涤纶碱减量废水中对苯二甲酸的兼性厌氧降解研究

针对碱减量废水中的乙二醇（EG）对对苯二甲酸（TA）的好氧生物降解产生不利影响,本实验采用水解酸化工艺在实验室条件下研究了TA和EG的兼性厌氧降解性能,并着重考察了TA在EG存在下的兼性厌氧降解规律,从而为碱减量工艺实际生产废水的生物处理工艺提供技术方案和科学依据。实验结果表明,TA在缺氧条件下的兼性厌氧降解率很低,在本实验条件下,其兼性厌氧平均降解率为6.1%,而兼性厌氧菌对EG具有较高的降解活性,其降解率达到58.9%～71.5%。在TA配制废水中投加EG时,EG首先得到降解,当EG完全降解后,TA才开始降解,并且其降解速率与TA作为惟一碳源时TA的降解速率相同。由实验结果可知,涤纶碱减量废水的处理不能仅仅采用兼性厌氧生物处理工艺,而应在好氧生物处理工艺为主的情况下,辅以兼氧或厌氧生物处理工艺。     

Use of ozone and/or UV in the treatment of effluents from board paper industry

The aim of this work has been to study the viability of ozone and/or UV in the treatment of cardboard industry effluents. Several model compounds have been chosen for the experiments: guaicol, eugenol, glucose, acetate and butyrate. Significant differences in the ozonisation rates are observed between phenolic products coming from lignin (eugenol and guaiacol) and aliphatic compounds. Reactions fit in all cases a pseudo-first order kinetics and are influenced by the pH of the solution. Real effluents have also been tested, and the COD decrease has been found to depend on the fatty acids/phenols ratio. Finally, respirometric studies have shown an increase in the BODst in effluents subjected to a mild oxidation, while under stronger conditions a BODst decrease is observed.     

芬顿-SBR-微波热解联合处理高浓度液晶废水

针对高浓度液晶废水可生化性差及难降解的问题,设计了芬顿-SBR-微波热解联合工艺。研究了芬顿-SBR-微波热解联合工艺实验条件;分析了SBR工艺运行稳定性;探讨了联合工艺处理液晶废水的反应机理。结果表明,在最佳实验条件下,芬顿-SBR联合工艺去除液晶废水COD高达99.6%,MLSS和SVI分别稳定在4 500 mg·L⁻¹和65%左右,出水COD为450~490 mg·L⁻¹,出水水质满足《污水排入城镇下水道水质标准》(GB/T 31962-2015)中B级标准。微波热解可把芬顿预处理产生的铁泥转热解成高附加值的氧化铁;芬顿预处理可将大分子有机物降解为小分子有机酸,提高出水的可生化性,为后续SBR的稳定运行提供保证。     

Use of electrochemical technology to increase the quality of the effluents of bio-oxidation processes. A case studied

In this work, it has been studied the use of conductive-diamond electrochemical oxidation (CDEO) as a refining technology to assure the quality of the effluents of door manufacturing processes (DMP). To do this, the raw effluents of these factories have been treated by a combination of physicochemical, biological and CDEO treatments. CDEO was found to be a feasible alternative to the refinement of a wooden DMP waste. It can successfully decrease the organic load of the effluents of the biological oxidation with low energy requirements. In addition, in case of incidents in the biological process, CDEO can treat successfully the effluents of the coagulation process. The effluents of the biological treatment have also been treated by CDEO in order to check the possible use of electrochemical technology to increase the biodegradability of the effluents and their possible recycle to the biological treatment. Unfortunately, electrochemical technology was found to be not adequate to increase the biodegradability of the effluents of a biological treatment. The hard oxidation conditions generated during CDEO do not lead to the accumulation of intermediates but to the almost direct formation of carbon dioxide. Lowering the current density or changing the electrodes can not enhance the biodegradability of the effluents of an electrochemical cell.     

管式O3/UV-BAF处理印染生化尾水的中试实验

以印染污水生化处理出水为研究对象,组建了集管式臭氧/紫外(O3/UV)反应系统、臭氧发生系统、气液分离系统、臭氧破坏系统和生物曝气滤池(BAF)系统为一体的中试集成设备。分别研究了各单元及O3/UV-BAF一体化设备的运行效果。结果表明,COD范围为62.3~102.1 mg·L-1,平均值为83.2 mg·L-1时的进水经过O3/UV处理后,BOD5浓度可增加3倍以上,该处理单元可提高污水的生化性能;而单独BAF处理,COD去除率仅为22.5％,表明该污水生化性能较差(BOD5/COD=0.117)且出水COD浓度也不能达到排放标准;O3/UV-BAF联合工艺对印染废水则呈现良好的处理,出水COD去除率达到46.93%,UV254去除率为39.73%。此外,该联合工艺对色度、TN和TP也具有较好的去除效果,去除率分别为54%、34.52%和53.81%,均可达到排放标准。通过对O3/UV-BAF一体化中试设备的评估,为管式O3/UV高级氧化大规模工程应用提供技术支撑。     

臭氧-过硫酸盐工艺深度处理垃圾焚烧渗沥液

针对垃圾焚烧渗沥液经"厌氧-缺氧-好氧"生物组合工艺处理后的出水COD仍在500 mg·L-1左右,且可生化性差（B/C=0.13）的问题,研究采用"臭氧-过硫酸盐"氧化体系进一步处理,以提高其可生化性。研究了臭氧和过硫酸盐投量对该废水处理的效果影响。结果表明,臭氧浓度和S2O2-8浓度分别为19.8 g·m-3和0.4 g·L-1时,且反应20 min,出水的B/C从0.13提高到0.49,表明该氧化体系适用于深度处理垃圾焚烧渗沥液生物组合工艺处理后的出水。采用紫外-可见光谱、三维荧光光谱、红外光谱和气质联用对处理系统废水中有机物进行表征分析,表明废水在"臭氧-过硫酸盐"氧化过程中芳香族化合物发生了开环、断链等反应,芳构化程度降低,不饱和的CC键被破坏,产生CO和C—O键,并生成一些结构简单的长链烷烃。自由基捕获研究表明,氧化体系中·OH和·SO4- 2种自由基均存在,以臭氧直接氧化为主。     

两级预处理/MBR工艺处理制药废水

湖北西北部某工业园已建成污水处理厂（反应沉淀/水解酸化/MBR工艺）以处理合成制药废水为主,由于其预处理段处理效果难以满足后续MBR工艺要求,导致出水水质不能达到国家相关标准,急需升级改造。针对该合成制药废水污染物成分复杂、污染当量大、冲击负荷高、可生物降解性差以及水量水质变化大等特点,采用铁碳微电解/水解酸化两级预处理工艺对该制药废水进行强化预处理,并建立两级预处理/MBR工艺进行小试实验,实验结果表明,铁碳投加量为400 g·L-1,铁碳质量比为4：5,HRT=3 h,pH=4,曝气量为3 L·min-1时,一级预处理效果较好,铁碳微电解对COD去除率达47.50%,废水可生化性由0.23提升到0.38;二级预处理水解酸化将废水可生化性由0.38提升至0.46,促使MBR工艺运行效果大幅提升,最终出水达到《化学合成类制药工业水污染排放标准》（GB 21904-2008）。     

超临界水氧化法改善有机污染物可生化性的研究

难生化有机污染物二甲基甲酰胺、乙睛、氨基萘磺酸或羟基萘磺酸的高浓度水溶液 (4777— 2 82 4 4mg/L) ,经超临界水氧化处理后 ,其可生化性都有了大幅度的提高。二甲基甲酰胺、乙睛、氨基萘磺酸和羟基萘磺酸处理前的BOD5/CODCr,分别为 8.4 %、1.5 6 %、1.5 6 %和 2 .73%。经过超临界水氧化处理 ,它们的BOD5/CODCr可分别达到 2 3.2 %、5 5 .1%、5 0 .2 %和 38.8%。且随着处理温度的升高和COD去除率的上升 ,可生化性越来越好。这表明 ,超临界水氧化法不仅可以用来彻底降解有机污染物 ,也可以用于难生化有机污染物的预处理 ,为难生化有机污染物的生物处理创造条件     

Treatment of landfill leachate by electrochemical oxidation and anaerobic process.

The removal performance of typical refractory organic compounds in landfill leachate was investigated during the electrochemical (EC) oxidation and anaerobic process combined treatment system in this paper. The results indicated that the treatment of landfill leachate by the combined system was highly effective. The toxicity of leachate was notably decreased after the electrochemical oxidation process and the biodegradability was improved. The concentration of the organic acid with low molecular weight in the leachate increased from 28% to 90% based on the biodegradability assays after the EC oxidation process. The anaerobic digestion could further remove the residual organic compounds. At a hydraulic retention time (HRT) of 16 hours and an organic loading rate (OLR) of 8 kg COD/m3 d, the concentration of COD, SS, ALK, VA, N-TKN, N-NH4+ and P-PO4(3)- [corrected] in UASB effluent were 532, 12, 6744, 400, 540, 455 and 11.6 mg/L, respectively, with approximately 90% removal efficiency of COD. The organic compounds in the landfill leachate revealed different degradation characteristics in the combined system. p-chloroaniline, bisphenol A, 6-methyl-2-phenyl-quinoline, dimethylnaphthaline and N'-(2-methyl-4-chlorophenyl)-N-cyclohexyformamidine, classified into the first group in this paper, were completely removed by the EC oxidation and did not reappear in the effluent of the UASB reactor. Phenylacetic acid, 3-methyl-indole and N-cyclohexyl-acetamide, called the second group, were completely removed, but reappeared in the UASB reactor. 4-methyl-phenol, 3,4-dihydroisoquinoline, 2(3H)-benzothiazolone, exo-2-hydroxycineole and benzothiazole, the third group, were degraded little in the EC oxidation process, but extensively removed by the anaerobic process. Benzoic acid, benzenepropanoic acid and 2-cyano-3,5-dimethyl-1-hydroxypyrrole, the fourth group, concentration obviously increased in the EC process, but was completely removed in the UASB reactor. The content of volatile fatty acids (VFAs) markedly increased from 0.68% in the leachate to 16.18% in the effluent from the electrochemical oxidation process (EC(effl)). In addition, the degradation rate of organic compounds from the landfill leachate was different in the EC oxidation and anaerobic process.     

臭氧-曝气生物滤池处理酸性玫瑰红染料废水

在实验室配制含酸性玫瑰红染料的印染废水，采用臭氧氧化-曝气生物滤池工艺开展处理试验。试验运行结果表明，臭氧氧化处理能提高模拟废水的可生化性，BOD／COD值由原水的0．18上升到0．36。经组合工艺处理后出水COD〈40mg／L，色度40倍以下，SS约50mg／L，处理效果良好。     

臭氧氧化降解含染料废水的研究

探讨了臭氧氧化技术处理染料 (酸性、直接、活性、分散和还原颜料 )模拟废水的影响因素———pH值、初始浓度和臭氧含量等对其的影响 ;臭氧氧化能提高染料废水的可生化性 ,可用来作为高浓度染料废水的预处理手段     

Treatment of oily port wastewater effluents using the ultraviolet/hydrogen peroxide photodecomposition system.

This paper presents the nonselective degradation of mechanically pretreated oily wastewater by hydrogen peroxide (H2O2) in the presence and absence of UV irradiation. The effect of chemical oxidation on wastewater biodegradability was also examined. The exclusive use of H2O2 photolyzed by daylight results in quite efficient degradation rates for the low peroxide concentrations used. Higher hydrogen peroxide concentrations inhibit degradation of organic contaminants in the wastewater. The degradation rates of all contaminants are relatively high with an advanced oxidation system (UV/H2O2), but degradation efficiencies are not distinguishably different when 20 or 45 minutes of UV irradiation is used. The excess of H2O2 used in the process can inhibit phenolic degradation and may lead to the formation of a new phenolic fraction. The biodegradability of port wastewater did not increase significantly following the application of the advanced oxidation process.     

An integrated test strategy for the assessment of anaerobic biodegradability of wastewaters

The anaerobic biodegradability of wastewaters from different chemical plants was determined by an integrated test strategy consisting of an anaerobic toxicity test, a static anaerobic biodegradation test and a continuously operated fixed bed reactor test. This integrated procedure offered a useful tool for screening wastewaters for anaerobic biodegradability. Four different wastewaters were tested for anaerobic toxicity and biodegradability. One wastewater was used in subsequent testing in a fixed bed reactor which aimed to illustrate a potential design of an anaerobic treatment plant.     

Ozone oxidation and aerobic biodegradation with spent mushroom compost for detoxification and benzo(a)pyrene removal from contaminated soil

The combination of ozonation and spent mushroom compost (SMC)-mediated aerobic biological treatment was investigated in the removal of benzo(a)pyrene from contaminated soil. The performances of the process alone and combined were evaluated in terms of benzo(a)pyrene removal efficiency, mineralization efficiency (as total organic carbon removal), and soil residual toxicity (phytotoxicity to Lepidium Sativum and toxicity to Vibrio fischeri). In spite of the removal efficiency (35%) obtained by SMC-mediated biological process as a stand-alone treatment, the combined process showed a benzo(a)pyrene concentration reduction higher than 75%; the best removal (82%) was observed after 10 min pre-ozonation treatment. In particular, ozonation improved the biodegradability of the contaminant, as confirmed by the increase of CO(2) production (close to 70% compared to the control), mineralization (greater than 60%) and bacterial density (which increased by two orders of magnitude). Moreover, according to phytotoxicity tests on L. Sativum, the aerobic biological process of pre-ozonated soil decreased toxicity. According to the results achieved in the present study, ozonation pre-treatment showed an high potential to overcome the limitation of bioremediation of recalcitrant compound, but it should be carefully operated in order to maximize PAH removal efficiency as well as to minimize soil residual toxicity which can result from the formation of the oxidation intermediates.     

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.     

铁炭微电解深度处理焦化废水的研究

采用曝气铁炭微电解工艺对焦化废水进行了深度处理.结果表明,在活性炭、铁屑和NaCl投加量分别为10 g/L、30 g/L和200 mg/L的条件下反应240 min,出水COD去除率在30%～40%;酸性条件可以进一步提高COD去除率;微电解可以去除原生化出水中的难降解有机物,出水物质的分子量主要集中于2000 Da以下,以脂类和烃类化合物为主;出水的可生化性有了大幅度提高,BOD5/COD由0.08增加到0.53.实验结果表明,铁炭微电解是深度处理焦化废水的一种有效工艺.     

Decolorization and biodegradability of photocatalytic treated azo dyes and wool textile wastewater

The photodegradation and biodegradability have been investigated for four non-biodegradable commercial azo dyes, Reactive YellowKD-3G, Reactive Red 15, Reactive Red 24, Cationic Blue X-GRL, an indicator. Methyl Orange, and one industrial wool textile wastewater, using TiO2 suspensions irradiated with a medium pressure mercury lamp. The color removal of dyes solution and dyeing wastewater reached to above 90% within 20-30 min. of photocatalytic treatment. Biochemical oxygen demand (BOD) was found to increase, while chemical oxygen demand (COD), total organic carbon (TOC) decreased, so that the ratio of BOD5/COD of the wastewater increased from original zero up to 0.75. The result implies that photocatalytic oxidation enhanced the biodegradability of the dye-containing wastewater and therefore relationship between decolorization and biodegradability exists. When the color disappeared completely, the wastewater biodegraded normally and could be discharged for further treatment. The experimental results demonstrate that it is possible to combine photocatalysis with conventional biological treatment for the remedy of wastewater containing generally non-biodegradable azo dyes.     

Decolorization and biodegradation of dye wastewaters by a facultative-aerobic process

BACKGROUND: Dye wastewater is one of the main pollution sources of water bodies in China. Conventional biological processes are relatively ineffective for color removal, the development of alternative treatment methods will become important. Our subjective was that of introducing a new biotreatment technology which combined a facultative biofilm reactor (FBR) with an aerobic reactor (AR) to treat a dye wastewater. The efficiencies of color and chemical oxygen demand (COD) removal and the mechanism of dye degradation were investigated. METHODS: The anthraquinone acid dye (acid blue BRLL) concentration, organic loading rate (OLR) and hydraulic retention time (HRT) were varied in the experiments to evaluate the treatment efficiency and process stability. The biodegradation products were detected by infrared (IR) and high performance liquid chromatography and mass spectrometry (HPLC-MS). RESULTS AND DISCUSSION: The results demonstrated that the facultative biofilm process was more effective for decolorization than the anaerobic stage of an anaerobic-aerobic process. Most color removal occurred in the facultative reaction (maximum to 88.5%) and the BOD (biochemical oxygen demand): COD of the FBR effluent increased by 82.2%, thus improving the biodegradability of dyes for further aerobic treatment. The dye concentration, OLR and HRT will be the factors affecting decolorization. Color removal efficiency falls as the influent dye concentration increases, but rises with increased HRT. The infrared and HPLC-MS analyses of the effluents of FBR and AR reveal that the dye parent compound was degraded in each reactor during the process. CONCLUSION: The Facultative-aerobic (F-A) system can effectively remove both color and COD from the dye wastewater. The FBR played an essential role in the process. The average overall color and COD in the system were removed by more than 93.9% and 97.1%, respectively, at an OLR of 1.1 kg COD m(-3) d(-1) and at the HRT of 18-20 hours in the FBR and 4-5 hours in the AR. The color removal mechanism in each reactor was not only a sort of biosorption on the floc materials, but even more an effect of biodegradation, especially in the facultative process. Recommendation and Outlook. In applying the F-A system to treat a dye wastewater, the control of facultative processes and the set up of appropriate operation conditions appear to be critical factors. Also, it is suggested a moderate COD loading rate and about a 24-hour HRT will favor the F-A system.     

Ti(Ⅳ)催化臭氧化预处理酸性难降解制药废水

考察了酸性条件下Ti(Ⅳ)催化臭氧化预处理医药废水的效能,关联了废水氧化度与可生化性(BOD5/COD)的关系。结果表明,酸性条件下O3和O3/H2O2的氧化效率明显低于Ti(Ⅳ)/H2O2/O3。原始pH条件(3.5)下,Ti(Ⅳ)/H2O2/O3体系Ti(Ⅳ)离子和H2O2的最佳浓度分别为10 mg/L和200 mg/L。调节pH值至5.0处理120 min,制药废水的化学需氧量(COD)和总有机碳(TOC)的去除率分别为56.13%和31.49%。此时水样氧化度从原来的0.388提升到了0.608,BOD5/COD值从原来的0.019升至0.297,两者呈现较好的正相关性。以上结果表明,增大pH可以提高Ti(Ⅳ)/H2O2/O3的处理效果;此外,可以考虑利用氧化度的大小来快速判断水样的可生化性。     

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.