Hybrid process for heavy metal removal from wastewater sludge.

Bioleaching processes have been demonstrated to be effective technologies in removing heavy metals from wastewater sludge, but long hydraulic retention times are typically required to operate these bioprocesses. A hybrid process (coupling biological and chemical processes) has been explored in laboratory pilot-scale experiments for heavy metals (cadmium [Cd], copper [Cu], chromium [Cr], and zinc [Zn]) removal from three types of sludge (primary sludge, secondary activated sludge, and a mixture of primary and secondary sludge). The hybrid process consisted of producing a concentrate ferric ion solution followed by chemical treatment of sludges. Ferric iron solution was produced biologically via oxidation of ferrous iron by A. ferrooxidans in a continuous-flow stirred tank (5.2 L) reactor (CSTR). Wastewater sludge filtrate (WSF) containing nutrients (phosphorus and nitrogen) has been used as culture media to support the growth and activity of indigenous iron-oxidizing bacteria. Results showed that total organic carbon (TOC) concentrations of the culture media in excess of 235 mg/L were found to be inhibitory to bacterial growth. The oxidation rate increased as ferrous iron concentrations ranged from 10 to 40 g Fe2+/L. The percentage of ferrous iron (Fe2+) oxidized to ferric iron (Fe3+) increased as the hydraulic retention time (HRT) increased from 12 to 48 h. Successful and complete Fe2+ oxidation was recorded at a HRT of 48 h using 10 g Fe2+/L. Subsequently, ferric ion solution produced by A. ferrooxidans in sludge filtrate was used to solubilize heavy metals contained in wastewater sludge. The best solubilization was obtained with a mixture of primary and secondary sludge, demonstrating a removal efficiency of 63, 71, 49, and 80% for Cd, Cu, Cr, and Zn, respectively.     

Major factors influencing bacterial leaching of heavy metals (Cu and Zn) from anaerobic sludge

Anaerobically digested sewage sludges were treated for heavy metal removal through a biological solubilization process called bacterial leaching (bioleaching). The solubilization of copper and zinc from these sludges is described in this study: using continuously stirred tank reactors with and without sludge recycling at different mean hydraulic residence times (1, 2, 3 and 4 days). Significant linear equations were established for the solubilization of zinc and copper according to relevant parameters: oxygen reduction potential (ORP), pH and residence time (t). Zinc solubilization was related to the residence time with a r2 (explained variance) of 0.82. Considering only t=2 and 3 days explained variance of 0.31 and 0.24 were found between zinc solubilization as a function of ORP and pH indicating a minor importance of those two factors for this metal in the range of pH and ORP experimented. Cu solubilization was weakly correlated to mean hydraulic residence time (r2=0.48), while it was highly correlated to ORP (r2=0.80) and pH (r2=0.62) considering only t of 2 and 3 days in the case of pH and ORP. The ORP dependence of Cu solubilization has been clearly demonstrated in this study. In addition to this, the importance of the substrate concentration for Cu solubilization has been confirmed. The hypothesis of a biological solubilization of Cu by the indirect mechanism has been supported. The results permit, under optimum conditions, the drawing of linear equations which will allow prediction of metal solubilization efficiencies from the parameters pH (Cu), ORP (Cu) and residence time (Cu and Zn), during the treatment. The linear regressions will be a useful tool for routine operation of the process.     

连续流反应器中培养好氧颗粒污泥的运行效能研究

在连续流完全混合反应器(CSTR)中,采用不同进水方式,以乙酸钠作为碳源配制的人工配水作为原水,对好氧颗粒污泥的运行效能进行了试验研究。研究表明,采用不同进水方式运行的2个反应器在颗粒污泥出现后,运行效能差别不大;好氧颗粒污泥反应器运行高效稳定,在水力停留时间为1.5h、COD容积负荷为1.0kg/(m3·d)的条件下,对COD、TP、NH4+-N和TN的去除率分别为90%、85%、95%和60%,并具有明显的脱氮除磷效果;反应器中存在同步硝化反硝化现象。     

某城市污水处理厂废水化学除磷沉淀特性及影响因素

通过对西安市某污水处理厂进水、厌氧池上清液、二沉池出水、污泥浓缩水、污泥脱水进行FeCI3·6H2O、PAC除磷实验,并以FeCI3·6H2O为沉淀剂对厌氧池上清液从pH、Fe/P摩尔比、腐殖酸、挥发性脂肪酸(VFA)等因素进行批次实验分析磷去除状况.实验显示,三氯化铁、PAC对进水除磷效果不佳,厌氧池上清液用FeCI3·6H2O为沉淀剂时磷去除率较低,二沉池出水、污泥浓缩水以及污泥脱水用FeCI3·6H2O、PAC时其正磷去除率均可达到80%左右.通过对比不同pH值、Fe/P摩尔比、腐殖酸和VFA浓度对厌氧池上清液除磷效果的影响,结果表明,在pH=4~5,Fe/P=1.3时磷的去除效果达到78%以上,腐殖酸浓度对磷去除率影响不大,VFA在低于10 mg/L和高于60 mg/L时对磷去除率影响较大.     

铬污染土壤的还原稳定化修复

以湖南某工业场地的铬污染土壤为修复对象,投加不同比例的FeSO4·7H2O、FeSO4·7H2O和Ca（OH）2混合物及NaHSO3,通过测定土壤及浸出液中六价铬、总铬以及铬的形态,比较3种稳定剂对该污染土壤的还原稳定化作用。结果表明,FeSO4·7H2O和NaHSO3对铬污染土壤的还原稳定效果都较好,可以有效还原土壤中六价铬并能降低土壤中总铬的浸出浓度。当FeSO4·7H2O投加量为2%时,土壤六价铬和总铬浸出浓度降幅分别达到99.0%和57.5%;当NaHSO3投加量为0.8%时,六价铬和总铬浸出浓度降幅分别达到97.7%和42.2%,与前二者相比,FeSO4·7H2O和Ca（OH）2混合物还原稳定化效果较差。投加FeSO4·7H2O能够将土壤中活性大的可交换态和碳酸盐态铬转化为稳定的有机态和残渣态铬;而NaHSO3主要将可交换态和碳酸盐态铬转化为相对稳定的铁锰氧化态铬,其稳定化效果要差于FeSO4·7H2O。     

MB(A2/O)处理城市污水富磷上清液的化学除磷研究

为开发新型除磷脱氮工艺,研制了将MBR和A2/O工艺相结合的新型MB(A2/O)反应器。研究了MB(A2/O)反应器处理城市污水厌氧富磷上清液的化学除磷,并分析了过程机理及特性。结果表明：对于TP在30～45 mg/L的富磷上清液,采用含20% Ca(OH)2的工业石灰与P的最佳投加质量比为22.5;纯Ca(OH)2与P的最佳投加质量比为5.6（摩尔比为2.5）;FeSO4·7H2O与P的最佳投加质量比为10.7（Fe2＋与P的摩尔比为1.3）;Al2(SO4)3·12H2O与P的最佳投加质量比为12（Al3＋与P的摩尔比为1.3）时,均可使出水TP稳定在0.3 mg/L以下;以石灰、NaOH的联合投加方式可大幅减少石灰投加量。     

规模化城市污水处理厂沉淀池模拟优化

高效沉淀池广泛应用于市政污水处理厂,其表面负荷是沉淀效率的关键指标。为将实际工程表面负荷稳定提升到12 m·h⁻¹,采用计算流体力学方法,模拟优化了高效沉淀池的负荷。结果表明,污泥特性和几何构型的协同关系是提高沉淀池表面负荷的关键。宽下降区、长挡墙有利于提升流场的均匀性,但远端出水堰的污泥流失风险限制了表面负荷提升。优化的挡墙长度、上升区/下降区(1/2.65)之比等几何构型特征,能够减少积泥斗污泥扰动,改善总体流场均匀性,从而将表面负荷提高到11~12 m·h⁻¹。污泥沉淀过程中的流变特性和流动本构认识不足,限制了表面负荷的进一步提升。上述结果提升了高效沉淀池工程负荷,深化了对高效沉淀池流态的认识,亦为污水处理系统的减污降碳协同增效提供运行优化工具及案例参考。     

Color and COD removal from wastewater containing Reactive Black 5 using Fenton's oxidation process

In this study, Reactive Black 5 (RB5) was removed from synthetic wastewater using Fenton's oxidation (FO) process. Experiments were conducted on the samples containing 100 and 200 mg l(-1) of RB5 to remove the dye toxicity. Seventy-five milligram per litre of RB5 caused 25% toxicity on 24-h born daphnids whereas 100 mg l(-1) of RB5 displayed 100% toxicity on Daphnia magna. The study was performed in a systematic approach searching optimum values of FeSO(4) and H(2)O(2) concentrations, pH and temperature. Optimum pH and temperature for 100 mg l(-1) of RB5 were observed as 3.0 and 40 degrees C, respectively, using 100 mg l(-1) of FeSO(4) and 400 mg l(-1) of H(2)O(2) resulted in 71% chemical oxygen demand (COD) and 99% color removal. For 200 mg l(-1) of RB5, 84% COD removal was obtained using 225 mg l(-1) of FeSO(4) and 1000 mg l(-1) of H(2)O(2) yielding 0.05 molar ratio at pH 3.0 and 40 degrees C. Color removal was also more than 99%. The optimum conditions determined in accordance with the literature data. The H(2)O(2) requirement seems to be related to initial COD of the sample. FeSO(4)/H(2)O(2) ratios found were not changed for both concentrations. The temperature affected the COD removal significantly at high degrees. Toxicity was completely removed for each concentration of RB5 at optimum removal conditions.     

BAF-MBR用于污水深度处理与同步化学除磷

以南方城镇生活污水为研究对象,对BAF-MBR组合系统进行研究。BAF-MBR组合系统运行稳定,去污完全,出水COD、NH4+-N、TN、TP的浓度分别达到7.11、0.16、8.85和0.34 mg·L-1,均达到了污水回用的最高要求。在后置MBR池内进行同步化学除磷时,FeSO4·7H2O的投加量为20 mg·L-1时,出水TP达到0.34 mg·L-1,一定程度上加剧了膜污染;Al2（SO4）3·18H2O的投加量为30 mg·L-1,出水TP达到0.33 mg·L-1,能有效减缓膜污染进程。     

Stabilization of heavy metals in municipal sewage sludge by freeze–thaw treatment with a blend of diatomite,FeSO4, and Ca(OH)2

In this work, the effects of diatomite with 15% FeSO₄?7H₂O and 7.5% Ca(OH)₂ on sludge stabilization were investigated using batch leaching tests. The influence of cell rupture caused by freezing and thawing on stabilization was also evaluated. The results indicated that the optimal diatomite percentage was 2%. Cell rupture by freezing and thawing reduced heavy metal leachability, followed by cell death and decrease of organic groups. The concentration of heavy metals in sludge leachate increased after cell rupture, indicating that the heavy metal leachability was reduced after freezing and thawings. Moreover, the stabilization effects were generally improved after freezing and thawing. As compared with the stabilization of the original sludge, the unstable fractions decreased and the residual fractions of the heavy metals increased in the stabilized sludge after cell rupture.

Implications: This study developed a method to stabilize heavy metals in municipal sewage sludge. Diatomite combined with FeSO₄·7H₂O and Ca(OH)₂ improved the treatment of sewage sludge contaminated by heavy metals. Cell lysis by freeze–thaw treatment reduced the risk of leaching heavy metals caused by cell death and decreased major organic groups in the sludge.     

利用逐级提高进料浓度的方法启动完全混合反应器处理鸡粪

为了改进完全混合反应器（continuous stirring tank reactor, CSTR）厌氧消化处理鸡粪的启动效果,通过逐级提高进料鸡粪浓度的方法在CSTR中进行中温（36 °C）厌氧消化的启动实验,实验分为2个步骤：污泥适应性驯化和消化能力提升,即通过间歇添加2%浓度鸡粪的方法驯化活性污泥;利用逐级提高进料鸡粪浓度（2.1%、3.2%和5.2%)的方法提高污泥消化能力。结果表明：通过逐级提升进料鸡粪浓度的方法能够驯化出处理一定浓度鸡粪的活性污泥,当进料鸡粪浓度达到5. 2%时,CSTR进料有机负荷（organic loading rate, OLR）、总固体含量（total solid, TS）去除率和产沼气量分别达到1.5 g·（L·d）-1、60%和1 L·（L·d）-1,甲烷体积分数稳定在（65±3）%左右,总氨氮浓度最高达到1 200 mg·L-1,没有出现氨抑制的现象,污泥活性随进料鸡粪浓度提升而逐步得到驯化,从而成功启动反应器正常运行。为CSTR厌氧消化处理高氮基质启动提供了新的方法,具有重要的理论和实践意义。     

The effect of heavy metals on the activated sludge process and its microbial community analysis using 16S ribosomal DNA

The effect of heavy metal shock loading on biological treatment systems was studied by traditional methods and molecular biological techniques. Two kinds of SBR (sequence batch reactor) operation units, unacclimated and acclimated activated sludge systems, were studied. The addition of special nutrients and powdered activated carbon (PAC) to stimulate heavy metal uptake and recovery were studied. The kinetic constants could be used to describe the effect of the inhibition of substance utilisation. The results showed that heavy metal shock loading had a greater effect on the unacclimated activated sludge system than on the acclimated one. The special nutrients greatly enhanced the uptake of copper, and the PAC improved sludge settling and decreased the turbidity of the effluent. The variation of dominant species and the diversity of the bacterial community were analysed using 16S ribosomal DNA. Compared with the slight change of dominant species during acclimation by copper, there was a great change in the acclimated system shocked by a high concentration of copper. The results confirmed that the acclimation could improve the resistance of microorganisms to heavy metal toxicity.     

快速Fenton反应器处理乳化液废水

采用快速Fenton反应器对乳化液废水处理效果进行研究。分别考察反应温度、H2O2和FeSO4投加量、反应时间、初始pH值等因素对COD去除率的影响,实验结果表明,在反应温度30℃,初始pH值4,反应时间20 min,H2O2浓度为116 mmol·L-1,Fe2+浓度为10 mmol·L-1条件下,COD平均去除率可达到60%。H2O2和FeSO4的用量是传统Fenton工艺的65%和10%,反应时间少于传统Fenton工艺的1/7。     

2种启动方式下CSTR厌氧甲烷发酵系统的运行特性比较

厌氧产甲烷菌生长缓慢,对生境环境尤为敏感,其富集难且慢,所以厌氧反应器的快速启动一直是热点研究问题。为摸清连续流搅拌槽式反应器（CSTR）处理糖蜜废水的适宜启动条件和调控方法,比较了两种启动方式下CSTR厌氧甲烷发酵系统的运行特性。结果显示,以啤酒废水污水处理车间的剩余污泥为种泥,在HRT为18 h、温度35℃条件下,进水COD为4 000 mg·L-1时直接启动CSTR厌氧反应器,系统因挥发酸积累,产甲烷菌群活性受限,难以富集培养,经过近103 d的运行,系统未形成高效的厌氧甲烷发酵微生物菌群结构体系;而当采用保持HRT18 h不变,进水COD阶段性提升至4 000 mg·L-1的启动方式时,产甲烷菌群活性较高,能在较短时间内得到有效富集和培养,CSTR能成功培养具有完整甲烷发酵功能的微生物菌,COD去除率可在65 d内达到56%,反应器成功启动。     

芬顿试剂预处理杀螟丹农药废水

利用芬顿试剂(Fenton)氧化预处理杀螟丹农药废水,分别考察了H2O2与FeSO4·7H2O投加量、初始pH、反应时间、温度和摇床转速对Fenton试剂处理杀螟丹废水的影响。结果表明,杀螟丹废水初始COD为676.8 mg/L时,取废水样100 mL,优化反应条件为Fenton试剂的用量1 g FeSO4·7H2O+4 mL H2O2,初始pH值为3,搅拌强度为160 r/min 的摇床转速,反应温度25℃,反应时间60 min。在优化反应条件下COD的去除率达到83.9%。通过Fenton降解,废水可生化性BOD5/COD从0.0745~0.0747上升至0.9066~0.9228,可生化性大幅提高,为后续生化处理创造了条件。考虑到运用于工业废水处理中经济成本等实际问题,建议选取Fenton试剂的用量0.5 g FeSO4·7H2O+1 mL H2O2,COD去除效率能达到65.5%。     

光-Fenton法处理电镀添加剂生产废水

本实验采用光-Fenton法处理电镀添加剂生产废水,探讨了反应时间、H2O2投加量、FeSO4·7H2O投加量、pH、草酸投加量和TiO2等因素对COD去除效果的影响。结果表明,光-Fenton法对COD的降解率达到了94.3%。并得出该方法的最佳操作条件:反应时间为60 min,pH=4,H2O2投加量为80 mL/L,FeSO4·7H2O投加量为6 g/L,Fe2+和H2O2的摩尔比为1∶36,草酸的投加量为12 g/L, TiO2投加量为1.0 g/L。     

镧铁负载给水厂污泥复合材料在完全混合式反应器中的动态吸附除磷特征

采用共沉淀法制备出一种镧铁负载给水厂污泥复合材料(LaFe-DWTR),研究其在完全混合式反应器(CSTR)中对模拟废水和城市污水处理厂二沉池出水的除磷效果以及水力停留时间(HRT)、LaFe-DWTR投加量和水力学条件的影响。结果表明,当CSTR进水PO₄³⁻-P质量浓度为50 mg·L⁻¹,HRT为3 h,LaFe-DWTR投加量为2 g·L⁻¹,反应区采用搅拌时,LaFe-DWTR对PO₄^3--P的去除率稳定在99%以上,吸附量可达24.82 mg·g⁻¹。对于CSTR进水初始PO₄³⁻-P质量浓度为2 mg·L⁻¹的城市污水处理厂二沉池出水,在3 h HRT,0.14 g·L⁻¹投加量时,CSTR出水的PO₄³⁻-P质量浓度稳定在0.2 mg·L⁻¹左右,已达到《城市污水处理厂污染物排放标准》(GB 18918–2002)一级A标准的要求。     

氧化亚铁硫杆菌浸出废弃挠性PCB中金属的影响因素分析

废弃挠性PCB是资源化价值高的电子废弃物之一,正需环境友好的方法回收其所含的多种有价金属。采用显微镜对破碎后的挠性PCB粉样进行解离情况观察,发现破碎法难以将挠性PCB中的金属与非金属解离。通过设计单因素实验,研究挠性PCB粉末粒度大小、添加量、培养液初始pH、菌接种量、活化时间以及FeSO4·7H2O添加量6个因素对氧化亚铁硫杆菌（Acidithiobacillus ferrooxidans,简称A.f菌）浸出挠性PCB中金属过程的影响。结果表明,A.f菌不能浸出挠性PCB中Au,但Cu、Ni可以有效浸出且最优化条件为：10 g·L-1挠性PCB、粒度0.25~0.42 mm、培养基初始pH 2.5、菌接种量5%、菌活化时间5 d、FeSO4·7H2O添加量30 g·L-1,金属Cu的浸出率达到90.1%,比未接种处理高出42.4%;金属Ni的浸出率达到了85.9%,比未接种处理高出了32.9%。因此,采用生物法可环境友好地回收挠性PCB中Cu、Ni,有利于废弃挠性PCB的资源化处理。     

Anion and cation leaching or desorption from activated carbons from municipal sludge and poultry manure as affected by pH.

The conversion of municipal sludge and poultry manure to activated carbon results in a significant ash fraction that contains several different anions and cations. The objectives of this study were to determine whether the select ions are released or leached from virgin carbon into the sorption medium at different pH values. Activated carbon was placed in solutions of pH 1, 5, or 7, and the leaching of six cations (cadmium, chromium, copper, nickel, lead, and zinc) and two anions (arsenate and selenate) was recorded. Considerable quantities of zinc and copper were removed at pH 1 from all carbon sources. However, the amounts leached at pH 5 and 7 were small or undetectable. Our results indicate that leaching or desorption from carbons made from municipal sludge or poultry manure is pH-dependent and occurs readily under highly acidic conditions but minimally under pH conditions typically seen in contaminated water or wastewater.     

Bioleaching of heavy metals from anaerobically digested sewage sludge using FeS2 as an energy source

The effect of using FeS2 as an energy source, on the bioleaching of heavy metals (Zn, Cr, Cu, Pb and Ni) and nutrients (nitrogen and phosphorus) from anaerobically digested sludge using isolated indigenous iron-oxidizing bacteria was investigated in this paper. Addition of FeS2 in the range of 0.5-4.0 g l(-1) accelerated the acidification of sludge and raised the oxidation-reduction potential of sludge medium with an inoculation of 15% (v/v) of active bacteria, thus resulting in an overall increase in metal dissolution efficiency. After 16 days of bioleaching at 28 degrees C and an initial pH of 3.0, up to 99% of Zn, 65% of Cr, 74% of Cu, 58% of Pb and 84% of Ni can be removed from the sludge. In contrast, only 94% of Zn, 12% of Cr, 21% of Cu, 32% of Pb and 38% of Ni were leached out in the control without inoculation of iron-oxidizing bacteria and the addition of FeS2. Less than 15% of nitrogen and 6% of phosphorous were lost after 16 days of bioleaching when using FeS2 as the energy source. Comparing to 39% and 45% loss respectively for these two nutrients when using FeSO4.7H2O as the energy source, FeS2 appears to be a more suitable energy source for preserving nutrients in sludge while removing heavy metals from sludge.