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.     

垃圾填埋场渗滤液物化深度处理研究

通过Fenton法和结合聚合硫酸铁的混凝作用，实现垃圾渗滤液氧化塘出水COD的深度处理；并利用水泥水化产物的凝胶物质，强化COD去除率。30％H2O2投加量为0．75mL／L、七水硫酸亚铁投加量为1．5g／L、n（H2O2）：n（Fe^2＋）=1．2：1（摩尔比）时，Fenton法对渗滤液COD的去除率可达52％；水灰比为2：1、搅拌24h的水泥水化物将Fenton法的出水pH值从4调至10，该工艺流程总的COD去除率为73．6％，较普通的Ca（OH）2调节法提高9．3％，出水COD可以从进水的1200mg／L降至315mg／L。     

MBR-NF截留液中腐植酸的纳滤分离浓缩特性

MBR-NF截留液是一类难处理的高浓度有机废水,其所含有机物几乎都是腐植酸,可考虑资源利用。实验室内采用纳滤对其所含腐植酸进行分离浓缩。引入分离因子来表征纳滤的分离效果。实验结果表明,分离因子(SF)与体积浓缩倍数(CF)有很好的线性关系,浓缩倍数为5时,截留液中有机碳浓度为9 413 mg/L,重金属浓度处于mg/L水平,分离因子达到2.76,表明纳滤可有效地将MBR-NF截留液中的腐植酸与无机盐分离,并进行浓缩。     

Hybrid zero valent iron (ZVI)/H2O2 oxidation process for landfill leachate treatment with novel nanosize metallic calcium/iron composite

A novel nanosize metallic calcium/iron dispersed reagent was synthesized and tested as coagulant/catalyst in a hybrid zero valent iron (ZVI)/H₂O₂ oxidation process to treat leachate. Two different types of leachates, one from municipal solid waste (MSW) tipping hall (MSWIL) and second from an MSW landfill site (MSWLL), were collected and characterized. The morphology, elemental composition, and mineral phases of the nano-Ca/CaO and nano-Fe/Ca/CaO were characterized by scanning electron microscopy–electron dispersive spectroscopy (SEM-EDS) and x-ray powder diffraction (XRD) analysis. The coagulation process with 2.5 g L^?1 nano-Ca/CaO attained 64.0, 56.0, and 20.7% removal of color, chemical oxygen demand (COD), and total suspended solids (TSS) in MSWLL. With only 1.0 g L^?1 of nano-Fe/Ca/CaO, relatively high color, COD and TSS removal was achieved in MSWLL at 67.5, 60.2, and 37.7%, respectively. The heavy metal removal efficiency reached 91–99% after treatment with nano-Fe/Ca/CaO in both leachate samples. The coupling process, using 1.0 g L^?1 of nano-Fe/Ca/CaO and 20 mM H₂O₂ doses, achieved enhancement removal of color, COD, and TSS, up to 95%, 96%, and 66%, respectively, without initial pH control. After this treatment, the color, COD, TSS, and heavy metals were significantly decreased, fitting the Korean discharge regulation limit. A hybrid coupled zero valent iron (ZVI)/H₂O₂ oxidation process with novel nanosized metallic calcium/iron dispersed reagent proved to be a suitable treatment for dealing with leachate samples.

Implications: Conventional treatments (biological or physicochemical) are not sufficient anymore to reach the level of purification needed to fully reduce the negative impact of landfill leachates on the environment. This implies that new treatment alternatives species must be proposed. A coupled zero valent iron (ZVI)/H₂O₂ oxidation process proved to be a suitable treatment for dealing with leachate samples. Coagulation with nFe/Ca/CaO allows 91–99% of heavy metals removal. The coupled coagulation–oxidation process by nFe/Ca/CaO reveals excellent ability to treat leachate. After coupled treatment the color, COD, and TSS were also much lower than the discharge regulation limit.     

Electrochemical oxidation of bisphenol A. Application to the removal of bisphenol A using a carbon fiber electrode

Leachate samples with a high strength of ammonium-nitrogen (NH4+-N) were collected from a local landfill site in Hong Kong. Two experiments were carried out to study (1) the inhibition of microbial activity of activated sludge by NH4+-N and (2) the chemical precipitation of NH4+-N from leachate as a preliminary treatment prior to the activated sludge process. The experimental results demonstrated that the efficiency of COD removal decreased from 97.7% to 78.1%, and the dehydrogenase activity of activated sludge decreased from 9.29 to 4.93 microg TF/mg MLSS, respectively, when the NH4+-N concentration increased from 53 to 800 mg/l. The experiment also demonstrated that the NH4+-N in the leachate can be quickly precipitated as MgNH4PO4 x 6H2O after addition of MgCl2 x 6H2O + Na2HPO4 x 12H2O. The NH4+-N concentration was reduced from 5618 to 112 mg/l within 15 min when a molar ratio of Mg2+:NH+:PO4(3-) = 1:1:1 was used. The optimum pH to reach the minimum solubility of MgNH4PO4 x 6H2O was found to be in the range of 8.5-9.0. Attention should be given to the high salinity formed in the treated leachate by using MgCl2 x 6H2O + Na2HPO4 x 12H2O, which may affect microbial activity in the following biological treatment processes. Using two other combinations of chemicals [MgO + 85%H3PO4 and Ca(H2PO4)2 x H2O + MgSO4 x 7H2O] could minimise salinity generation after precipitation, while they were less efficient for NH4+-N removal.     

Ti（Ⅳ）催化臭氧／过氧化氢预处理酸性难降解废水

在Ti（Ⅳ）和过氧化氢存在条件下，考察了臭氧化酸性苯乙酮溶液、硝基苯溶液和垃圾渗滤液（浙江衢州某垃圾填埋场）的预处理效能。结果表明，在pH2．86条件下，单独臭氧化处理对苯乙酮、硝基苯和垃圾渗滤液的COD去除率分别为10．1％、44％和28．6％。BOD，／COD值分别从原来的0．039、0．060和0．085提高到了0．130、0．158和0．174，仍属生化难降解废水。当体系加入Ti（Ⅳ）后，臭氧化苯乙酮和硝基苯的COD去除率分别达到了75．5％和65％，BOD；／COD则提高到了0．679和0．314，可生化性提升明显。对于垃圾渗滤液，只有当体系加入Ti（Ⅳ）和H22后，臭氧化COD的去除率达到66．6％，BOD、／COD提高至0．425。上述结果对酸性难降解废水的处理实际意义非常突出。     

垃圾渗滤液生化出水的脱色研究

分别采用脉冲电解法、混凝沉淀法、芬顿氧化法、高铁酸钾氧化法对垃圾渗滤液生化出水进行处理，考察了处理效果。结果表明：铁电极电解法和芬顿试剂氧化法均能脱除垃圾渗滤液的色度，去除有机物质。铁电极电解对色度的去除率可达98．4％，COD去除率可达84．4％；芬顿试剂氧化对色度的去除率可达99％，COD去除率可达85．8％。两种方法均能使出水达到排放标准。同时比较了各种处理方法的运行成本，在达到同样出水标准的前提下，铁电极电解运行成本远低于芬顿试剂氧化，为3．67元／t水，而芬顿试剂药剂成本为8．67元／t水。     

回灌型准好氧填埋场脱氮特性及加速稳定化研究

采用2个模拟填埋生物反应器,1号柱渗滤液简单回灌,2号柱为渗滤液回灌准好氧联合运行方式,研究了渗滤液回灌准好氧生物反应器填埋场的脱氮特性及加速垃圾稳定化特性.研究结果表明:渗滤液回灌准好氧填埋场具有很强的脱氮能力,2号柱由厌氧运行方式改为准好氧条件下,渗滤液中的氨氮和凯式氮浓度分别由最大值的3 198 mg/L和3 345 mg/L降低到第160 d的73 mg/L和81 mg/L,去除率分别为97.7%和97.6%,pH快速升高到8.0左右,COD浓度快速降低.渗滤液中溶解性有机物(DOM)分级结果表明,2号柱HA和FA含量的增加明显快于1号柱.2号柱DOM的三维荧光光谱特性发生了较大变化,荧光基团从60 d结构简单的类蛋白物质转变为95 d结构复杂的类胡敏酸和富里酸物质,而l号柱渗滤液DOM荧光基团一直是结构简单的类蛋白物质.结果表明回灌准好氧生物反应器填埋场的稳定化速度远快于简单回灌的生物反应器填埋场.     

磷酸铵镁沉淀法预处理垃圾渗滤液

探讨了用磷酸铵镁沉淀法预处理垃圾渗滤液时,沉淀剂种类、pH值、物质摩尔配比和反应时间等因素对氨氮去除效果的影响。得出了处理氨氮浓度为2 677.34 mg/L的垃圾渗滤液时,在兼顾所用镁盐量尽量低和处理出水氨氮或磷酸盐的残留量都比较低的较佳实验条件为:沉淀剂种类为:MgSO4.7H2O和Na2HPO4.12H2O,反应时间为20 min,pH=9.5,n(Mg)∶n(P)∶n(N)=1.3∶1.15∶1.0。在较佳实验条件下,垃圾渗滤液的NH3-N去除率为97.05%,处理出水PO34--P含量为8.35 mg/L,NH3-N含量为75.86 mg/L。对所得沉淀物进行了成分分析和X-衍射光谱、扫描电镜表征,表明大部分沉淀物为磷酸铵镁物质。     

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.     

支撑气膜法脱除／回收垃圾渗滤液中氨氮

利用由微孔疏水性聚丙烯中空纤维制成的工业级膜组件对垃圾渗滤液中氨氮进行支撑气膜法脱除研究，考察了泡沫分离．石灰絮凝等预处理技术对垃圾渗滤液表面张力及COD值的处理效果，在此基础上研究了物料因素和操作因素对膜传质性能的影响，并对该工艺的长期操作稳定性进行了研究。实验结果表明该预处理技术不仅可显著提高垃圾渗滤液的表面张力，还可大大降低其色度和COD值。当进料流量为100L／h、进料氨氮浓度为1000～3000mg／L、硫酸吸收液流量为200L／h、硫酸浓度为6％～10％、温度为20～30℃时，支撑气膜过程（两级膜组件串联）可有效脱除垃圾渗滤液中99％以上的氨氮，同时得到含10％～15％硫酸铵的水溶液作为副产品。工业级支撑气膜组件在连续运行的2个月内保持了良好的传质稳定性。     

EGSB反应器处理城市生活垃圾沥滤液

采用膨胀颗粒污泥床(EGSB)反应器对城市生活垃圾焚烧厂产生的垃圾沥滤液进行处理。实验结果表明:中温条件下,当COD浓度为55 000 mg/L左右,有机容积负荷(OLR)为22.8 kg COD/(m3.d)时,EGSB对垃圾沥滤液具有较好的的处理效果,COD去除率可达94.2%。当进水COD为72 000 mg/L左右时,为保证反应器的稳定运行,OLR应降低至18.2 kg COD/(m3.d),此时COD去除率可以达到88%左右,出水COD平均为9 103 mg/L。垃圾沥滤液和EGSB处理出水均以小分子量有机物为主,其中<4 kDa的有机物分别占76.5%和74.4%。EGSB对整个分子量区间的溶解性有机物都有较好的处理效果,其中对大分子有机物的处理效率相对更高。     

Iron-loaded mangosteen as a heterogeneous Fenton catalyst for the treatment of landfill leachate

Iron-loaded mangosteen shell powder (Fe-MSP) was found as an effective heterogeneous Fenton catalyst for the treatment of stabilized landfill leachate. Sonolytically produced catalyst has higher efficiency than other catalysts. At the optimal conditions (pH 3, catalyst concentration of 1,750 mg/L and hydrogen peroxide concentration of 0.26 M), 81 % of the chemical oxygen demand (COD) was removed effectively from the landfill leachate. But, the efficiency of Fe-MSP was reduced in the first recycling due to the poisoning of active sites. A metal leaching study indicated that the degradation of the pollutant is mainly due to solid Fe ions present in Fe-MSP rather than the leached ferrous and ferric ions. Hydroxyl radical production in the system was confirmed by the Fenton oxidation of benzoic acid. Compared to the homogeneous Fenton process, the heterogeneous Fenton process using Fe-MSP had higher COD removal efficiency, indicating the practical applicability of the prepared catalyst.     

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。     

组合工艺去除垃圾渗滤液中的DBP和DEHP

探讨了采用实验室规模的生物处理组合工艺(上流式厌氧污泥床+曝气生物滤池+缺氧反应器+膜生物反应器,UASB+BAF+ANO+MBR)处理垃圾渗滤液过程中,邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DE-HP)两种内分泌干扰物在各工艺段的去除效率和机理。测定结果表明,对于DBP和DEHP浓度分别为164.4μg/L和215.0μg/L的原水,总出水浓度分别降至11.8μg/L和10.4μg/L,去除率分别达到92.9%和95.2%,处理效果良好。其中DBP在处理工艺中逐级降解,主要是微生物的降解作用。MBR是DEHP的主要去除工艺段,去除比例达到56.6%,膜截留效果明显。采用生物处理组合工艺可实现对垃圾渗滤液中DBP和DEHP的同时高效去除。     

太阳光Fenton法处理垃圾渗滤液中有机污染物

研究利用太阳光Fenton法处理垃圾渗滤液。根据太阳光辐射强度随时间的变化规律，选择重庆7、8月份的晴天，在中午12：00到下午14：00时进行试验，研究太阳光辐射时间、pH值、Fenton试剂用量对垃圾渗滤液COD去除率的影响。研究结果表明：太阳光Fenton法对垃圾渗滤液的COD有较好的去除效果，COD去除率达86.2%。太阳光Fenton法处理垃圾渗滤液的优化条件是：日光辐射时间为120 min，pH值为2.5，Fe²⁺浓度为5 mmol/L，H₂O₂浓度为570 mmol/L。同时，论文还对太阳光Fenton法处理垃圾渗滤液的动力学进行分析。研究结果显示：太阳光Fenton法处理垃圾渗滤液，其表观动力学方程为-dC/dt=2.6×10^-8×P^1.92×F^1.79×E^1.67。     

光电芬顿氧化法深度处理垃圾渗滤液研究

采用光电芬顿氧化法对北京市某垃圾填埋场已经生化处理后的垃圾渗滤液进行深度处理，分别考察了电流强度和铁的不同价态等因素对渗滤液总有机碳（TOC）、化学需氧量（COD）以及色度去除效果的影响，并对阳极氧化、电芬顿和光电芬顿不同反应过程进行了对比。通过分析渗滤液UV-Vis光谱(200～500 nm)变化和渗滤液中有机污染物的分子量变化，发现光电芬顿反应可以明显改善渗滤液生化性。深入研究了反应过程中铁价态的变化规律。试验结果发现，以高比表面积的活性炭纤维(ACF)为阴极的光电芬顿反应可以有效降解垃圾渗滤液，在pH为3，Fe²⁺ 浓度为1 mmol/L，电流为0.5 A，O₂通入量为250 mL/min条件下降解360 min，垃圾渗滤液TOC和COD去除率分别达到78.9%和62.8%，色度完全去除。     

A novel design for anaerobic chemical oxygen demand and nitrogen removal from leachate in a semiaerobic landfill

The removal capacity of carbon and nitrogen from an artificial leachate was evaluated by using laboratory-scale columns, and a design was proposed to remove nitrogen more efficiently from a semiaerobic landfill. Five columns (i.e., two artificial municipal waste columns under anaerobic and semiaerobic conditions, an artificial construction waste column under semiaerobic conditions, and two crushed stone columns under anaerobic and semiaerobic conditions) were used. The influent load rates of organics [g chemical oxygen demand (COD)/m3 x day], NH4+, NO3- and aeration conditions for the columns were varied, and the removal capacities of the columns for COD, NH4+-N, and NO3--N were measured. Among the packed column materials, crushed stone was shown to be most effective in removing COD, NH4+ N, and NO3--N from artificial leachate. Average removal rates of crushed column under the semiaerobic condition (column D) for COD and NH4+-N were estimated at about 150 g COD/m3 x day and 20 g COD/m3 x day, while those of crushed column under anaerobic condition (column E) for COD and NO3--N at about 400 and 150 g COD/m3 x day, respectively. It also was found that denitrification and nitrification reactions in column D occurred at the same time, and the ratio of denitrification to nitrification was estimated to be about 80%. Therefore, an anaerobic structure, which could be attached to the bottom of a main pipe in a semiaerobic landfill, is suggested to remove nitrogen and organic substances more effectively.     

The biological treatment of landfill leachate using a simultaneous aerobic and anaerobic (SAA) bio-reactor system

A set of simultaneous aerobic and anaerobic (SAA) bio-reactor system was used for the removal of organic pollutants and ammonia in the landfill leachate generated from Datian Shan Landfill in Guangzhou, China. The influent concentrations of COD and NH(4)(+)-N were 1000-3300 and 80-230 mg L(-1), respectively. The average effluent concentrations of COD and NH(4)(+)-N were 131 and 7 mg L(-1), respectively. The concentrations of COD and NH(4)(+)-N had reached the Chinese second grade effluent standard (COD<300 mg L(-1), NH(4)(+)-N<25 mg L(-1)) for this kind of wastewater. Gas chromatogram-mass spectrum (GC/MS) analysis was used to measure the organic pollutants in the landfill leachate. About 87 organics were detected in this landfill leachate, and 16 of them belong to the list of environmental priority pollutants established by the US Environmental Protection Agency. About 31 of the 87 organic pollutants were completely removed by the SAA bio-reactor, the concentrations of further 14 organic pollutants were reduced by more than 80%, and the removal efficiencies of the other 25 organic pollutants were over 50%.     

准好氧矿化垃圾反应床＋超声／芬顿联用技术处理垃圾渗滤液

针对垃圾渗滤液污染物浓度高、可生化性差等特点，采用准好氧矿化垃圾反应床＋超声／芬顿联用技术对垃圾渗滤液进行预处理。准好氧矿化垃圾床处理后渗滤液中COD、氨氮、总磷、色度的去除率分别为80％、85％、92％和85％。通过单因素实验和正交实验，确定了超声／Fenton法最佳工艺条件。经该组合工艺后，渗滤液中COD、氨氮、总磷和色度的最高去除率分别可达96％、86％、94％和95％，且出水无臭，颜色为淡黄色，BOD5／COD从0．16增至0．35左右，可生化性基本满足后续生物处理需要，且COD、总磷这2个指标达到《生活垃圾填埋场污染控制标准》（GB16889—2008）规定的排放标准。