臭氧预氧化-BAF工艺深度处理垃圾渗滤液

以广东省江门市垃圾填埋场垃圾渗滤液为研究对象，对经SBR生化处理和聚合硫酸铁混凝后的垃圾渗滤液，采用臭氧-BAF(曝气生物滤池)工艺进行深度处理。该工艺优点在于：臭氧高级氧化技术使大分子有机污染物降解成二氧化碳和水，或者小分子有机污染物，有利于后继BAF的生化处理，且臭氧处理过后废水的色度明显降低，是废水处理的有效方法之一。而后采用曝气生物滤池对垃圾渗滤液进行进一步处理，对COD进一步去除。结果表明，当臭氧的加入量为150 mg/L，BAF停留时间＞4 h，出水COD低于85 mg/L，稳定达到国家GB 16889-1997《生活垃圾填埋污染控制标准》一级排放标准，臭氧氧化法处理每吨垃圾渗滤液的费用为4.8元。     

聚铁混凝-臭氧-BAF对晚期垃圾渗滤液深度处理的研究

联合运用聚铁混凝-臭氧-曝气生物滤池(BAF)对晚期垃圾场的渗滤液进行深度处理。在废水进水COD=601mg/L,色度=400倍时,提出最佳工艺条件:聚铁0.6 mL/L,臭氧用量144 mg/L,BAF停留时间7 h。研究表明,聚铁去除大部分悬浮性有机物,臭氧降解难生物降解有机物并提高废水的可生化性,BAF进一步降解有机物,最终出水COD为75 mg/L,深度处理成本仅为5.5元/t。     

生物接触氧化处理渗滤液有机物的动力学模型研究

以重庆黑石子垃圾填埋场渗滤液生物接触氧化工艺为依托,针对其处理效果的局限性,设计了强化预处理-生物接触氧化反应器,并进行生物接触氧化反应器试验及其有机物降解动力学模型研究,旨在优化运行参数,提高渗滤液处理效果.结果表明,改进后系统比原工艺处理效果好,COD、NH4 -N、TN平均去除率分别达到95.83%、97.60%、85.60%;出水水质得到大幅度提高,出水COD、NH4 -N、TN平均质量浓度分别为235、35、199 mg/L.对生物接触氧化反应器内垃圾渗滤液有机物降解生化反应过程进行量化研究,得到微生物生长动力学模型为1/θc=0.918 7q-0.002 5;根据生物接触氧化反应器内基质消耗过程的物料平衡,得到生物接触氧化反应器处理垃圾渗滤液有机物生物降解的动力学模型为q=1.09S/(10 230 S).试验结果为生物接触氧化反应器的优化控制、设计与放大提供了参考依据.     

回灌对垃圾填埋初期渗滤液化学需氧量的影响

通过模拟柱实验 ,研究了回灌对垃圾填埋场初期渗滤液 CODCr的影响。研究结果表明 ,模拟降雨雨水的渗入且无渗滤液回灌的参照柱 ,其渗滤液出水 CODCr最高 ,一般在 70 0 0 0 mg/L 左右 ;模拟渗滤液原液回灌 ,从第 4周起因脂肪酸的积累导致渗滤液的 p H低于 6,从而抑制了微生物的生化反应 ;模拟好氧生物处理后渗滤液的回灌 ,能加速垃圾层 CODCr的溶出和甲烷化阶段的建立 ,且此时渗滤液的 CODCr变化规律符合指数方程 ;当垃圾层建立甲烷化阶段后 ,回灌 CODCr在 2 0 0 0 0 m g/L 左右的渗滤液 ,仍可促使垃圾中有机物迅速转化为气态物     

焦化废水臭氧催化氧化过程的污染物降解特征

为了考察焦化废水臭氧催化氧化深度处理过程中污染物的降解特征,对处理过程中的废水进行了COD、TOC、BOD、紫外可见光谱、高效液相色谱、气相色谱-质谱联用(GC-MS)和凝胶色谱等多种分析。结果表明:经臭氧催化氧化处理后,废水的COD、TOC和UV_(254)均降低,降低速度大小为UV_(254)CODTOC;臭氧催化氧化可提高废水的可生化性,但氧化时间进一步延长,可生化性反而降低;液相色谱表明非极性物质优先得到去除;凝胶色谱表明分子量较小的物质优先去除;GC-MS结果表明焦化废水混凝出水中主要成分为苯酚类、杂环化合物、多环芳烃及其衍生物,臭氧催化氧化处理后这些化合物都得到有效降解。     

铁-碳微电解法预处理老龄垃圾填埋场渗滤液的研究

由于老龄垃圾填埋场渗滤液属于难降解废水,直接生物处理效果不佳。用微电解法预处理老龄垃圾填埋场渗滤液后,结果表明,其COD、NH3-N和色度的去除率最高分别达到74％、79％和97.5％,可生化性也有很大提高,BODs/CODCr从0.04提高到0.29,为后续的生化处理创造了良好的条件。     

臭氧对化工园区废水厂二级出水的选择性氧化

以化工园区废水厂二级出水作为实验废水,采用臭氧氧化工艺对其进行处理,采用分子量分级、亲疏水性分离和傅里叶红外等手段对臭氧氧化前后水质进行了系统分析。结果表明,在进水COD为126 mg/L,臭氧氧化60 min的条件下,COD和UV254的去除率分别为37.9%和55%;臭氧氧化对水中疏水性物质去除效率高于亲水性物质,部分疏水性物质氧化成亲水性小分子有机物。臭氧氧化可以改变废水中有机物的分子结构,使水中分子量小于1×103k Da的有机物比例从56.3%提高至71.2%,分子量大于1×105k Da的有机物比例由原来的24.2%下降至9.6%。红外光谱分析表明,臭氧氧化具有一定的选择性,可显著去除水中含不饱和键、酚类、醇类等有机物,但对饱和烷烃基本无降解效果。     

臭氧化对垃圾填埋场后期渗滤液的预处理研究

应用自制微孔扩散式接触反应器,考察了不同pH条件下垃圾填埋场后期渗滤液的臭氧化预处理效果.结果表明,渗滤液初始pH值升高,臭氧利用率增大,垃圾渗滤液中COD、腐殖酸的去除速率加快;当初始pH为10时,经臭氧化处理120 min后,模拟废水的BOD5/COD可从初始的0.17提高到0.36,改善了废水的可生化性,同时渗滤液的色度、浊度、腐殖酸和SS也有较高的去除率.     

垃圾渗滤液臭氧氧化的铜镍负载型催化剂筛选

为了合成能够与臭氧联用催化氧化垃圾渗滤液中污染物的高效催化剂,采用浸渍法制备了以活性氧化铝为载体的75种不同铜镍负载率的催化剂,使之分别与臭氧联用进行垃圾渗滤液催化氧化处理。结果表明,铜镍催化剂能够提高臭氧催化氧化垃圾渗滤液中污染物的能力,与单独臭氧氧化相比,铜镍催化剂与臭氧联用对垃圾渗滤液中COD的去除率可提高20百分点左右,合成的铜镍催化剂可重复使用3次;浸渍液(氯化铜溶液、氯化镍溶液)质量浓度均为0.250 0mg/L,Cu2+与Ni 2+的摩尔比为1.00,焙烧温度为800℃下制得的铜镍催化剂(催化剂41#)对垃圾渗滤液中COD和氨氮的去除效果最佳,其铜镍负载率为2.676 4%;针对催化剂41#的表征分析结果表明,其合成过程中生成了新物质Cu2HIO6·2H2O和NiAl10O16。     

混凝-Fenton-BAF深度处理垃圾渗滤液中试研究

针对经过SBR处理后,难以再进一步生化降解的垃圾渗滤液,提出混凝-Fenton-曝气生物滤池(BAF)工艺进行深度处理.首先利用混凝去除SBR出水的悬浮性有机物,降低Fenton试剂的处理成本;然后采用Fenton试剂进行氧化处理,既降低垃圾渗滤液的COD值,又提高其可生化性,最后通过BAF工艺去除有机物,实验结果表明,在SBR出水COD为600～800 mg/L的情况下,最终出水的COD低于80 mg/L,处理成本仅为2.6元/t.     

A new approach to characterize biodegradation of organics by molecular mass distribution in landfill leachate

This study provides biodegradability of organics in leachate according to their molecular mass distributions (<0.5, 0.5 to 1, 1 to 3, 10, and >10 KDa). Organics with molecular mass values lower than 0.5 KDa were the predominant species in the raw leachate filtrate, and the aerated lagoon process was very effective in treating these highly biodegradable organics; the Fenton's oxidation process was very effective in treating not-so-biodegradable organics with molecular mass values higher than 0.5 KDa, but a portion of these organics were converted into organics <0.5 KDa after Fenton's oxidation. An oxygen uptake measurement using a respirometer was more sensitive than a conventional biochemical oxygen demand measurement to evaluate bioactivities, especially when bioactivities were low.     

“老龄期”填埋场渗滤液COD蒸发规律研究

“老龄期”填埋场渗滤液由于可生化性差而难于处理。采用常规蒸发、减压蒸发和载气蒸发处理不同pH值的“老龄期”渗滤液。实验结果表明，3种蒸发方式下，冷凝液CODF降过程中均存在明显的浓度转折点，转折点之后COD维持较低水平，为“老龄期”渗滤液的“三分处理法”提供理论依据。与常规蒸发相比，减压蒸发和载气蒸发的前期冷凝液COD较高，且浓度转折点偏后。     

"老龄期"填埋场渗滤液COD蒸发规律研究

"老龄期"填埋场渗滤液由于可生化性差而难于处理.采用常规蒸发、减压蒸发和载气蒸发处理不同pH值的"老龄期"渗滤液.实验结果表明,3种蒸发方式下,冷凝液COD下降过程中均存在明显的浓度转折点,转折点之后COD维持较低水平,为"老龄期"渗滤液的"三分处理法"提供理论依据.与常规蒸发相比,减压蒸发和载气蒸发的前期冷凝液COD较高,且浓度转折点偏后.     

Approach for detecting mutagenicity of biodegraded and ozonated pharmaceuticals, metabolites and transformation products from a drinking water perspective

Many pharmaceuticals and related metabolites are not efficiently removed in sewage treatment plants and enter into surface water. There, they might be subject of drinking water abstraction and treatment by ozonation. In this study, a systematic approach for producing and effect-based testing of transformation products (TPs) during the drinking water ozonation process is proposed. For this, two pharmaceutical parent substances, three metabolites and one environmental degradation product were investigated with respect to their biodegradability and fate during drinking water ozonation. The Ames test (TA98, TA100) was used for the identification of mutagenic activity present in the solutions after testing inherent biodegradability and/or after ozonation of the samples. Suspicious results were complemented with the umu test. Due to the low substrate concentration required for ozonation, all ozonated samples were concentrated via solid phase extraction (SPE) before performing the Ames test. With the exception of piracetam, all substances were only incompletely biodegradable, suggesting the formation of stable TPs. Metformin, piracetam and guanylurea could not be removed completely by the ozonation process. We received some evidence that technical TPs are formed by ozonation of metformin and piracetam, whereas all tested metabolites were not detectable by analytical means after ozonation. In the case of guanylurea, one ozonation TP was identified by LC/MS. None of the experiments showed an increase of mutagenic effects in the Ames test. However, the SPE concentration procedure might lead to false-positive results due to the generation of mutagenic artefacts or might lead to false-negative results by missing adequate recovery efficiency. Thus, these investigations should always be accompanied by process blank controls that are carried out along the whole ozonation and SPE procedure. The study presented here is a first attempt to investigate the significance of transformation products by a systematic approach. However, the adequacy and sensitivity of the methodology need to be further investigated. The approach of combining biodegradation and ozonation with effect-based assays is a promising tool for the early detection of potential hazards from TPs as drinking water contaminants. It can support the strategy for the evaluation of substances and metabolites in drinking water. A multitude of possible factors which influence the results have to be carefully considered, among them the selectivity and sensibility of the mutagenicity test applied, the extraction method for concentrating the relevant compounds and the biocompatibility of the solvent. Therefore, the results have to be carefully interpreted, and possible false-negative and false-positive results should be considered.     

Treatment of landfill leachate by ozone-based advanced oxidation processes

In this study, laboratory experiments are conducted to compare the efficacy using several ozone-based advanced oxidation processes (AOPs), such as O3, O3/H2O2, and O3/UV, to treat landfill leachate. Raw leachate was initially coagulated by ferric chloride (FeCl3) at the experimental-determined optimal dosage of 900 mgl(-1), and the ozone-based AOPs were subsequently applied. Results indicate that all AOPs would result in a significant increase on the ratio of BOD5/COD from 0.06 to 0.5 at the applied ozone dosage of 1.2 gl(-1). The increase on biodegradability for ozonated leachate indicates that these AOPs would be beneficial to the subsequent biological treatment process. To better explain the alteration of high organic molecules after oxidation, ultrafiltration was used to separate the leachate by several molecular weight cutoffs (MWCO). The COD distribution for coagulated leachate is 34% for MWCO>10 kDa, 7% for MWCO between 5 and 10 kDa, 22% for MWCO between 1 and 5 kDa, and 37% for MWCO<1 kDa. Following ozonation or AOPs, the predominant distribution of COD would be obviously shifted to the MWCO less than 1000 gmol(-1) (72-85%) over the other MWCO ranges. In addition, Gel Permeation Chromatograph (GPC) analysis has showed a substantial agreement on the cleavage of larger organic compounds into smaller ones. O3/UV was found to be the most effective approach among these ozone-based AOPs to enhancing the biodegradability and eliminating the color of leachate.     

Ozonation of an azo dye C.I. Remazol Black 5 and toxicological assessment of its oxidation products

The effect of ozonation (20.5 mgl(-1)) on the degradation processes of an azo dye, Remazol Black 5 (RB5; CI) was studied. Conventional parameters such as chemical oxygen demand (COD), total organic carbon (TOC), pH, conductivity, colour removal, biodegradability (BOD(5/28)), and toxic potential of the dye and its degradation products were monitored during the process. The results obtained indicated that ozonation is a highly effective way to remove the colour of a corresponding dye solution. However, a considerable organic load still remained as indicated by high COD and TOC residues. The COD, TOC reductions were about 40% and 25% for 6 h ozonation of 2 gl(-1) RB5 aqueous solution. During the ozonation process the rapid decrease of pH and the sharp increase of conductivity indicated the formation of acidic by-products and small fragments and ions which were identified by high performance ion chromatography. The BOD28 data revealed that first by-products after partial ozonation (10-150 min) of RB5 were more biodegradable than the parent compound and ozonation can enhance the biodegradability of azo dyes. During the first 150 min of total 360 min of oxidation, the formation of first by-products with high toxic potential took place as it could be confirmed by two acute toxicity-screening tests, the bioluminescence test (Vibrio fischerii) and the neutral red cytotoxicity assay (rat hepatoma cells). The significant enhancement of microbial biodegradability after long-term ozonation could also be seen as a decrease of toxic intermediates in correlation with the ozonation time as indicated in BOD28 biological degradation test results.     

Variables affecting efficiency of molasses fermentation wastewater ozonation

The main operating variables affecting ozonation efficiencies of wastewater from beet molasses alcoholic fermentation have been studied. Semibatch experiments have been performed in order to analyze the influence of pH, bicarbonate ion, temperature and stirring rate on color and organic matter removals. The efficiencies were similar regardless of the pH, which indicates that direct reactions of ozone with wastewater organics were predominant to radical reactions. Gel permeation chromatography confirmed the reduction in the concentration of organics absorbing light at 475 nm after ozonation. The elimination of bicarbonate ion, strong inhibitor of hydroxyl radical reactions, yielded an improvement in both color and COD reduction efficiencies. Acidification for removing bicarbonate ions produced a shift of colored compounds to smaller molecular weights. The highest efficiencies were achieved at 40 degrees C. Color and COD reductions at 40 degrees C were about 90% and 37%, respectively. In no case, the percentage of TOC removed was higher than 10-15%. Stirring rate had a slightly positive effect during the first stage of the ozonation showing that mass transfer played a role only during the initial reaction phase when direct attack of ozone molecules to aromatic/olefinic structures of colored substances was the predominant pathway.     

臭氧氧化法处理反渗透浓缩垃圾渗滤液

采用臭氧氧化法处理经反渗透膜处理后的浓缩垃圾渗滤液，考察了反应时间、臭氧投量、pH和温度对COD，色度以及浓缩液中腐殖酸的去除影响，通过BOD₅/COD变化分析了臭氧氧化对浓缩液生化性的提高作用。结果表明：在pH 8.0，温度30℃，臭氧投量5 g/h，反应时间90 min的条件下，浓缩液的COD、色度以及浓缩液中腐殖酸的去除率分别达到67.6%、98.0%和86.1%， BOD₅/COD从0.008提升到0.26，生化性有很大提高。     

Ozonation of oxytetracycline and toxicological assessment of its oxidation by-products

Antibiotic formulation effluents are well known for their difficult elimination by traditional bio-treatment methods and their important contribution to environmental pollution due to its fluctuating and recalcitrant nature. In the present study the effect of ozonation on the degradation of oxytetracycline (OTC) aqueous solution (100mgl(-1)) at different pH values (3, 7 and 11) was investigated. Ozone (11mgl(-1) corresponds the concentration of ozone in gas phase) was chosen considering its rapid reaction and decomposition rate. The concentration of oxytetracycline, chemical oxygen demand (COD), biochemical oxygen demand (BOD) and BOD5/COD ratio were the parameters to evaluate the efficiency of the ozonation process. In addition, the toxic potential of the OTC degradation was investigated by the bioluminescence test using the LUMIStox 300 instrument and results were expressed as the percentage inhibition of the luminescence of the marine bacteria Vibrio fischeri. The results demonstrate that ozonation as a partial step of a combined treatment concept is a potential technique for biodegradability enhancement of effluents from pharmaceutical industries containing high concentration of oxytetracycline provided that the appropriate ozonation period is selected. At pH 11 and after 60min of ozonation of oxytetracycline aqueous solutions (100 and 200mgl(-1)) the BOD5/COD ratios were 0.69 and 0.52, respectively. It was also shown that COD removal rates increase with increasing pH as a consequence of enhanced ozone decomposition rates at elevated pH values. The results of bioluminescence data indicate that first by-products after partial ozonation (5-30min) of OTC were more toxic than the parent compound.