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.     

矿化污泥生物反应器处理生活垃圾填埋场老龄渗滤液

经长时间稳定化形成的矿化污泥中,含有种类丰富和数量繁多的降解性微生物,具有处理渗滤液的潜力。建立3个矿化污泥生物反应器,即C1(粉煤灰0%),C2(粉煤灰9.1%),C3(粉煤灰16.7%),以处理垃圾填埋场老龄渗滤液。在单级矿化污泥反应器中,当进水COD和NH3-N分别约为1350和900 mg/L时,水力负荷为17.7～70.8 L/(m3.d),COD去除率可超过65%,氨氮的去除率可超过94%。粉煤灰的加入一定程度上降低了COD去除率,但有助于氨氮的去除。在二级矿化污泥生物反应器中(即C3～C1串联),水力负荷为35.4 L/(m3.d)的工况下,当COD、TOC、IC和NH3-N分别为1 500～2 500,500～900,1 200～1 600和1 200～1 450 mg/L时,出水可达到COD<300 mg/L,TOC<180 mg/L,IC<100 mg/L,NH3-N<5 mg/L。但是,矿化污泥生物反应器对渗滤液总氮的去除率较低,仅为20%左右。     

超声波-膜生物法联合处理垃圾焚烧厂渗滤液

采用超声波-膜生物法(MBR)联合处理垃圾渗滤液,探讨了超声波辐射时间和MBR的水力负荷对COD、NH3-N和TP去除的影响。结果表明,(1)超声波单独处理时,超声波辐射时间在30～90 s时,COD、NH3-N最大增加率分别34.31%、3.36%,而对TP的去除没有影响;(2)超声波-膜生物(MBR)联合处理时,超声波辐射时间为300 s,MBR的水力负荷为6.4 L/(m2.d)时,COD、NH3-N和TP的最佳去除率分别为92.20%、80.10%和91.12%;MBR的水力负荷为12.8 L/(m2.d),超声波辐射时间在5～20 min时,COD、NH3-N的最佳去除率分别为92.34%、79.93%,TP的浓度低于0.2 mg/L;MBR反应时间为7 h,超声波辐射时间为5～20 min,与未进行超声波辐射处理(超声波辐射时间为0 min)相比,COD、NH3-N的去除率增加了11.37%、15.26%;超声波预处理有助于提高后续MBR对COD、NH3-N的去除作用。     

微波诱导AC/Cu、AC/Fe催化非均相Fenton 反应催化降解垃圾渗滤液

采用活性炭载体负载Cu、Fe为催化剂,在微波诱导作用下,对垃圾渗滤液污染物进行降解。实验结果表明,活性炭负载金属前经适当浓度硝酸浸泡处理后,催化剂对COD去除率提高可超过15%,过高硝酸盐浓度对COD去除有不利影响;催化剂对COD去除率随Cu、Fe金属负载量增加呈先增加后降低的趋势,催化剂对Cu、Fe的最佳负载量分别为质量百分比2.11%和1.12%。对于AC-Cu体系,在初始pH=3,H2O2投加量为4.98×103mg/L,催化剂用量为5.0×103mg/L,420 W功率下微波辐射10 min时,垃圾渗滤液COD去除率可达到84.13%;对于AC-Fe体系,当H2O2投加量为0.33×103mg/L,催化剂AC-Fe用量为2.0×104mg/L,420 W功率下微波作用10 min时,垃圾渗滤液COD去除率为60.16%。分析2种催化剂对COD去除差异的原因,可能是催化剂AC-Cu表面单分子分布的阈值比AC-Fe高。降解液的pH值对AC-Cu体系、AC-Fe体系COD去除影响存在拐点,最高COD去除率点对应的降解液pH值为3。微波辐射功率较低时,体系COD去除率随辐射功率增加而增加;辐射功率较高时,高温下垃圾渗滤液中有机硫化物分解成小分子硫化物,对催化剂活性存在一定抑制作用。     

A Novel Design for Anaerobic Chemical Oxygen Demand and Nitrogen Removal from Leachate in a Semiaerobic Landfill

Abstract

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 ·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·day and 20 g COD/m³ ·day, while those of crushed column under anaerobic condition (column E) for COD and NO₃ ^?-N at about 400 and 150 g COD/m³ ·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.     

Fenton氧化降解垃圾渗滤液中COD的动力学研究

对絮凝预处理后的垃圾渗滤液进行Fenton氧化处理。通过微分法对Fenton氧化的反应级数进行求解,确定其反应级数为2,并初步建立了Fenton氧化的动力学模型,即1/c=1/c0+kt,由此建立起来的降解的动力学模型与实验数据相吻合;在4个实验基准条件下———初始COD浓度为960 mg/L、pH值4、H2O2投加量0.4 mol/L、nH2O2/nFe2+3∶1,探讨了其中某一变量对反应速率的影响。实验水样为絮凝反应出水,进水COD浓度为912～960 mg/L,出水COD浓度为80～112 mg/L,COD去除率在87%～92%之间,表明Fenton试剂能够有效地处理垃圾渗滤液。     

垃圾渗滤液处理工艺运行参数优化与技术比较

垃圾渗滤液是公认的一种成分复杂且难以处理的高浓度有机废水,笔者在北京市海淀区六里屯垃圾填埋场通过2007—2010年垃圾渗滤液处理的工程实践,以COD和氨氮的去除率为指标,研究了不同的垃圾渗滤液处理工艺组合,以及不同运行参数条件下对垃圾渗滤液的处理效果。结果表明,在中温UASB和A/O的平均水力停留时间(HRT)缩短1/3的情况下,通过改进A/O段曝气方式,优化系统的pH、DO等运行参数,用MBR替代絮凝工艺,使整个组合工艺对COD的年平均去除率达到了94.3%,氨氮的去除率维持在99.5%以上,出水氨氮稳定在10 mg/L以内,而改造前的COD与氨氮的年平均去除率仅为82.2%与55.3%。与改造前的UASB+A/O+絮凝工艺组合相比,改造后的UASB+A/O+MBR工艺组合具有更高的污染物去除能力、更好的抗缓冲性和稳定性。     

Nitrogen removal via the nitrite pathway during wastewater co-treatment with ammonia-rich landfill leachates in a sequencing batch reactor

The biological treatment of ammonia-rich landfill leachates due to an inadequate C to N ratio requires expensive supplementation of carbon from an external carbon source. In an effort to reduce treatment costs, the objective of the study was to determine the feasibility of nitrogen removal via the nitrite pathway during landfill leachate co-treatment with municipal wastewater. Initially, the laboratory-scale sequencing batch reactor (SBR) was inoculated with nitrifying activated sludge and fed only raw municipal wastewater (RWW) during a start-up period of 9 weeks. Then, in the co-treatment period, consisting of the next 17 weeks, the system was fed a mixture of RWW and an increasing quantity of landfill leachates (from 1 to 10 % by volume). The results indicate that landfill leachate addition of up to 10 % (by volume) influenced the effluent quality, except for BOD₅. During the experiment, a positive correlation (r ²?=?0.908) between ammonia load in the influent and nitrite in the effluent was observed, suggesting that the second step of nitrification was partially inhibited. The partial nitrification (PN) was also confirmed by fluorescence in situ hybridisation (FISH) analysis of nitrifying bacteria. Nitrogen removal via the nitrite pathway was observed when the oxygen concentration ranged from 0.5 to 1.5 mg O₂/dm³ and free ammonia (FA) ranged from 2.01 to 35.86 mg N-NH₃/dm³ in the aerobic phase. Increasing ammonia load in wastewater influent was also correlated with an increasing amount of total nitrogen (TN) in the effluent, which suggested insufficient amounts of assimilable organic carbon to complete denitrification. Because nitrogen removal via the nitrite pathway is beneficial for carbon-limited and highly ammonia-loaded mixtures, obtaining PN can lead to a reduction in the external carbon source needed to support denitrification.     

污泥活性炭强化SBR法处理垃圾渗滤液的实验研究

为了进一步处理垃圾渗滤液,试验采用污泥活性炭强化序批式间歇反应器（SBR）法进行处理,通过对比普通SBR法试验,得出投加污泥活性炭强化SBR法处理垃圾渗滤液的效果要远远高于普通SBR法。当污泥活性炭的投加量为1.2 g/L,容积负荷为0.5～1.5 kg BOD₅/(m³·d)时,进水1 h,曝气10 h,沉淀1.5 h,闲置1.5 h,处理效果最好,COD的去除率达到了85%,NH³-N的去除率达到了90%。     

Treatment and detoxification of a sanitary landfill leachate

The leachate from an old sanitary landfill (Gramacho Metropolitan Landfill, Rio de Janeiro) was characterized and submitted to coagulation and flocculation treatment followed by ozonation and ammonia stripping. The performance of the treatment was assessed by monitoring the removal of organic matter (COD and TOC), ammonium nitrogen and metals. Detoxification was assessed by determining acute toxicity, using the following organisms: Vibrio fisheri, Daphnia similis, Artemia salina and Brachydanio rerio. Membrane fractionation was employed to infer the range of molecular masses of the pollutants found in the effluent, as well as the toxicity associated to these fractions. Of the techniques under investigation, coagulation and flocculation followed by ammonia stripping were the most effective for toxicity and ammonium nitrogen removal. Membrane fractionation was effective for COD removal; however, acute toxicity was almost the same in all the fractionated samples. Ozonation was moderately effective for COD removal, but significant toxicity removal was only attained when high ozone doses were used.     

某生活垃圾卫生填埋场渗滤液的梯度分离与表征

目前,渗滤液中污染物的粒度分布及其在渗滤液污染控制中的作用日益受到关注。通过系列微滤膜(1.2μm及0.45μm)对某生活垃圾卫生填埋场渗滤液各处理单元的渗滤液进行梯度分离,发现悬浮物对COD、浊度的影响较大;COD主要在胶体态和可溶解态间分配,不同渗滤液中的分配情况不同;磷主要与胶体、悬浮物以各种形式结合而存在;细胶粒和溶解态等小分子对TN的贡献大;不同粒度物质对pH的影响不明显;总残渣在可溶态组分中所占比例较大。膜微滤处理渗滤液可以有效的去除一部分物质,使COD、TP、TN、浊度、电导率都有不同程度的降低,pH逐渐升高,但对总N、残渣的去除效果不好。     

聚合氯化铝与粉末活性炭联合强化混凝处理垃圾渗滤液

研究了联合粉末活性炭与聚合氯化铝(PAC)强化混凝对垃圾渗滤液原水的处理效果。结果表明,在原水COD为4 100 mg/L、浊度为147 NTU、UV254为20的条件下,粉末活性炭的加入可以有效增加垃圾渗滤液中有机物的去除率,PAC投加量为0.6 g/L时,投加0.6 g/L粉末活性炭,COD的去除率由21.6%提高到29.1%,UV254去除率由29.8%提高到39.9%,剩余浊度由138 NTU降到133 NTU。该强化混凝过程使原水中溶解性小分子有机物的去除率提高显著,PAC投加量为0.6 g/L时,投加0.6 g/L粉末活性炭,在分子量小于1 kDa的范围内,UV254去除率由2.9%上升为10%。     

UASB处理硫酸盐有机废水的启动

为了考察上流式厌氧污泥床反应器(UASB)处理含硫酸盐有机废水的特性,采用有效容积为10 L的UASB,研究了启动运行过程中COD和SO2-4降解情况、出水VFA和pH值、产气量及颗粒污泥比产甲烷活性(SMA)变化状况。结果表明,接种厌氧颗粒污泥,保持进水COD为1 500 mg/L,SO2-4浓度为100 mg/L,将HRT由24 h缩短至12 h以提高负荷,经历55 d成功启动了UASB反应器;当HRT为12 h,进水COD和SO2-4负荷为3.0 kg/(m3·d)和0.20 kg/(m3·d),COD和SO2-4的去除率分别达到80%和89%,出水VFA为3 mmol/L,产气量达9.5 L/d,颗粒污泥的SMA为86.4 mL/(g VSS·d)。     

混凝+芬顿法对中晚期垃圾渗滤液色度去除

垃圾渗滤液经一般生化处理后色度很大。对混凝和芬顿法结合深度处理垃圾渗滤液对色度去除进行了研究。混凝段通过中心复合设计(简称CCD)和响应面方法(简称RSM)分析了混凝的色度去除率的响应特征,建立了实际因素的最终方程模型:Y(色度去除率,%)=-553.40+73.74A+229.06B+0.38AB-34.16A2-22.67B2,(Y、A、B分别代表色度去除率、投加量和pH)并对絮凝条件进行优化,得到混凝反应的最佳优化条件:投加量1.11 g/L,pH 5.06,及在此条件下的去除率67.2%。在芬顿段,将芬顿反应对水中亲水性有机物相对含量(UV254)与对色度的去除特征相结合进行了研究,证明色度的去除跟该类有机物的去除有关,色度去除率最优值条件选择为H2O2/COD=1.0,Fe2+/H2O2=0.35∶1,而初始pH=2.5时对色度的去除达到99%以上。整个工艺出水可达到达标排放标(GB16889-2008)。     

混凝与Fenton联用处理垃圾渗滤液的效能及成本

为对混凝/Fenton工艺与Fenton/混凝工艺处理垃圾渗滤液的效果和成本进行比较,分别对年轻渗滤液和老龄渗滤液原液按照混凝/Fenton工艺与Fenton/混凝工艺2种技术路线进行处理。实验结果表明,Fenton试剂对年轻垃圾渗滤液和老龄垃圾渗滤液COD去除率最高的反应条件为pH=3.5、H2O2和Fe2+的摩尔比为6、H2O2和渗滤液原液的COD质量比为3、反应时间4 h;在PAC与渗滤液原液的COD质量比为0.6时,PAC混凝对渗滤液原液的COD去除率最高。在对渗滤液COD去除率最高的Fenton反应和PAC混凝反应条件下,混凝/Fenton工艺对年轻渗滤液和老龄渗滤液的COD去除率分别为90.56%和86.56%;Fenton/混凝工艺对年轻渗滤液和老龄渗滤液的COD去除率分别为89.99%和85.99%,2种技术路线对渗滤液COD的去除率相差不大,但先PAC混凝后Fenton氧化工艺比先Fenton后混凝工艺每t节省62.6元,是更优化的渗滤液处理工艺。     

城市垃圾焚烧渗沥液中Ca2+对厌氧EGSB处理效果的影响简

研究了城市生活垃圾焚烧厂渗沥液中Ca²⁺对厌氧颗粒污泥膨胀床反应器（EGSB）处理效果的影响,并采用静态实验方法考察了Ca²⁺对厌氧颗粒污泥产甲烷活性的影响。实验结果表明,进水COD为17 000 mg/L的条件下,当Ca²⁺浓度低于6 000 mg/L时,EGSB对COD去除率达93%以上;当Ca²⁺浓度高于6 000 mg/L时,COD去除率随运行时间明显下降,并在污泥中形成大量沉淀。静态实验结果表明,废水中低浓度Ca²⁺促进了厌氧颗粒污泥的产甲烷活性,但高浓度Ca²⁺明显抑制了其产甲烷活性,这是导致高Ca²⁺浓度条件下EGSB对COD去除率降低的主要原因。研究表明,颗粒污泥产甲烷活性恢复程度随Ca²⁺浓度增加而减弱。     

利用水泥处理垃圾渗滤液生物处理出水的研究

利用水泥的表面吸附和水化反应性质处理垃圾渗滤液生物处理出水可以取得很好的效果,COD的去除率可达69.5%.处理效果与水灰比、反应时间密切相关,低水灰比和较长反应时间对COD的去除更为有利.对处理前后水样的COD和TOC分析表明,水泥对非TOC贡献的COD有很强的去除效果.     

垃圾渗滤液生物处理出水的深度处理组合工艺

采用"混凝-电解氧化-完全混合式活性污泥法(CSTR)"组合工艺深度处理垃圾渗滤液生物处理出水。探索了工艺的组合及各种工艺操作条件对垃圾渗滤液深度处理效果的影响,并对其影响机理进行了初步探讨。结果表明,以PAC为混凝剂时,在pH和药剂(有效成分)投加量分别为6.0和600 mg/L条件下,渗滤液COD去除率达到50%,有效降低了难溶惰性COD含量,缩短了后续电化学处置时间。混凝工艺后,采用电化学工艺处理,在最优工艺条件下:pH为6.0、电流I为1.2 A(电流密度为18.18 mA/cm2)、Cl-投加量为1 000 mg/L、极板距离为2 cm,电解30 min渗滤液COD去除率达到36%,同时,难降解有毒物含量明显降低,渗滤液可生化性TbOD/COD由10%提升至最大值64%。最后采用CSTR处理渗滤液电解出水,系统出水COD、氨氮和色度分别为100~150 mg/L、7~13 mg/L和25倍,为反渗透(RO)工序提供了良好的水质条件。     

UASB启动及不同HRT对老龄垃圾渗滤液处理效果的影响

在UASB反应器中接种好氧污泥培养厌氧颗粒污泥进行启动,研究不同HRT对老龄(13年)垃圾渗滤液对处理效果的影响情况。通过保持进水COD浓度不变、逐步缩短HRT从而提高容积负荷到40 g COD/(L.d)的方法,可以培育出直径为1～3 mm颗粒污泥,最终产气量稳定在100 L/d,甲烷含量在60%～70%之间,COD去除率保持在90%左右,污泥层最底部MLSS为81 g/L。逐步提高HRT依次为6、12、24、48和72 h考察其对处理效果的影响,当HRT为24 h时处理效果最好,COD去除率最高达到35%左右。     

生化-调碱后垃圾渗滤液的Fenton深度处理效果

针对上海老港垃圾填埋场经过厌氧-曝气塘处理后的渗滤液难进一步处理的问题,对其采用厌氧滤池-好氧接触法、氧化钙2种方式预处理,在此预处理基础上,考察了Fenton法深度处理的效果,探讨了H2O2/Fe2+投加比、初始pH、H2O2投加量、反应时间和Fenton试剂投加方式对渗滤液COD去除效果的影响。研究发现:经过生物预处理后,渗滤液的COD和TP分别降低了24%和25%;氧化钙调碱可以进一步使COD和TP去除率分别达到42%和96%;后续Fenton深度氧化的最佳条件为:初始pH为2,H2O2投加量为2.4 g/L,H2O2/Fe2+摩尔比为5∶1,Fenton试剂一次投加,反应时间为2 h。在此条件下,渗滤液的COD从1 340 mg/L降到198 mg/L,总COD去除率达到85%。