难降解混合化工废水预处理试验研究

对某化工开发区混合化工废水进行预处理试验研究，分别对铁还原后加中和混凝沉淀以及直接中和混凝沉淀两种预处理方法进行了试验，重点讨论了铁还原工艺的各种影响因素。研究了曝气与不曝气，加炭与不加炭以及不同CODCr、不同pH值对铁还原处理效果的影响，并考察了铁的消耗与废水中铁离子的作用及变化情况。     

UV/Fenton技术处理某工厂高浓度乳化油废水

研究了UV/Fenton技术对高浓度金属清洗乳化油废水的处理效果,考察了亚铁与双氧水浓度、pH、反应时间和搅拌对COD去除效果的影响。实验结果表明,UV/Fenton技术对高浓度乳化油废水(COD平均浓度为35 000 mg/L)具有较高的去除效果,最佳工艺条件为:亚铁与双氧水浓度分别为2 400 mg/L和6 000 mg/L,pH为3,经过2 h反应,COD可降低至1 050 mg/L,去除率为97%。搅拌会降低COD的去除率。研究表明,UV/Fenton技术对高浓度乳化油废水具有很好的降解效果,且药品消耗较低,为目前此类高浓度有机废水的处理提供了技术参考。     

热镀锌厂酸洗废水和锌灰中回收硫化锌

从热镀锌厂的酸洗废水和锌灰中回收硫化锌,采用X射线能谱仪(EDS),X射线衍射仪(XRD),傅里叶红外光谱仪(FTIR)和场发射透射电镜(FETEM)表征样品ZnS性质,电感耦合等离子发射体(ICP-OES)分析上清液性质,并研究该反应动力学过程。EDS和ICP分析表明,样品ZnS纯度达到85.45%,其上清液含有高浓度铁,含量为2 g/L,可用于制备复合亚铁絮凝剂,而其他重金属离子浓度均低于电镀废水排放标准。XRD分析表明,样品ZnS是立方晶型,调节pH和采用滴加方式能有效改善样品ZnS的晶型。采用Scherrer公式计算晶体粒径,结果表明,晶粒大小在3~6 nm之间。FTIR分析表明,样品ZnS呈现良好的红外透明性,且温度、pH和滴加方式对样品的红外透光性基本没有影响。FETEM结合XRD图表明,该纳米晶呈片状,近似为球形,呈多层叠加,分散性不明显,有团聚现象。动力学实验表明,逆一级动力学方程适合描述硫化沉淀的反应动力学过程,活化能为39.04 kJ/mol,沉淀过程受化学反应和扩散联合控制。     

含锌离子模拟废水沉淀研究及污泥表征

采用氢氧化钙、碳酸钠和硫化钠处理含锌废水,在溶液pH、锌离子浓度、颗粒粒径、颗粒Zeta电位、上清液浊度和污泥体积等指标测定的基础上,结合沉淀产物表征,探讨了沉淀剂用量对锌离子去除率的影响及沉淀机理。研究结果表明,n(Ca(OH)2∶n(Zn)=1.5,去除率达到最大值99.65%,n(Na2CO3)∶n(Zn)=1.5,去除率达到最大值99.89%,n(Na2S)∶n(Zn)=2.5,去除率达到最大值99.95%。X-射线衍射和热重分析表明,氢氧化钙与废水生成的沉淀物为碳酸钙和氧化锌,碳酸钠与废水生成的沉淀物为氧化锌和碱式碳酸锌,硫化钠与废水生成的沉淀物为硫化锌,这对污泥处理处置以及回收利用有指导意义。     

氯化铁混凝剂中亚铁含量对混凝效果的影响

以城市污水处理厂原水为实验水样,研究了液体FeCl3混凝剂中亚铁含量对其混凝效果的影响。结果表明,液体FeCl3混凝剂中亚铁的含量与其对污水中总磷和COD的去除效果呈非线性相关性,当FeCl3中亚铁含量为25%时,16.0 mg/L的投加量即可使上清液COD降至195 mg/L,去除率达56.7%,总磷降至1.7 mg/L,去除率达70.7%;当FeCl3中亚铁含量继续降低至0.4%时,COD、总磷的去除率仅提高1.1%和1.3%。因此从性价比来讲,FeCl3混凝剂用于污水厂原水混凝时,可适当放宽产品质量标准中亚铁含量限值的规定,有利于降低氯化铁混凝剂的生产成本。     

Stabilization of mercury-containing wastes using sulfide

This paper summarizes the findings of our studies on mercury stabilization using sulfide. Primary stabilization variables such as stabilization pH and sulfide/mercury molar ratio were tested. Mercury stabilization effectiveness was evaluated using the Toxicity Characteristic Leaching Procedure (TCLP) and the constant pH leaching tests. The influence of interfering ions on mercury immobilization was also tested. The experimental results indicate that the sulfide-induced treatment technology is an effective way to minimize mercury leaching. It was found that the most effective mercury stabilization occurs at pH 6 combined with a sulfide/mercury molar ratio of 1. The combined use of increased dosage of sulfide and ferrous ions ([S]/[Hg]=2 and [Fe]/[Hg]=3 at pH=6) can significantly reduce interferences by chloride and/or phosphate during sulfide-induced mercury immobilization. The sulfide-treated waste stabilization efficiency reached 98%, even with exposure of the wastes to high pH leachants.     

亚铁羟基络合物还原转化水溶性偶氮染料

偶氮染料是印染工艺中应用最广泛的一类染料,目前染料废水脱色是污水处理难题。亚铁混凝处理染料废水过程中可能存在亚铁的还原作用,本实验制备了比溶解态亚铁更具还原反应活性的亚铁羟基络合物(ferrous hydroxycomplex,FHC),以5种不同类型的水溶性偶氮染料为目标污染物,研究FHC还原水溶性偶氮染料的脱色性能。实验结果表明,FHC对活性艳红X-3B、酸性大红GR和阳离子红X-GRL有较好的还原脱色效果,仅投加含铁89.6 mg/L的FHC,染料脱色率达到90%以上,继续增大FHC投加量可以完全脱色;中性枣红GRL的FHC还原脱色效果较差,需加入313.6 mg/L的FHC才能达到90%以上脱色率;134.4 mg/L的FHC能够将直接耐酸大红4BS完全脱色,但其脱色主要以混凝沉淀为主;溶液pH对FHC的还原性能产生重要影响,FHC还原染料脱色的适宜的pH值范围为4～10。该研究为亲水性染料脱色提供了一种新的技术,也为FHC运用于印染废水脱色提供了理论基础。     

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.     

臭氧生物活性炭工艺处理某多金属硫化矿浮选废水的小试研究

某多金属硫化矿选矿厂浮选废水水量大,目前该厂对浮选废水的处理方法为尾矿库砂滤治理,但该方法存在效率低、周期长、回用影响选矿指标等众多弊端。为高效低成本的处理浮选废水,结合浮选废水的特点(低COD、难降解、高pH),开展了臭氧氧化-生物活性炭吸附工艺处理选矿废水的小试研究。选矿废水中各残留有机药剂及pH对浮选指标的影响研究表明,废水中残留有机药剂及pH对浮选指标均有不同程度的影响。臭氧氧化-生活活性炭吸附工艺处理选矿废水的小试研究表明,水力停留时间为4 h、反应器臭氧浓度为33.3 mg/L,可获得COD去除率57%、pH降低到8的废水处理效果。将处理后的废水回用于选矿,基本消除残留药剂及pH对浮选指标的影响。本研究提供了一种处理浮选废水的新思路,对臭氧生物活性炭工艺处理浮选废水的工业应用具备参考价值。     

Citric acid-modified Fenton's reaction for the oxidation of chlorinated ethylenes in soil solution systems

Fenton's reagent, a solution of hydrogen peroxide and ferrous iron catalyst, is used for an in situ chemical oxidation of organic contaminants. Sulfuric acid is commonly used to create an acidic condition needed for catalytic oxidation. Fenton's reaction often involves pressure buildup and precipitation of reaction products, which can cause safety hazards and diminish efficiency. We selected citric acid, a food-grade substance, as an acidifying agent to evaluate its efficiencies for organic contaminant removal in Fenton's reaction, and examined the impacts of using citric acid on the unwanted reaction products. A series of batch and column experiments were performed with varying H2O2 concentrations to decompose selected chlorinated ethylenes. Either dissolved iron from soil or iron sulfate salt was added to provide the iron catalyst in the batch tests. Batch experiments revealed that both citric and sulfuric acid systems achieved over 90% contaminant removal rates, and the presence of iron catalyst was essential for effective decontamination. Batch tests with citric acid showed no signs of pressure accumulation and solid precipitations, however the results suggested that an excessive usage of H2O2 relative to iron catalysts (Fe2+/H2O2<1/330) would result in lowering the efficiency of contaminant removal by iron chelation in the citric acid system. Column tests confirmed that citric acid could provide suitable acidic conditions to achieve higher than 55% contaminant removal rates.     

昆明市污水排水系统产甲烷规律的模拟实验研究

通过对昆明市餐饮和居民生活污水厌氧模拟实验研究,初步探讨生活污水中CH4的产生规律,实验结果表明,在自然条件下,餐饮和居民生活污水中产生的甲烷浓度最大值分别为1.63 mg/L和3.82 mg/L。并且将COD、硫酸盐、硫化物、TN的浓度变化与甲烷浓度变化进行Pearson简单相关性分析,结果表明,1/COD、COD/硫酸盐和1/TN与甲烷在置信度为0.01时极显著相关,硫化物与甲烷在置信度为0.05时不相关;COD、硫酸盐和TN浓度的变化对生活污水中甲烷的产生起关键性作用。对居民生活污水中甲烷产生规律进行温度和pH控制分析研究,实验结果表明,生活污水在25~30℃时,24 h内甲烷产生量最大值为8.6494 mg/L,明显大于其他温度段的甲烷产生量;在pH为7~8之间时,甲烷的产生量在24 h内达到的最大值为3.0477 mg/L,明显高于其他pH控制段的甲烷产生量。     

Removal of As,Mn, Mo,Se, U,V and Zn from groundwater by zero-valent iron in a passive treatment cell: reaction progress modeling

Three treatment cells were operated at a site near Durango, CO. One treatment cell operated for more than 3 years. The treatment cells were used for passive removal of contamination from groundwater at a uranium mill tailings repository site. Zero-valent iron [Fe(0)] that had been powdered, bound with aluminosilicate and molded into plates was used as a reactive material in one treatment cell. The others used granular Fe(0) and steel wool. The treatment cells significantly reduced concentrations of As, Mn, Mo, Se, U, V and Zn in groundwater that flowed through it. Zero-valent iron [Fe(0)], magnetite (Fe3O4), calcite (CaCO3), goethite (FeOOH) and mixtures of contaminant-bearing phases were identified in the solid fraction of one treatment cell. A reaction progress approach was used to model chemical evolution of water chemistry as it reacted with the Fe(0). Precipitation of calcite, ferrous hydroxide [Fe(OH)2] and ferrous sulfide (FeS) were used to simulate observed changes in major-ion aqueous chemistry. The amount of reaction progress differed for each treatment cell. Changes in contaminant concentrations were consistent with precipitation of reduced oxides (UO2, V2O3), sulfides (As2S3, ZnS), iron minerals (FeSe2, FeMoO4) and carbonate (MnCO3). Formation of a free gas phase and precipitation of minerals contributed to loss of hydraulic conductivity in one treatment cell.     

混凝沉淀法处理含砷选矿废水

某钨矿含砷选矿废水砷含量高且砷以As(V)为主要存在形态,采用混凝沉淀法处理,详细考察了生石灰、硫酸亚铁和六水三氯化铁3种混凝剂对废水中砷的去除效果。实验结果表明,在PAM投加量40 mg/L,静沉时间60 min条件下,比较分析3种混凝剂对砷的去除效果,三氯化铁为最佳除砷混凝剂。三氯化铁最佳除砷工艺条件为:pH 7.5,三氯化铁投加量986.67 mg/L,混凝反应时间25 min,PAM投加量为40 mg/L,静沉60 min,含砷选矿废水经该工艺处理后,砷去除率可达99.14%,出水砷浓度降至0.361 mg/L,达到国家污水综合排放标准(GB8978-1996)。     

Hydrogen sulfide gas treatment by a chemical-biological process: chemical absorption and biological oxidation steps

In order to remove high concentrations of hydrogen sulfide (H2S) gas from anaerobic wastewater treatments in livestock farming, a novel process was evaluated for H2S gas abatement involving the combination of chemical absorption and biological oxidation processes. In this study, the extensive experiments evaluating the removal efficiency, capacity, and removal characteristics of H2S gas by the chemical absorption reactor were conducted in a continuous operation. In addition, the effects of initial Fe2+ concentrations, pH, and glucose concentrations on Fe2+ oxidation by Thiobacillus ferrooxidans CP9 were also examined. The results showed that the chemical process exhibited high removal efficiencies with H2S concentrations up to 300 ppm, and nearly no acclimation time was required. The limitation of mass-transfer was verified as the rate-determining step in the chemical reaction through model validation. The Fe2+ production rate was clearly affected by the inlet gas concentration as well as flow rate and a prediction equation of ferrous production was established. The optimal operating conditions for the biological oxidation process were below pH 2.3 and 35 degrees C in which more than 90% Fe3+ formation ratio was achieved. Interestingly, the optimal glucose concentration in the medium was 0.1%, which favored Fe2+ oxidation and the growth of T. ferrooxidans CP9.     

吹脱法预处理皮革废水的实验研究

对某皮革厂综合废水进行吹脱预处理实验,综合考察了影响氨氮去除的各个因素(pH值、汽液比、吹脱温度、氨氮初始浓度),同时对该预处理工艺去除铬、SS(悬浮固体浓度)、COD和硫化物的条件进行了优化,并进行了能耗及运行成本估算。结果表明:该厂皮革废水的最佳吹脱工况为pH=11,气液比=1 800,温度25~35℃,在此条件下,当进水ρ(NH3-N)=304.7 mg/L、ρ(Cr)=65.0 mg/L、ρ(SS)=1 700 mg/L、ρ(COD)=2 700 mg/L、ρ(S2-)=112.3 mg/L时,相应的去除率可达78.1%~83.5%、96.4%、88.2%、45.6%和85.0%,且吹脱法对氨氮具有较高的抗冲击负荷能力,吨水处理成本约为3.61元,可作为皮革废水的预处理工艺。     

The effect of manipulating sediment pH on the porewater chemistry of copper- and zinc-spiked sediments

Spiking of sediment with metal cations that readily hydrolyse causes the sediment pH to decrease. Displaced iron and manganese also oxidise and hydrolyse, further lowering sediment pH. The lower pH of metal-spiked sediments requires a subsequent sediment neutralisation. This research compared the pH adjustment of Cu- and Zn-spiked sediments using single and multiple additions of 1M NaOH. Sediment pH, redox potential, and porewater metal concentrations were monitored over 40 days. Depth profiles were also measured to investigate stratification. A single pH adjustment to pH 7 and 8 initially counteracted the pH change caused by metal additions, however, pH continued to decrease slowly thereafter. Multiple pH adjustments diminished porewater Cu, Zn and Fe concentrations to a greater extent than a single pH adjustment, but the ongoing oxidative precipitation of porewater metals continued to consume OH(-) ions and impede pH maintenance. Displacement of high iron(II) concentrations and the opposing rates of iron(II) oxidative precipitation and bacterially-mediated iron(II) production, affected the partitioning of the added metals between the sediment and pore water. Despite similar pH over the spiked-metal concentration gradient following pH adjustment, sediments spiked with higher metal concentrations produced lower porewater Fe concentrations, possibly due to toxicity to iron(III) oxyhydroxide reducing bacteria. Distinct stratification of redox potential and dissolved Fe and Cu developed over a depth of 6cm during the 40-day equilibration period. Recommendations are provided on methods for preparing metal-spiked sediments in which the partitioning of metals between dissolved and particulate phases better resembles that of in situ (field) metal-contaminated sediments.     

pH dependence of ferrous sorption onto two smectite clays

This work examines the abilities of two smectite minerals (SWa-1 and Wyoming montmorillonite) to adsorb ferrous iron at concentrations from 0.037 mM (2 ppm) to 2.5 mM (240 ppm) over a range of pHs from 4.0 to 8.0. Both sorption isotherm and sorption edge data are presented. Ferrous sorption (Fe(aq)2+ = 0.1 mM) to both SWa-1 and Wyoming montmorillonite over the pH range 4.0-6.75 is relatively constant at approximately 1000 l kg(-1) for both minerals. Sorption in this pH range is attributed to the cation exchange capacity of the clay along the basal surfaces. At pH values above 6.75 the amount of ferrous iron sorbed increases dramatically. At pH 8, sorption (Fe(aq)+ = 0.1 mM) reaches 6600 l kg(-1) and 8000 l kg(-1) for Swa-1 and Wyoming montmorillonite respectively. This is attributed to the specific interaction between ferrous ions and surface sites along mineral edges. The overriding geochemical implication is that in reduced sediments containing more than a few percent clay, the pool of sorbed ferrous iron is vast. This pool of reduced iron is both redox labile and bio-available and is not readily indicated by simple measurement of dissolved Fe2+.     

生物接触氧化法处理选矿废水的影响因素

选矿废水主要来源于有色金属矿山,具有水量大、悬浮物浓度高、重金属浓度高、有机浮选药剂浓度高等明显特征。选矿废水若直接排放,对环境的危害相当大。采用生物接触氧化法对模拟选矿废水进行了处理实验研究,考察了不同工艺条件对苯胺黑药、黄药及乙硫氮等浮选药剂去除效果的影响,结果表明:接触氧化反应器的最佳停留时间为8 h,进水最佳pH为6～7,葡萄糖投加量为0.1 mg/L时,降解效果达到最佳;此外,接触氧化反应器中微生物承受硫化物的浓度可达到120 mg/L。     

微电解-混凝法处理抛光液废水

采用微电解-混凝处理抛光液废水,考察了铁水比、进水pH值、铁炭比、振荡时间对微电解处理效果的影响.通过单因素实验与正交实验找出了影响较大的因素,进水pH、铁水比、振荡时间都对去除率影响较大.最佳微电解条件为铁水比为0.375,进水pH为3,铁炭比为1∶1,振荡时间为150 min.同时,当混凝剂硫酸亚铁的投加量为160 mg/L、三氯化铁的投加量为20 mg/L时,COD去除率可达到83.8％,金属铜离子去除率可达到96％.     

Selective removal of heavy metals from metal-bearing wastewater in a cascade line reactor

Goal, Scope and Background This paper is a part of the research work on ‘Integrated treatment of industrial wastes towards prevention of regional water resources contamination — INTREAT’ the project. It addresses the environmental pollution problems associated with solid and liquid waste/effluents produced by sulfide ore mining and metallurgical activities in the Copper Mining and Smelting Complex Bor (RTB-BOR), Serbia. However, since the minimum solubility for the different metals usually found in the polluted water occurs at different pH values and the hydroxide precipitates are amphoteric in nature, selective removal of mixed metals could be achieved as the multiple stage precipitation. For this reason, acid mine water had to be treated in multiple stages in a continuous precipitation system-cascade line reactor. Materials and Methods All experiments were performed using synthetic metal-bearing effluent with chemical a composition similar to the effluent from open pit, Copper Mining and Smelting Complex Bor (RTB-BOR). That effluent is characterized by low pH (1.78) due to the content of sulfuric acid and heavy metals, such as Cu, Fe, Ni, Mn, Zn with concentrations of 76.680, 26.130, 0.113, 11.490, 1.020 mg/dm³, respectively. The cascade line reactor is equipped with the following components: for feeding of effluents, for injection of the precipitation agent, for pH measurements and control, and for removal of the process gases. The precipitation agent was 1M NaOH. In each of the three reactors, a changing of pH and temperature was observed. In order to verify efficiency of heavy metals removal, chemical analyses of samples taken at different pH was done using AES-ICP. Results Consumption of NaOH in reactors was 370 cm³, 40 cm³ and 80 cm³, respectively. Total time of the experiment was 4 h including feeding of the first reactor. The time necessary to achieve the defined pH value was 25 min for the first reactor and 13 min for both second and third reactors. Taking into account the complete process in the cascade line reactor, the difference between maximum and minimum temperature was as low as 6°C. The quantity of solid residue in reactors respectively was 0.62 g, 2.05 g and 3.91 g. In the case of copper, minimum achieved concentration was 0.62 mg/dm³ at pH = 10.4. At pH = 4.50 content of iron has rapidly decreased to < 0.1 mg/dm³ and maintained constant at all higher pH values. That means that precipitation has already ended at pH=4.5 and maximum efficiency of iron removal was 99.53%. The concentration of manganese was minimum at pH value of 11.0. Minimum obtained concentration of Zn was 2.18 mg/dm³ at a pH value of 11. If pH value is higher than 11, Zn can be re-dissolved. The maximum efficiency of Ni removal reached 76.30% at a pH value of 10.4. Discussion Obtained results show that efficiency of copper, iron and manganese removal is very satisfactory (higher than 90%). The obtained efficiency of Zn and Ni removal is lower (72.30% and 76.31%, respectively). The treated effluent met discharge water standard according to The Council Directive 76/464/EEC on pollution caused by certain dangerous substances into the aquatic environment of the Community. Maximum changing of temperature during the whole process was 6°C. Conclusion This technology, which was based on inducing chemical precipitation of heavy metals is viable for selective removal of heavy metals from metal-bearing effluents in three reactor systems in a cascade line. Recommendations and Perspectives The worldwide increasing concern for the environment and guidelines regarding effluent discharge make their treatment necessary for safe discharge in water receivers. In the case where the effluents contain valuable metals, there is also an additional economic interest to recover these metals and to recycle them as secondary raw materials in different production routes. ESS-Submission Editor: PhD Hailong Wang, hailong.wang@ensisjv.com