O2生成羟基自由基的规律

利用电子自旋共振-自旋捕集技术(ESR)研究了不同条件下Fenton和类Fenton反应中羟基自由基的变化规律.结果表明,Fenton和类Fenton在起始反应阶段羟基自由基的生成速率都随着H₂O₂和Fe³⁺或Fe²⁺浓度的增大而增大,但Fenton反应在起始阶段羟基自由基生成速率显著高于类Fenton反应.Fenton反应pH在2.5～3.5,而类Fenton反应pH在2.8～3.0范围内有较高的自由基生成速率.起始反应完成后,反应过程中Fenton与类Fenton反应自由基的生成速率也存在显著差异.结果表明,两体系在反应起始和反应过程中都存在着机制的差异.     

填埋场渗滤液水质特性在Fenton处理过程中的变化

在CSTR和间歇操作两种模式下考察了早、晚期渗滤液水质特性在Fenton处理过程前后的变化。结果表明NH₃-N ,NO₃- -N ,Cl- 质量浓度变化很小 ,F- 质量浓度则有较大的增加 ,而IC(无机碳 )值下降较多。渗滤液中的COD_Cr和TOC均得到不同程度的去除 ,且晚期渗滤液的去除率高些 ,造成这种不同处理效果的原因主要是渗滤液中高分子量有机物 (HighMolecularWeightOrganicMatter ,HMWOM)与低分子量有机物(LowMolecularWeightOrganicMatter,LMWOM)的比例存在较大的差异。此外 ,文中COD_Cr和TOC的去除率大多低于文献 [1]的数值.      

超声波诱导催化氧化处理有机化学实验室废水的初步试验

采用超声波诱导催化氧化处理有机化学实验室废水,探讨了超声辐射时间等因素对有机化学实验室废水处理效果的影响,获得了最佳工艺条件：100mLCOD为4632mg／L的废水（初始pH值=3）在超声辐射反应时间50min,Fe^2＋离子浓度为100mg/L,H2O2浓度为800mg／L的条件下,COD去除率达到79％。     

O3-BAC深度处理石化废水厂尾水的特性及菌群结构分析

采用连续流O_3-BAC对华北某石化废水处理厂尾水进行了中试处理实验,研究了O_3氧化对COD及UV254处理效果的影响,同时对处理过程中有机物的变化特性及稳定运行30 d时BAC填料中的微生态环境进行了分析.结果表明,在O_3接触时间为40 min,O_3投加量为20 mg·L-1,BAC单元空床停留时间为1.5 h条件下,O_3-BAC工艺出水COD为24 mg·L-1,平均去除率为40.4%,相对于单独BAC工艺去除率提高10.0%,UV254的平均去除率为55.1%,且COD与UV254之间呈一定的相关性,相关系数R2为0.89;O_3氧化后相对分子质量1×103的比例由尾水中的69.0%提高到了87.0%,O_3-BAC工艺中NPOC的去除率为45.8%,较单独BAC工艺提高23.0%,且BAC单元去除的NPOC主要由相对分子质量1×103的组分所贡献;经GC-MS图谱及有机物统计分析,经O_3氧化后烷烃类、不饱和酯类及酚类等有机物得到明显的去除;O_3氧化后BAC单元的微生态环境得到明显改善,其中微生物种类(丰度在1.0%以上)由6种增加到了11种.O_3-BAC工艺可以有效应用于石化尾水的深度处理中.     

厌氧水解-SBR工艺处理高浓度有机废水运行工序的优化

将ASBR反应器和SBR反应器结合组成厌氧水解-SBR工艺用于养猪场废水的处理,ASBR反应器作为厌氧水解反应器,主要完成对有机物的水解,达到初步降解有机物的目的,在反应器每次进水量和排水量不大于其有效容积70%的前提下,研究了ASBR反应器厌氧搅拌段的时间对污水可生化性和对后续SBR脱氮处理效果的影响.结果表明,厌氧搅拌36h的污水既保持了较高的可生化性,出水BOD/COD保持在0.4左右,又能在后续SBR处理中取得较好的脱氮效果,经SBR反应器处理后出水NH₄⁺-N<10mg/L.通过实验分析进一步确定了好氧SBR反应器运行的最佳工序,厌氧水解-SBR运行工序优化后,BOD5的总去除率达到98%以上,NH₄⁺-N去除率达到99%以上,但出水COD_Cr达不到排放标准,经混凝沉淀处理后方能达标排放.     

Fenton 试剂处理草酸化工废水的实验研究

利用Fenton工艺对草酸化工废水进行预处理,试验结果表明：针对该废水,温度为制约其反应的最重要的影响因素,升温至40℃时,可达到最佳处理效果;Fenton预反应后可能出现pH不升反降的现象,pH＝3时处理效果较好;对沉淀时间较长的间歇式处理,絮凝剂PAM的投加意义不大。试验表明,在温度为40℃,pH＝3,投加2％的双氧水（双氧水和硫酸亚铁的摩尔比为1：4）时,COD总去除率可达到78％。     

微好氧水解酸化在石化废水预处理中的应用研究

应用微好氧水解酸化技术对北方某石化污水厂进行了改造,投产后对其进行了跟踪监测.结果表明,在进水COD为490.3~673.2 mg·L-1,水力停留时间(HRT)为24 h以及溶解氧(DO)控制在0.2~0.35 mg·L-1条件下,监测阶段内COD的平均去除率为11.7%,出水和进水相比,BOD5/COD提高了12.4%,UV254值降低了11.2%,挥发性脂肪酸(VFA)浓度升高了23.0%.相对分子质量分布测定和好氧生物降解性试验结果表明:石化废水采用微好氧水解酸化预处理后,小分子有机物(1×103)所占比例由59.5%提高至82.1%,而大分子有机物(100×103)所占比例由31.8%降低到14.0%.经微好氧水解酸化预处理后降解性有显著提高,原水COD经48 h好氧处理可降至102.2 mg·L-1,而微好氧水解酸化出水COD经48 h好氧处理可降解至71.5 mg·L-1.微好氧水解酸化出水的SO2-4浓度[(930.7±60.1)mg·L-1]高于进水[(854.3±41.5)mg·L-1],表明微好氧环境对硫酸盐还原菌(SRB)有抑制作用.由于硫酸盐的还原受到抑制,减少有毒和恶臭类气体产生,改善了周围环境.     

Effect of organic matter on phosphorus recovery from sewage sludge subjected to microwave hybrid pretreatment

Microwave (MW) hybrid processes are able to disrupt the flocculent structure of complex waste activated sludge, and help promote the recovery of phosphorus as struvite. In this study, to optimize struvite yield, (1) the characteristics of matter released in MW-hybrid treatments were compared, including MW, MW-acid, MW-alkali, MW-H₂O₂, and MW-H₂O₂-alkali. The results showed that selective release of carbon, nitrogen, phosphorus, Ca^2 +, and Mg^2 + achieved by sludge pretreatment using MW-hybrid processes. MW-H₂O₂ is the recommended sludge pretreatment process for phosphorus recovery in the form of struvite. The ratio of Mg^2 +:NH₄⁺-N:PO₄^3 −-P was 1.2:2.9:1 in the supernatant. (2) To clarify the effects of organic matter on struvite recovery, the composition and molecular weight distribution of organic matters were analyzed. Low molecular weight COD was found to facilitate the removal rate of NH₄⁺-N and PO₄³-P via crystallization, and the amorphous struvite crystals (< 1 kDa) from the filtered solutions had high purity. Therefore, the present study reveals the necessity of taking into consideration the interference effect of high molecular weight organic matters during struvite crystallization from sewage sludge.     

有机氯农药污染土壤的Fenton氧化修复研究

研究了Fenton氧化对某实际有机氯农药污染场地土壤的修复效果。结果显示:Fenton氧化能够快速有效地降解污染土壤中的六氯和DDTs。当Fe2+浓度为80 mmol/L,Fe2+与H2O2的摩尔浓度比为1∶5,水土比10∶1时,反应6 h,土壤中六氯和总DDT的去除率分别为:96.7%和78.2%。每方土的修复成本估算为951元。     

Characterization of refuse landfill leachates of three di erent stages in landfill stabilization process

Landfill leachates with di erent ages (mature leachate, 11 years; semi-mature leachate, 5 years; fresh leachate, under operation) were collected from Laogang Refuse Landfill, Shanghai to characterize the colloid size distribution and variations of leachate. These leachates were separated using micro-filtration and ultra-filtration into specific size fractions, i.e., suspended particles (SP) (> 1.2 m), coarse colloids (CC) (1.2–0.45 m), fine colloids (FC) (0.45 m, 5 kDa/1 kDa molecular weight (MW)), and dissolved organic matters (DM, < 5 kDa/1 kDa MW). The specific colloids in each size fraction were quantified and characterized through chemical oxygen demands (COD), total solid (TS), pH, NH4 +-N, total organic carbon (TOC) and fixed solid (FS). It was found that COD, NH4 +-N and TS in leachate decreased significantly over ages, while pH increased. The dissolved fractions (< 5 kDa/1 kDa) dominated (over 50%) in three leachates in terms of COD, and the organic matter content in dissolved fraction of leachates decreased and the inorganic matter increased as the disposal time extended, with the TOC/COD ratio 30%–7%. Dissolved fractions decreased from 82% to 40% in terms of TOC as the disposal time extended, suggested that the organic matter remained in leachate would form into middle molecular weight substances during the degradation process.     

Electrochemical oxidation of recalcitrant organic compounds in biologically treated municipal solid waste leachate in a flow reactor

Biologically-treated municipal solid waste （MSW） leachate still contains many kinds of bit-recalcitrant organic matter. A new plate and frame electrochemical reactor was designed to treat these materials under flow conditions. In the electrochemical oxidation process, NH3 and color could be easily removed by means of electro-generated chlorinefaypochlorite within 20 min. The effects of major process parameters on the removal of organic pollutants were investigated systematically. Under experimental conditions, the optimum operation parameters were current density of 65 mA/cm^2, flow velocity of 2.6 cm/sec in electrode gap, and initial chloride ion concentration of 5000 mg/L. The COD in the leachate could be reduced below 100 mg/L after 1 hr of treatment. The kinetics and mechanism of COD removal were investigated by simultaneously monitoring the COD change and chlorine/hypochlorite production. The kinetics of COD removal exhibited a two-stage kinetic model, and the decrease of electro-generated chlorine/hypochlorite production was the major mechanism for the slowing down of the COD removal rate in the second stage. The narrowing of the electrode gap is beneficial for COD removal and energy consumption.