钙钛矿型催化剂催化湿式氧化处理煤气化废水纳滤浓缩液

采用溶胶-凝胶法制备了Mn掺杂钙钛矿型催化剂LaFexMn1-xO3,并以其为催化剂催化湿式双氧水氧化处理煤气化废水纳滤浓缩液。采用XRD,SEM,FTIR技术对催化剂进行了表征。表征结果显示：制备的催化剂均具有标准的钙钛矿型结构,其中,LaFe0.9Mn0.1O3的结构稳定,比表面积大。实验结果表明：制备的催化剂中LaFe0.9Mn0.1O3的催化活性最高,且稳定性好,连续使用5次后催化活性未见明显减弱;在H2O2投加量3.0 g/L、n（H2O2）∶n（LaFe0.9Mn0.1O3）=12∶1、反应温度160 ℃、反应压力1 MPa、浓缩液pH 3、反应时间60 min的最优条件下,COD、UV254和TOC的去除率分别达到80.9%、95.2%和68.0%,BOD5/COD由0.02提升至0.40,可生化性大幅提高。     

The use of alum, ferric chloride and ferrous sulphate as coagulants in removing suspended solids, colour and COD from semi-aerobic landfill leachate at controlled pH.

Suspended solids, colour and chemical oxygen demand (COD) are among the main pollutants in landfill leachate. Application of physical or biological processes alone is normally not sufficient to remove these constituents, especially for leachate with a lower biochemical oxygen demand (BOD)/ COD ratio. The main objective of this research was to investigate the efficiency of coagulation and flocculation processes for removing suspended solids, colour and COD from leachate produced in a semi-aerobic landfill in Penang, Malaysia. A 12-month characterization study of the leachate indicated that it had a mean annual BOD/COD ratio of 0.15 and was partially stabilized, with little further biological degradation likely to occur. Particle size analysis of the raw leachate indicated that its 50th percentile (d50) was 11.68 microm. Three types of coagulants were examined in bench scale jar test studies: aluminium sulphate (alum), ferric chloride (FeCl3) and ferrous sulphate (FeSO4). The effects of agitation speed, settling time, pH, coagulant dosages and temperature were examined. At 300 rpm of rapid mixing, 50 rpm of slow mixing, and 60 min settling time, higher removals of suspended solids (over 95%), colour (90%) and COD (43%) were achieved at pH 4 and 12. FeCl3 was found to be superior to other coagulants tested. At pH 4 and 12, fair removal of suspended solids was observed at a reasonably low coagulant dose, i.e., 600 mg L(-1); hHowever, about 2500 mg L(-1) of coagulant was required to achieve good removals at pH 6. Better removals were achieved at higher temperature. The d50 of sludge after coagulation at pH 4 with a 2500 mg L(-1) FeCl3 dose was 60.16 microm, which indicated that the particles had been removed effectively from the leachate. The results indicate that coagulation and flocculation processes can be used effectively in integrated semi-aerobic leachate treatment systems, especially for removing suspended solids, colour and COD.     

Use of Sphagnum peat moss and crushed mollusk shells in fixed-bed columns for the treatment of synthetic landfill leachate

A laboratory bench-scale fixed-bed column study operated as a down-flow configuration was conducted to evaluate Sphagnum peat moss and crushed mollusk shells as natural low-cost adsorbents for the removal of heavy metals from aerated and unaerated synthetic landfill leachate. Columns were packed with 15 cm of prepared peat moss, or 15 cm adsorbent mixtures made up of peat moss and crushed mollusk shells (4.0–4.75 mm) from Lake Ontario at different bed depth ratios. Peat was found to have the best adsorption capacities in columns treating aerated synthetic leachate for cadmium and nickel with 78.6% and 83.8% removal efficiencies, respectively. The removal of chemical oxygen demand (COD) and total nitrogen from the synthetic leachate was also monitored to evaluate the potential effects of biological activity on heavy metal adsorption. Columns receiving unaerated raw synthetic leachates did not show any significant removal of COD and total nitrogen, whereas some reduction in COD and total nitrogen was noted in the columns treating aerated synthetic landfill leachate. The results suggested that biological activity and biofilm growth could positively contribute to heavy metal retention within the fixed-media biosorption columns.     

Report: anaerobic digestion of a sulphate-rich high-strength landfill leachate: the effect of differential dosing with FeCl3.

The effect of different dose concentrations of FeCl3 on the performance of a mesophilic anaerobic digester treating a highly alkaline, high-strength and sulphate-rich landfill leachate was tested. The results indicated that sulphate reduction was the predominant reaction and methanogenic processes were entirely inhibited in the reactor without FeCl3 addition. Adding FeCl3 into the reactor restored some methanogenic activity and also improved the rates of sulphate reduction. A combination of sulphate reduction and methanogenic activity resulted in up to 75% chemical oxygen demand (COD) removal and 85% sulphate removal. Sulphate reduction remained the principle mechanism by which COD removal took place with a methane yield of only between 0.14 and 0.18 m3 CH4 kg(-1) COD removed being achieved. The process was, however, stable and offered advantages for the further treatment or conveyance of the anaerobically treated leachate.     

Landfill leachate treatment using sub-surface flow constructed wetland by Cyperus haspan

Performance evaluation of pilot scale sub-surface constructed wetlands was carried out in treating leachate from Pulau Burung Sanitary Landfill (PBSL). The constructed wetland was planted with Cyperus haspan with sand and gravel used as substrate media. The experiment was operated for three weeks retention time and during the experimentation, the influent and effluent samples were tested for its pH, turbidity, color, total suspended solid (TSS), chemical oxygen demand (COD), biochemical oxygen demand (BOD(5)), ammonia nitrogen (NH(3)-N), Total phosphorus (TP), total nitrogen (TN) and also for heavy metals such as iron (Fe), magnesium (Mg), manganese (Mn) and zinc (Zn) concentrations. The results showed that the constructed wetlands with C. haspan were capable of removing 7.2-12.4% of pH, 39.3-86.6% of turbidity, 63.5-86.6% of color, 59.7-98.8% of TSS, 39.2-91.8% of COD, 60.8-78.7% of BOD(5), 29.8-53.8% of NH(3)-N, 59.8-99.7% of TP, 33.8-67.0% of TN, 34.9-59.0% of Fe, 29.0-75.0% of Mg, 51.2-70.5% of Mn, and 75.9-89.4% of Zn. The significance of removal was manifested in the quality of the effluent obtained at the end of the study. High removal efficiencies in the study proved that leachate could be treated effectively using subsurface constructed wetlands with C. haspan plant.     

甲苯对UASB反应器中溶解性微生物产物的影响

以乙酸钠为外加碳源,考察了UASB反应器内甲苯对可溶性微生物产物（SMP）的影响。实验结果表明：低质量浓度（20~70 mg/L）的甲苯对微生物有刺激作用,使得污泥增殖速率变小,SMP的质量浓度也逐渐减少,经过一段时间的驯化后,系统COD和TOC的去除率分别达到93%和94%以上,下降趋势较小;较高质量浓度（70~200 mg/L）的甲苯对微生物有抑制作用,污泥活性下降,反应器运行状况开始恶化,SMP的质量浓度也逐渐增大,经过一段时间的驯化后,系统COD和TOC的去除率分别维持在81%和83%以上;当甲苯质量浓度超过200 mg/L时,表现为污泥活性严重下降,对COD的去除效果极差。     

Landfill leachate treatment by electrochemical oxidation

This study investigated the electrochemical oxidation of stabilized leachate from Pulau Burung semi-aerobic sanitary landfill by conducting laboratory experiments with sodium sulfate Na₂SO₄ (as electrolyte) and graphite carbon electrodes. The control parameters were influent COD, current density and reaction time, while the responses were BOD removal, COD removal, BOD:COD ratio, color and pH. Na₂SO₄ concentration was 1 g/L. Experiments were conducted based on a three-level factorial design and response surface methodology (RSM) was used to analyze the results. The optimum conditions were obtained as 1414 mg/L influent COD concentration, 79.9 mA/cm² current density and 4 h reaction time. This resulted in 70% BOD removal, 68% COD removal, 84% color removal, 0.04 BOD/COD ratio and 9.1 pH. Electrochemical treatment using graphite carbon electrode was found to be effective in BOD, COD and color removal but was not effective in increasing the BOD/COD ratio or enhancing biodegradability of the leachate. The color intensity of the treated samples increased at low influent COD and high current density due to corrosion of electrode material.     

Longitudinal data analysis in support of functional stability concepts for leachate management at closed municipal landfills

Landfill functional stability provides a target that supports no environmental threat at the relevant point of exposure in the absence of active control systems. With respect to leachate management, this study investigates “gateway” indicators for functional stability in terms of the predictability of leachate characteristics, and thus potential threat to water quality posed by leachate emissions. Historical studies conducted on changes in municipal solid waste (MSW) leachate concentrations over time (longitudinal analysis) have concentrated on indicator compounds, primarily chemical oxygen demand (COD) and biochemical oxygen demand (BOD). However, validation of these studies using an expanded database and larger constituent sets has not been performed. This study evaluated leachate data using a mixed-effects regression model to determine the extent to which leachate constituent degradation can be predicted based on waste age or operational practices. The final dataset analyzed consisted of a total of 1402 samples from 101 MSW landfills. Results from the study indicated that all leachate constituents exhibit a decreasing trend with time in the post-closure period, with 16 of the 25 target analytes and aggregate classes exhibiting a statistically significant trend consistent with well-studied indicators such as BOD. Decreasing trends in BOD concentration after landfill closure can thus be considered representative of trends for many leachate constituents of concern.     

Monitoring operational and leachate characteristics of an aerobic simulated landfill bioreactor

Long-term biodegradation of MSW in an aerobic landfill bioreactor was monitored as a function of time during 510 days of operation. Operational characteristics such as air importation, temperature and leachate recirculation were monitored. The oxygen utilization rates and biodegradation of organic matter rates showed that aerobic biodegradation was feasible and appropriate to proceed in aerobic landfill bioreactor. Leachate analyses showed that the aerobic bioreactor could remove above 90% of chemical oxygen demand (COD) and close to 100% of biochemical oxygen demand (BOD5) from leachate. Ammonium (NH4+), nitrate (NO3-) and sulphate (SO4(2-)) concentrations of leachate samples were regularly measured. Results suggest that nitrification and denitrification occurred simultaneously, and the increase in nitrate did not reach the levels predicted stoichiometrically, suggesting that other processes were occurring. Leachate recirculation reduced the concentrations of heavy metals because of the effect of the high pH of the leachate, causing heavy metals to be retained by processes such as sorption on MSW, carbonate precipitation, and hydroxide precipitation. Furthermore, the compost derived from the aerobic biodegradation of the organic matter of MSW may be considered as soil improvement in the agricultural plant production. Bio-essays indicated that the ecotoxicity of leachate from the aerobic bioreactor was not toxic at the end of the experiment. Finally, after 510 days of degradation, waste settlement reached 26% mainly due to the compost of the organic matter.     

Size-fractionation and characterization of landfill leachate and the improvement of Cu2+ adsorption capacity in soil and aged refuse

Leachate was collected from an anaerobic lagoon at Shanghai Laogang refuse landfill, the largest landfill in China, and the sample was separated into six fractions using micro-filtration membranes, followed by ultra-filtration membranes. Several parameters of the samples were measured, including chemical oxygen demand (COD), total organic carbon (TOC), total solids (TS), pH, total phosphate (TP), total nitrogen (TN), fixed solids (FS), NH4+, orthophosphate, color, turbidity, and conductivity. These parameters were then quantitatively correlated with the molecular weight cutoff of the membrane used. Organic matter in the dissolved fraction (MW<1kDa) predominated in the leachate, accounting for 65% of TOC. Thermal infrared spectroscopy was used to characterize the filter residues. Asymmetric and symmetric stretching of methyl and methylene groups, and of functional groups containing nitrogen and oxygen atoms, were observed. In addition, the ability of two different samples to adsorb heavy metals was tested. Cu2+ was chosen as the representative heavy metal in this study, and the samples were soil; aged refuse, which had spent 8 years in a conventional sanitary landfill; and samples of soil and aged refuse treated for 48h with leachate in the ratio of 5g of sample per 50ml of leachate. Cu2+ uptake by the raw soil was approximately 4.60microg/g, while uptake by the leachate-contacted soil and leachate-contacted aged refuse were 5.66 and 5.11microg/g, respectively. These results show that the organic matter in the leachate enhanced the capacity of aqueous solutions to adsorb Cu2+.     

高盐有机化工废水中COD与TOC的相关性

以COD为指标评价废水的有机物污染程度存在诸多不足,而TOC能更好地反映废水中有机物的含量。以高盐有机化工废水为研究对象,利用多级活性炭吸附工艺对其进行预处理,对原水、吸附出水、再生液中COD与TOC的相关性进行了分析。分析结果表明：在一定范围内,原水COD与TOC满足关系式COD = 56.537 7+ 0.967 04TOC;废水在吸附处理过程中,COD与TOC仍呈线性相关关系,但不同工段需各自建立独立的回归方程;TOC测定结果的精密度较好,且远优于COD直接测定的精密度,回收率范围98.59%~110.69%;利用线性回归方程根据TOC测定结果预测COD,预测结果准确、可靠、精密度好。     

UASB反应器反硝化处理对氨基二苯胺生产废水

采用UASB工艺处理橡胶助剂对氨基二苯胺（RT培司）生产废水。实验结果表明：UASB启动初期（1~16 d）,COD去除率由60.8%降至24.2% ,TOC去除率由75.6%降至37.2%;UASB运行16 ~50 d,COD去除率逐渐提高;运行50 d时COD去除率为69.4%,TOC去除率高达90.0%。在进水COD负荷不超过6 kg/（m³·d）的条件下,UASB对COD的去除率为42.7%~69.4%,TOC去除率为58.0%~90.0%,NO_{3^--N去除率接近100%。本实验最佳进水TOC 与TN 比为2.0,UASB进水pH可调节为4.5左右,反应温度为18~34 ℃时对UASB反硝化处理效果影响不大。UASB对苯系化合物的去除率从高至低顺序为对硝基酚>苯酚>苯胺。}     

Kinetics of biochemically driven metal precipitation in synthetic landfill leachate

This study investigates the effectiveness of using metal sulphide and carbonate precipitation mechanisms combined with a landfill‐derived mixed bacterial population. The study was conducted under controlled substrate conditions in anaerobic batch reactors. High chemical oxygen demand (COD):sulphate ratios, butyrate, propionate, and acetate were used anaerobically by bacteria for growth with associated sulphate reduction as well as sulphide and carbonate generation. Propionate and butyrate degradation occurred during sulphate reduction by sulphate‐reducing bacteria while acetate degradation was associated with methanogenesis by methanogenic bacteria. Using low COD, sulphate ratios showed limited acetate utilization, but sulphate reduction still occurred. Precipitation of Cd, Cu, Zn, Ni, and Fe sulphides occurred quickly and was completed in 15 to 30 days, while Ca, Mn, and Mg carbonates formed after 40 to 50 days and some soluble metal remained even after 120 days. The rate of metal precipitation was in the order of Cd>Cu>Zn>Ni>Fe>Mn>Mg>Ca. Bacterially mediated metal precipitation occurred slower than that recognized for chemical precipitation. These findings suggest that contaminant transport models based on chemical equilibrium metal behaviors may over‐predict metal removal by bio‐precipitation. © 2002 Wiley Periodicals, Inc.     

微电解—Fenton试剂氧化—A/O工艺处理制药废水

采用微电解—Fenton试剂氧化—A/O组合工艺处理高浓度制药废水。实验结果表明:经微电解—Fenton试剂氧化工艺预处理后,COD去除率可达50%~60%,BOD5/COD提高到0.3以上;预处理后的废水与清洗废水和生活污水混合,采用生化法进一步处理,出水COD小于100 mg/L,BOD5小于20 mg/L,ρ(NH3-N)小于50 mg/L,SS小于70 mg/L,满足GB 8978—1996《污水综合排放标准》中的三级排放标准。     

Self-Bonding Boards From Plantain Fiber Bundles After Enzymatic Treatment: Adhesion Improvement of Lignocellulosic Products by Enzymatic Pre-Treatment

Self-bonding boards were manufactured with treated fibers at different concentrations of a laccase enzyme. This enzyme induced the generation of phenoxy radicals in the fiber lignin which can generate covalent bonds and cross-linked by radical–radical coupling. The effect of laccase concentration on the properties of obtained fiberboards was evaluated. The formation of free radicals and changes in the lignin macromolecule was measured using scavenging activity test, infrared spectroscopy, electron paramagnetic resonance and scanning electron microscopy. Thermal and mechanical properties of the resulting fiberboards were determined by differential scanning calorimetry, thermo gravimetric analysis and flexion tests. Increased thermal stability, modulus of elasticity and modulus of rupture and also, a reduction in thickness swelling and water absorption, were observed at higher concentrations of laccase. These results are ascribed to the effect of the free radicals that were generated during the enzymatic treatment.     

酯化废水铁还原预处理的研究

用铁还原－中和－混凝沉淀法进行酯化废水预处理试验,原废水不稀释,铁还原处理在曝气条件下运行,还原时间为７￣８ｈ,处理过程中的耗铁量为每升废水１２０ｍｇ左右,全过程ＣＯＤ去除率可达３０％以上,ＢＯＤ５去除率可达４０％以上,色度降低５０％。     

UASB反应器反硝化处理工业废水

采用絮状污泥成功启动升流式厌氧污泥床(UASB)反应器处理含甲酸、苯胺、环已酮、NO3-等的工业废水。UASB反应器以低负荷启动,10天后逐渐提高进水COD,出水COD保持在710~770 mg/L,COD去除率为40%~60%;出水TOC保持在115~314 mg/L,TOC去除率由60.3%逐渐升高至87.2%,最终维持在81%左右;出水中ρ(NO3-)维持在134~176 mg/L,NO3-去除率为90%左右,系统稳定后NO3-去除率几乎为100%。在进水COD容积负荷不超过5.00 kg/(m3·d)的条件下,实际COD容积负荷稳定在2.00 kg/(m3·d)左右,实际TOC容积负荷稳定在1.00 kg/(m3·d)以上。当进水COD容积负荷不大于4.48 kg/(m3·d)时,COD去除率为55%~74%,TOC去除率为63%~87%,NO3-去除率大于95%。     

Treatment of anti-osmotic drug based pharmaceutical effluent in an upflow anaerobic fluidized bed system

During the production of Cephradine (a main constituent of anti-osmotic drug) a large quantity of concentrated effluent was produced. The main polluting compounds in this effluent are osmotic drug, acetic acid and ammonia. The feasibility of using a fluidized bed reactor under anaerobic condition with bioaugmentation to treat anti-osmotic drug based pharmaceutical effluent was evaluated. The main objective of the study was to show that bioaugmentation could be used to promote biological treatment to applications where conventional operation might be difficult or unfavourable. The effluent with chemical oxygen demand (COD) of 14000-18000 mg/l was treated in a fluidized bed reactor with a hydraulic retention time of 3-12 h. The reactor was unable to maintain consistent removal in conventional mode of operation due to an inability to retain and grow biomass. The COD reduction (%) after inoculation from a sequencing batch reactor was related to influent concentration, mass of inoculum and hydraulic retention time characterized by calculating the initial food to microorganism ratio. The role of volatile fatty acid (VFA) as cosubstrate was assessed with respect to COD reduction (%). Continuous COD reduction (%) attained a maximum value of 88.5% using bioaugmentation through periodic addition of acclimated cells every 2 days with 30-73.2 g of cells from an off-line enricher reactor.     

Influence of composition on the biomethanation potential of restaurant waste at mesophilic temperatures

A synthetic waste was used to study the effect of waste composition on anaerobic degradation of restaurant waste. It was made by blending melted pork lard, white cabbage, chicken breast, and potato flakes, to simulate lipids, cellulose, protein, and carbohydrates, respectively. Four blends of the four constituents with an excess of each component were assayed and compared with a fifth blend containing an equal amount of chemical oxygen demand (COD) of each of the four components. The methane production and the time course of soluble COD and volatile fatty acids were assessed in batch assays. A high reduction of volatile solids (between 94% and 99.6%) was obtained in all the assays. The methane yield was between 0.40 m(3) CH(4)/kg VS(initial) (excess of carbohydrates) and 0.49 m(3) CH(4)/kg VS(initial) (excess of lipids). The degradation of the lipid-rich assays differed from the others. Fifty percent of the biochemical methane potential was obtained after 3-6 days for all of the assays, except for the one with excess of lipids which achieved 50% methanation only after 14.7 days of incubation. In the assay with excess of lipids, a considerable fraction of COD remained in the liquid phase, suggesting an inhibition of the methanogenic process that was likely due to the accumulation of long chain fatty acids. The hydrolysis rate constants, assuming first order kinetics, over the first 6 days were between 0.12d(-1) (excess of lipids) and 0.32 d(-1) (excess of carbohydrates). The results indicate that anaerobic digestion facilities with large variations in lipid input could have significant changes in process performance that merit further examination.     

石墨毡电极预处理模拟邻甲酚废水

采用聚丙烯腈基石墨毡电极,以NaCl为电解质,在恒流电解的条件下,对质量浓度为1 000 mg/L、COD=3 672 mg/L的模拟邻甲酚废水进行预处理。研究了电解时间、初始废水pH、NaCl加入量、电流密度对邻甲酚去除率的影响,考察了废水的COD变化,并探讨了反应机理。实验结果表明：石墨毡电极具有较好的导电性、吸附性,对邻甲酚具有较好的电化学氧化性能;常温常压下,初始废水pH为6~7、电流密度为90 A/m2、向300 mL废水中加入0.5 g NaCl时,经4 h电解,邻甲酚的去除率达到97.1%,COD的去除率达到47.3%;处理后废水的BOD5/COD由0.04提高至0.33,可不经稀释直接进行生物处理。