丙烯酸生产外排废水化学需氧量与总有机碳相关性研究

化学需氧量（COD_Cr）与总有机碳（TOC）指标均可用来表征废水的有机物污染程度.不过,以COD_Cr表征有机物污染程度一般只能反映水中部分有机物的量,而TOC能更全面地反映废水中有机物的含量.以丙烯酸生产外排废水为研究对象,分析结果表明：在一定范围内,废水中COD_Cr与TOC满足关系式y=1.147 4x+74.75（R²=0.955 26）,回收率范围98%~115%,TOC测定结果的精密度高、可靠、准确,在一定条件下,可使用TOC来间接换算COD_Cr.     

Landfill leachate treatment using the sequencing batch biofilm reactor method integrated with the electro-Fenton process

A study was conducted on the treatment of landfill leachate by combining the sequencing batch biofilm reactor (SBBR) method with the electro-Fenton method. The reduction of chemical oxygen demand (COD), biological oxygen demand (BOD₅), and ammonia nitrogen (NH ₄ ⁺ -N) from the leachate by the SBBR method was investigated. For the electro-Fenton experiment, the changes in COD and total organic carbon (TOC) with the increase in H₂O₂ dosage and electrolysis time under optimal conditions were also analysed. The results showed that the average efficiencies of reduction of COD, BOD₅, and NH ₄ ⁺ -N achieved using the SBBR method were 21.6 %, 54.7 %, and 56.1 %, respectively. The bio-effluent was degraded by the subsequent electro-Fenton process, which was rapid over the first 30 min then subsequently slowed. After 60 min of the electro-Fenton treatment, the efficiencies of reduction of TOC, COD, and BOD₅ were 40.5 %, 71.6 %, and 61.0 %, respectively. There is a good correlation between the absorbance of leachate at 254 nm (UV₂₅₄) and COD or TOC during the electro-Fenton treatment.     

The coulometric determination of chemical oxygen demand

The chemical oxygen demand (COD) of solutions containing various organic compounds is calculated from the net faradaic charge (Q_net) estimated for the total electrolytic oxidation of Cr^III generated during oxidative degradation of the organic compounds in acidic media containing excess Cr^VI. Values of Q_net for conversion of Cr^III to Cr^VI are estimated from the linearized chronoamperometric data plotted as In {i_{tat, t}} vs. t. This procedure is preferred over determinations of Q_net from the total integrals of i_tot over the entire electrolysis period because of large errors that can result from uncertainty in the background current (i_bkg) for t → ∞. The proposed coulometric procedure offers the benefit that reagent solutions can be reused, thereby minimizing the need for disposal of wastes containing toxic Cr^VI. This procedure was applied in a single digest solution for consecutive determinations of COD. Average COD values for potassium acid phthalate and glucose were 103.8% (s - 6.0, N - 10) and 100.2% (s - 4.2, N - 11), respectively, based on the theoretical degradation to CO₂. In comparison for these same samples, an EPA approved method, based on colorimetric determination of Cr^III, gave COD values of 101.4% (S - 1.4, N - 5) and 100.1% (s - 1.4, N - 5) of the theoretical. Statistical tests indicate no significant difference in the COD values determined for these compounds using the coulometric and EPA methods.     

Preparation of the Mn-Fe-Ce/γ-Al2O3 ternary catalyst and its catalytic performance in ozone treatment of dairy farming wastewater

The quality of dairy farming wastewater in different regions is particular and different. In Southern China, the Chemical Oxygen Demand (COD_Cr) and colourity of effluent from conventional dairy farming wastewater treatment processes are similar. Catalytic ozonation is a very promising technical method. In this paper, the Mn-Fe-Ce/γ-Al₂O₃ catalyst was prepared via the optimized preparation method of impregnation roasting using γ-Al₂O₃ as the carrier, and this catalyst was used in the ozonation of actual dairy farming wastewater from treatment facilities. The performance of the Mn-Fe-Ce/γ-Al₂O₃ catalyst on dairy farming wastewater was investigated using a simulated dynamic test. The effects of the reaction time, pH and catalyst dosage on COD_Cr and the colourity removal ratio were investigated. The results show that the optimum treatment conditions were a reaction time of 20 min, pH 9, and catalyst dosage of 15 g/L. The COD_Cr removal ratio reached 48.9% and the colourity was 95% under the optimum conditions. BOD₅/COD_Cr increased from 0.21 to 0.54 after catalytic ozonation, indicating that the biodegradability of wastewater was significantly improved. This research provides a new method and theoretical guidance for dairy farming wastewater treatment.     

Operation of industrial-scale electron beam wastewater treatment plant

Textile dyeing processes consume large amount of water, steam and discharge filthy and colored wastewater. A pilot scale e-beam plant with an electron accelerator of 1 MeV, 40 kW had constructed at Daegu Dyeing Industrial Complex (DDIC) in 1997 for treating 1,000 m³ per day. Continuous operation of this plant showed the preliminary e-beam treatment reduced bio-treatment time and resulted in more significant decreasing TOC, COD_Cr, and BOD₅. Convinced of the economics and efficiency of the process, a commercial plant with 1 MeV, 400 kW electron accelerator has constructed in 2005. This plant improves the removal efficiency of wastewater with decreasing the retention time in bio-treatment at around 1 kGy. This plant is located on the area of existing wastewater treatment facility in DDIC and the treatment capacity is 10,000 m³ of wastewater per day. The total construction cost for this plant was USD 4 M and the operation cost has been obtained was not more than USD 1 M per year and about USD 0.3 per each m³ of wastewater.     

Electrocatalytic Sensor for the Determination of Chemical Oxygen Demand Using a Lead Dioxide Modified Electrode

An amperometric method that makes use of a nano‐PbO₂ modified electrode as an electrocatalytic sensor for the determination of chemical oxygen demand (COD) is described. The sensor signal was observed as a result of the detection of the oxidation current due to electrocatalytic oxidation of organic compounds in the sample solution. This sensor responded linearly to the COD_Cr of standard samples in the range of 5–3 000 ppm and the detection limit was 2.5 ppm. When using the sensor to determine real samples, it displays short analysis time, simplicity and no sample pretreatment. The sensor was stable for over 20 days in real wastewater samples and has successfully been applied to the determination of COD in real wastewater samples.     

掺氮TiO2可见光降解有机污染物的比较研究

用溶胶-凝胶法制备了不同掺杂量的N/TiO₂复合纳米粉末, 采用X射线衍射(XRD)、扫描透镜(TEM)、紫外-可见反射吸收光谱(UV-vis)对催化剂进行了初步表征. 通过X射线光电子能谱(XPS)、元素分析仪(EA)测定其含氮量. XPS分析结果显示TiO₂晶格中的氧被氮原子取代, N/TiO₂表面存在Ti^3＋离子; 紫外-可见反射吸收光谱测得不同掺杂量的N/TiO₂的禁带宽度(E_g), 推测在TiO₂价带上方生成了由N诱导产生的中间带, 当氮、钛摩尔比为0.0880时N/TiO₂的E_g最小, 为2.50 eV. 在可见光下, 以酸性桃红(SRB)和无色小分子对氯苯酚(4-CP)作为可见光活性实验的探针反应, 确定了最佳掺杂比为n_N/n_Ti＝0.0880. 结果表明, 最佳掺杂量下N/TiO₂能显著降解SRB和4-CP, 通过测定ESR, IR, TOC, COD, 重点比较了TiO₂在掺杂N前后在降解SRB和4-CP时的差异, 包括氧化物种、矿化率、最终产物等, 证明在可见光下, N/TiO₂的降解机理为电子从独立的N 2p轨道激发到Ti 3d轨道, 产生羟基自由基等氧化物种, 达到降解有机物的目的.     

Ultrasonic Decomposition of Ammonia‐Nitrogen and Organic Compounds in Coke Plant Wastewater

The investigations of the ultrasonic decomposition of NH₃‐N and organic compounds (i.e., COD_Cr) in coke plant wastewater are presented in this work. The process parameters were controlled with respect to the presence (or absence) of air atmosphere, initial pH value, initial concentration, and ultrasonic power density in the process of ultrasonic decomposition. It is noted that the ultrasonic removal efficiencies for both the NH₃‐N and the COD_Cr were increased in the presence of the air atmosphere and significantly affected by the initial pH value. The removal efficiencies increased with increasing the ultrasonic power density while they decreased with increasing the initial concentration. The effects of n‐butyl alcohol as an effective OH radical scavenger on the removal efficiencies indicates that the ultrasonic decomposition of the NH₃‐N was carried out mainly via the mechanism of thermal decomposition in cavitation bubbles or in the interfacial region, whereas the ultrasonic decomposition of the COD_Cr mainly resulted from the reactions with OH radicals in the bulk solution. The GC/MS analysis indicates that most of the organic compounds in the wastewater were effectively destroyed by ultrasound.     

Gliding Arc Discharge for Decolorization and Biodegradability of Azo Dyes and Printing and Dyeing Wastewater

Gliding arc discharge process was used for the pretreatment of four azo dye solutions, which are classified to acidic, reactive and chemical indicator, as well as printing and dyeing wastewater with the objective of improving their overall biodegradability. The percentage color removal of all samples were found to be over 92% after 40?min treatment, and the color disappearance of four azo dyes followed the first-order kinetics completely. The biochemical oxygen demand (BOD₅)/chemical oxygen demand (COD) ratio increased from 0.02 to 0.46 for acid orange II (AO7), 0.173 to 0.55 for methyl orange, 0.019 to 0.4 for direct fast black, 0 to 0.65 for reactive red K-2BP. The decolorization of printing and dyeing wastewater achieved 97.5% and the COD removal efficiency was 76.6%. The BOD₅/COD ratio increased to 0.55 after 20?min treatment. The experimental results indicates it is possible to combine gliding arc discharge with conventional biological treatment for the remedy of wastewater containing generally non-biodegradable dye.     

Performance of a photocatalytic hybrid system coupled with a stainless steel membrane for removal of humic acid

The objective of this study was to evaluate the performance of a photocatalysis/H₂O₂/metal membrane hybrid system in the degradation of humic acid. A metal membrane of nominal pore size 0.5 μm was used in the experiment for separation of TiO₂ particles. Hydrogen peroxide was tested as an oxidant. The efficiency of removal of COD_Cr and color increased rapidly for initial hydrogen peroxide concentrations up to 50 mg L⁻¹. The efficiency of removal of COD_Cr and color by 50 mg L⁻¹ initial hydrogen peroxide concentration was approximately 95 and 98%, respectively. However, addition of hydrogen peroxide over 50 mg L⁻¹ inhibited the efficiency of the system. Addition of hydrogen peroxide to a UV/TiO₂ system enhanced efficiency of removal of COD_Cr and color compared with no addition of hydrogen peroxide. This may be ascribed to capture electrons ejected from TiO₂ and to the production of OH radicals. Application of the metal membrane in the UV/TiO₂/H₂O₂ system enhanced the efficiency of removal of COD_Cr and color because of adsorption by the metal membrane surface and the production of OH radicals. By application of a metal membrane with a nominal pore size of 0.5 μm, TiO₂ particles were effectively separated from the treated water by metal membrane rejection. The photocatalytic metal membrane had much less resistance than the humic acid, TiO₂, and humic acid/TiO₂ because of the degradation of humic acid by the photocatalytic reaction.     

球磨法制备Y3+/TiO2光催化剂及处理海水养殖废水

采用机械球磨法制备Y~(3+)修饰TiO_2光催化剂,利用紫外-可见漫反射光谱(UV-Vis DRS)、X射线光电子能谱(XPS)、X射线粉末衍射(XRD)、扫描电镜(SEM)等对其进行表征,在紫外光下,以亚甲基蓝(MB)为去除物来考察催化剂活性并优化球磨工艺。将最佳条件下制得的Y~(3+)/TiO_2光催化剂负载于不同半径的塑料浮球上,分别在紫外光和模拟太阳光照射下处理海水养虾废水,通过CODCr(chemical oxygen demand)及三维荧光观察有机物含量变化。结果表明,当Y~(3+)的物质的量分数为2%,球磨时间4 h,球料质量比4∶1,转速为500 r·min~(-1)时,MB光催化降解反应速率常数可达0.111 3 min~(-1),是纯TiO 2的4.2倍。由UV-Vis DRS、XPS、N_2吸附-脱附、XRD、SEM等表征结果显示,2%Y~(3+)/TiO_2样品的禁带宽度降低至3.05 eV,光吸收发生红移,并产生可见光响应,表面吸附氧含量明显增加,比表面积增大到104 m~2·g~(-1)。采用纯TiO_2及2%Y~(3+)/TiO_2为光催化剂处理养虾废水,在可见光和紫外光下CODCr的去除率分别为14.7%和18.8%、26.9%和37.5%。考察3种直径分别为1、2、3 cm负载Y~(3+)/TiO_2浮球的光催化效果,显示直径为2 cm浮球效果最佳,CODCr去除率可达38.5%。     

Simple and efficient treatment of high-strength industrial waste water using commercial zero-valent iron

The zero-valent iron (ZVI)/H₂O₂ Fenton system can be considered as an effective solution for the removal of many of the organic pollutants present in the waste waters generated by the drug manufacturing industry. The hydrogen peroxide concentration and dosage rate were studied in order to improve the efficiency of the oxidant in the TOC reduction and, thereby enhance the overall catalytic performance of the ZVI/H₂O₂ Fenton system. TOC reductions of up to 80 % and BOD₅/COD ratios of up to 0.6 were achieved in the waste water as received without dilution (TOC_O approximately 5 g L^?1) using hydrogen peroxide dose-staggering. This showed that the ZVI/H₂O₂ process led not only to a decrease in TOC removal but also to an increase in the biodegradability of the by-products formed. The hydrogen peroxide was consumed more efficiently and very low concentrations of iron dissolved (7 mg L^?1) were obtained in the final effluents. The final values of COD, BOD₅, the suspended solids’ content and the conductivity of the treated waste water met the limits of the Spanish legal industrial discharge, Decree 57/2005 (Ministry of Environment, Local Government and Planning, Community of Madrid, 2005). In addition, the composite thus formed, consisting of zero-valent iron and iron oxide-oxyhydroxides, can be readily removed from the treated effluent, avoiding any post-treatment step.     

Effect of an Electromagnetic Field on Anaerobic Digestion: Comparing an Electromagnetic System (ES), a Microbial Electrolysis System (MEC), and a Control with No External Force

This study examined the application of an electromagnetic field to anaerobic digestion by using an electromagnetic system (ES), a microbial electrolysis cell (MEC), and a control with no external force. The experimental work was performed by carrying out biochemical methane potential (BMP) tests using 1 L biodigesters. The bioelectrochemical digesters were supplied with 0.4 V for 30 days at 40 °C. The electromagnetic field of the ES was generated by coiling copper wire to form a solenoid in the BMP system, whereas the MEC consisted of zinc and copper electrodes inside the BMP system. The best performing system was the MEC, with a yield of 292.6 mL CH₄/g chemical oxygen demand removed (COD_removed), methane content of 86%, a maximum current density of 23.3 mA/m², a coulombic efficiency of 110.4%, and an electrical conductivity of 180 µS/cm. Above 75% removal of total suspended solids (TSS), total organic carbon (TOC), phosphate, and ammonia nitrogen (NH₃-N) was also recorded. However, a longer exposure (>8 days) to higher magnetic intensity (6.24 mT) on the ES reduced its overall performance. In terms of energy, the MEC produced the greatest annual energy profit (327.0 ZAR/kWh or 23.36 USD/kWh). The application of an electromagnetic field in anaerobic digestion, especially a MEC, has the potential to maximize the methane production and the degradability of the wastewater organic content.     

阴阳离子双隔膜三室电解槽电渗析处理垃圾渗滤液

采用阴阳离子双隔膜三室电解槽,将电渗析技术与Ｆｅｎｔｏｎ试剂法结合,去除垃圾渗滤液中氨氮和ＣＯＤ_Ｃｒ。垃圾渗滤液中的氨氮通过电渗析技术富集到阴极液中,随后用化学沉淀法加以去除。同时,在铁阳极上生成的Ｆｅ^２＋离子,与滴加入阳极液中的Ｈ_２Ｏ_２反应生成Ｆｅｎｔｏｎ试剂,降解有机物,降低ＣＯＤ_Ｃｒ。实验结果表明,模拟废水中的氨氮透过率达８０％,垃圾渗滤液中氨氮浓度和ＣＯＤ_Ｃｒ由原来的１９８２和２２４８ ｍｇ／Ｌ分别降至２００和１２７ ｍｇ／Ｌ。     

A chemiluminescence biochemical oxygen demand measuring method

A new chemiluminescence biochemical oxygen demand (BOD_CL) determining method was studied by employing redox reaction between quinone and Baker's yeast. The measurement was carried out by utilizing luminol chemiluminescence (CL) reaction catalyzed by ferricyanide with oxidized quinone of menadione, and Saccharomyces cerevisiae using a batch-type luminometer. In this study, dimethyl sulfoxide was used as a solvent for menadione. After optimization of the measuring conditions, the CL response to hydrogen peroxide in the incubation mixture had a linear response between 0.1 and 100 μM H₂O₂ (r² = 0.9999, 8 points, n = 3, average of relative standard deviation; R.S.D._av = 4.22%). Next, a practical relationship between the BOD_CL response and the glucose glutamic acid concentration was obtained over a range of 11-220 mg O₂ L⁻¹ (6 points, n = 3, R.S.D._av 3.71%) with a detection limit of 5.5 mg O₂ L⁻¹ when using a reaction mixture and incubating for only 5 min. Subsequently, the characterization of this method was studied. First, the BOD_CL responses to 16 pure organic substances were examined. Second, the influences of chloride ions, artificial seawater, and heavy metal ions on the BOD_CL response were investigated. Real sample measurements using river water were performed. Finally, BOD_CL responses were obtained for at least 8 days when the S. cerevisiae suspension was stored at 4 °C (response reduction, 69.9%; R.S.D. for 5 testing days, 18.7%). BOD_CL responses after 8 days and 24 days were decreased to 69.9% and 35.8%, respectively, from their original values (R.S.D. for 8 days involving 5 testing days, 18.7%).     

Use of flow injection analysis based on iodometry for automation of dissolved oxygen (Winkler method) and chemical oxygen demand (dichromate method) determinations

Summary Two analytical methods for water analysis were miniaturized and partly automated by the flow injection analytical approach. In the standard Winkler method for dissolved oxygen determination, the final step, the titration of liberated iodine with Na₂S₂O₃, was replaced by amperometric detection in a flowing stream. The concentration of dissolved oxygen was determined by the standard addition method using KIO₃ as a standard reagent. The dichromate method for chemical oxygen demand determinations was also miniaturized. Oxidation of organic substances by K₂Cr₂O₇ in H₂SO₄ (1+1) medium was carried out under standard conditions and the excess of dichromate ions was determined electrochemically via measurement of released I₂ after addition of KI in a continuous stream. The chemical oxygen demand of a sample was calculated on the basis of the current without standard addition.

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Anwendung der iodometrischen Fließinjektionsanalyse zur Automation der Bestimmung von gelöstem Sauerstoff (Winkler-Methode) und chemischem Sauerstoffbedarf (Dichromat-Methode)

     

Semi-continuous Cultivation of <Emphasis Type="Italic">Chlorella vulgaris</Emphasis> for Treating Undigested and Digested Dairy Manures

The present study, based on a previous batch-wise experiment, investigated a lab-scale semi-continuous cultivation of green microalgae Chlorella vulgaris (UTEX 2714), as a useful means for nutrient reduction as well as production of algal biomass which can be used as potential feedstock for the production of biofuel and other commodities, on 20× diluted dairy manures. Both undigested and digested samples were applied in parallel experiments for comparison regarding the requirements of hydraulic retention times (HRTs), removal efficiencies of nitrogen, phosphorus, and chemical oxygen demand (COD), biomass productivities, and CO₂ sequestration abilities. It was demonstrated that algae grown in undigested dairy manure achieved removal rates of 99.7%, 89.5%, 92.0%, and 75.5% for NH₄⁺–N, TN, TP, and COD, respectively, under a 5-day HRT, while the HRT had to extend to 20 days in order to achieve 100.0% removal of NH₄⁺–N in digested one with simultaneous removals of 93.6% of TN, 89.2% of TP, and 55.4% of COD. The higher organic carbon contained in undigested dairy manure helped boost the growth of mixotrophic Chlorella, thus resulting in a much shorter HRT needed for complete removal of NH₄⁺–N. Moreover, algae grown in digested dairy manure provided more penitential than those grown in undigested one in CO₂ sequestration per milligram of harvested dried biomass (1.68 mg CO₂/mg dry weight (DW) vs 0.99 mg CO₂/mg DW), but did not surpass in total the amount of CO₂ sequestered on a 15-day period basis because of the better productivity gained in undigested dairy manure.     

Gamma ray irradiation for sludge solubilization and biological nitrogen removal

This study was conducted to investigate the effects of gamma ray irradiation on the solubilization of waste sewage sludge. The recovery of an organic carbon source from sewage sludge by gamma ray irradiation was also studied. The gamma ray irradiation showed effective sludge solubilization efficiencies. Both soluble chemical oxygen demand (SCOD) and biochemical oxygen demand (BOD₅) increased by gamma ray irradiation. The feasibility of the solubilized sludge carbon source for a biological nitrogen removal was also investigated. A modified continuous bioreactor (MLE process) for a denitrification was operated for 20 days by using synthetic wastewater. It can be concluded that the gamma ray irradiation was useful for the solubilization of sludge and the recovery of carbon source from the waste sewage sludge for biological nitrogen removal.     

Bioremediation of effluent from a uranium mill tailings repository in South China by <Emphasis Type="Italic">Azolla</Emphasis>–<Emphasis Type="Italic">Anabaena</Emphasis>

Hydroponic experiments were conducted on the removal of uranium, heavy metals and nutrients from the effluent of a uranium mill tailings repository in South China by Azolla–Anabaena. The plant–microbe symbiont was kept in the effluent for 30 days, and it was found that U, Fe, Mn, Cu, Zn, Pb, Cd, total phosphorus (TP), total nitrogen (TN) and SO₄^2? reduced by 87.6, 99.1, 98.8, 88.2, 91, 78.3, 77.5, 93.4, 98.7 and 76.7%, respectively. Specifically, the concentration of uranium reduced to 0.039 mg L^?1, which is below the limits of contaminants by the Department of Environmental Protection of China. The concentration of Fe, Cu, Zn, Pb, TP and TN in the effluent reached the quality standard for drinking water. The results showed that Azolla–Anabaena can be used for the bioremediation of the effluent from the uranium mill tailings repository.