电絮凝-超滤组合技术处理含铜废水

采用电絮凝-超滤（electrocoagulation-ultrafiltration,EC-UF）组合技术对含铜废水中的铜离子进行了处理实验研究。讨论了电流密度、初始pH、初始铜浓度和初始电导率等因素对铜的去除效果和膜污染的影响,并分析了这些影响因素对EC-UF组合技术效率的作用机制。结果表明,在电流密度J=50 A·m-2、初始铜浓度C（Cu2+）≤40 mg·L-1、初始pH=4~8、初始电导率σ=2 mS·cm-1、电解时间20 min的条件下,废水中铜的去除率达到99.6%并有效的减缓了膜污染。本研究为EC-UF组合技术除铜的实践应用提供了科学依据。     

Copper and cadmium removal from synthetic industrial wastewater using chitosan and nylon 6

Purpose

Chitosan with nylon 6 membranes was evaluated as adsorbents to remove copper and cadmium ions from synthetic industrial wastewater.

Methods

Chitosan and nylon 6 with glutaraldehyde blend ratio with (1:1+Glu, 1:2+Glu, and 2:1+Glu) have been prepared and these were used as membranes to remove copper and cadmium ions from synthetic industrial wastewater. Characterization of the synthesized membrane has been done with FTIR, XRD, TGA/DTA, DSC, and SEM. Chemical parameters for quantities of adsorption of heavy metal contamination have been done and the kinetics of adsorption has also been carried out.

Results

The optimal pH for the removal of Cd(II) and Cu(II) using chitosan with nylon 6. Maximum removal of the metals was observed at pH 5 for both the metals. The effect of adsorbent dose also has a pronounced effect on the percentage of removal of the metals. Maximum removal of both the metals was observed at 5 g/100 ml of the adsorbent.

Conclusion

Copper and cadmium recovery is parallel at all time. The percentage of removal of copper increased with increase in the pH from 3 to 5. In the case of cadmium containing wastewater, the maximum removal of metal occurred at pH 5. The uptake amount of Cu²⁺ ions on chitosan increased rapidly with increasing contact time from 0 to 360 min and then reaches equilibrium after 360 min; the equilibrium constant for copper and cadmium ions is more or less the same for the adsorption reaction.     

Macrophyte growth in a pilot-scale constructed wetland for industrial wastewater treatment

A pilot-scale wetland was constructed to assess the feasibility of treating the wastewater from a tool industry in Santo Tomé, Santa Fe, Argentina. The wastewater had high conductivity and pH, and contained Cr, Ni and Zn. This paper describes the growth of vegetation in the experimental wetland and the nutrient and metal removal. The wetland was 6 x 3 x 0.4 m. Water discharge was 1000 l d(-1) and residence time was 7d. After the wetland was rendered impermeable, macrophytes from Middle Paraná River floodplain were transplanted. Influent and effluent quality was analyzed every 15 d. TP, Cr, Ni and Zn concentrations in leaves, roots and sediment (inlet and outlet) were measured monthly. Cover and biomass of predominant species were estimated. Also, greenhouse experiments were carried out to measure the effects of conductivity and pH on floating species. The variables measured in the influent were significantly higher than those in the effluent, except for HCO(3)(-) and NH(4)(+). TP and metal concentrations in sediment at the inlet were significantly higher than those at the outlet. Conductivity and pH of the incoming wastewater were toxic for the floating species. Typha domingensis displaced the other species and reached positive relative cover rate and biomass greater than those at the undisturbed natural environment. T. domingensis proved to be highly efficient for the treatment of wastewater. For that reason, it is the advisable species for the treatment of wastewater of high conductivity and pH enriched with metals, characteristic of many industrial processes.     

Influence of clay on the adsorption of heavy metals like copper and cadmium on chitosan

The influence of clay on the adsorption of heavy metals like copper and cadmium on chitosan from simulated industrial wastewater is evaluated. Chitosan–clay blend with ratio of (1:1), (1:2), and (2:1) have been prepared, and these were used as membranes to remove copper and cadmium ions from synthetic industrial wastewater. The chemical parameters for quantities of adsorption of heavy metal contamination have been done, and the kinetics of adsorption has also been carried out. Clay provides enough absorbable sites to overcome mass transfer limitations. The number of absorbable sites for cadmium is more compared to copper, and thus the rate of recovery of cadmium is faster than copper, and the percentage removal of cadmium is more than copper at all times on clay over nylon 6. This difference indicates the influence of clay in the adsorption of heavy metals in comparison to synthetic polymer nylon 6. Rate constant for first-order kinetics of adsorption, k ₁, for copper and cadmium is less than that of clay, which clearly indicates that clay, which is a natural polymer, is more kinetically favored compared to synthetic polymer. The difference in the intraparticle diffusion in both the natural and synthetic polymer is not much, and it suggests that the particle diffusion mechanism is the same in both cases. Copper and cadmium recovery is parallel at all times. The percentage of removal of copper increased with an increase in pH from 3 to 5. In the case of cadmium containing wastewater, the maximum removal of metal occurred at pH 5. The uptake amount of Cu²⁺ ions on chitosan increased rapidly with increasing the contact time from 0 to 360 min and then reaches equilibrium after 360 min, and the equilibrium constant for copper and cadmium ions are more or less the same for the adsorption reaction. There are more adsorption sites for cadmium in the presence of clay and mass transfer limitation is avoided without resorting to rotation, which is the highlight of the present work. And more so, this is pronounced in the case of natural polymer compared to synthetic polymer.     

Application of flotation for the separation of metal-loaded zeolites

Several industrial wastewater streams may contain heavy metal ions, which must be effectively removed, before the discharge or reuse of treated waters could take place. Different bonding materials, presenting selectivity and fast reaction kinetics for the removal of metals, have been examined for this purpose. The objective of the present paper was to investigate the application of dispersed-air flotation for the separation of metal-loaded sorbents. Two similar zeolite samples were applied as effective bonding agents for the removal of zinc, a toxic metal commonly found in many industrial wastewaters. This combined process, termed sorptive flotation, involves the preliminary scavenging of metal ions, by using the appropriate sorbent particles (usually present as ultrafine particulates), followed by flotation for the effective separation of them. The obtained results were very promising, as both metal and sorbent were effectively removed/separated from the dispersion.     

Effect of operational parameters on heavy metal removal by electrocoagulation

In the present paper, the performance of electrocoagulation (EC) for the treatability of mixed metals (chromium (Cr), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn)) from metal plating industrial wastewater (EPW) has been investigated. The study mainly focused on the affecting parameters of EC process, such as electrode material, initial pH, distance between electrodes, electrode size, and applied voltage. The pH 8 is observed to be the best for metal removal. Fe–Fe electrode pair with 1-cm inter-electrode distance and electrode surface area of 40 cm² at an applied voltage of 8 V is observed to more efficient in the metal removal. Experiments have shown that the maximum removal percentage of the metals like Cr, Ni, Zn, Cu, and Pb are reported to be 96.2, 96.4, 99.9, 98, and 99.5 %, respectively, at a reaction time of 30 min. Under optimum conditions, the energy consumption is observed to be 51.40 kWh/m³. The method is observed to be very effective in the removal of metals from electroplating effluent.     

新型DTC类络合重金属捕集剂的合成及其在废水处理中的应用

为了更有效地去除废水中络合态重金属离子且不添加任何絮凝剂, 合成了一种新型的重金属捕集剂聚-二硫代氨基甲酸铵（PADTC）, 并采用傅里叶红外光谱, 核磁共振, 元素分析和凝胶渗透色谱推测产物结构。考察反应时间, pH对重捕剂去除效果的影响, 结果表明：在pH=6、反应时间为20 min时, Cu2+、Ni2+和Zn2+的最大吸附能力分别为246、234和227 mg·g-1;同时还探讨了不同络合剂的吸附影响, 其去除顺序为TA > CA > EDTA。在实际废水处理中, PADTC取得了良好的处理效果。通过FT-IR、SEM-EDS和XPS表征证实了PADTC对络合重金属的抓捕机理。使用PADTC从废水中去除重金属可能具有良好的工业发展前景。     

Biosorption of cadmium and copper contaminated water by Scenedesmus abundans

Experiments were conducted comparing the individual removals of cadmium and copper from water via biosorption using Scenedesmus abundans, a common green algae, to removal in a multi-component system to determine competitive effects, if any, between the metals. The goal was to characterize the biological treatment of water contaminated with heavy metals using live aquatic species. In addition, experiments were performed to measure cell viability as a function of metal concentration and also to compare metal removal using living species to that using nonliving ones. It was shown that, while both living and nonliving S. abundans removed cadmium and copper from water, living algae significantly outperformed nonliving algae. Further, in characterizing biosorption by three concentrations of live S. abundans, capacity curves were created comparing the metal biosorbed per mass algae to the initial metal concentration in solution. The algae concentration was not a factor in the biosorption of either metal individually, such that the capacity of the algae for the metal increased with decreasing algae concentration. At the lowest algae concentration considered, competitive effects were observed at copper and cadmium concentrations above 4 mg/l each. At the highest algae concentration considered, no competitive effects were observed in the range of cadmium and copper concentrations studied (1-7 mg/l). It was concluded that biological treatment of heavy metal contaminated water is possible and that at adequately high algae concentrations, multi-component metal systems can be remediated to the same level as individual metals.     

基于减压脱水干燥技术的高浓度工业污水中重金属的去除与资源化

工业污水中高浓度重金属的去除一直是环境污染治理领域的一个难题。至今为止,在实验室水平上有很多可以借鉴的技术,但能在实际工程领域实用的技术还比较缺乏。为此,通过利用改进的减压脱水干燥装置,对多种含有重金属（Cu、Zn、Ni、Pb）的高浓度工业废水的处理流程和技术进行研究。结果表明,无论污染源和污水种类如何,减压脱水干燥装置对废水中Cu、Zn、Pb、Ni的去除效果都非常明显,去除率均保持在93.33%~99.99%,对高浓度重金属去除率可达99.99%。浓缩以后的重金属可以回收再利用;不同类型工业废水中悬浮物（SS）、有机物（COD和BOD5）和油类的浓度高低,不影响其中重金属的去除;除了重金属以外,本技术对其他污染物质也有明显的去除效果,去除效果的排序为：重金属 > SS > COD > BOD5 > 油类。本装置处理过程无需添加药剂、对废水的前处理要求低、它的封闭性减轻了气味和噪音,是一种操作简便且高效环保的污水处理系统。     

Removal of insoluble heavy metal sulfides from water

The necessity of heavy metal removal from wastewater has led to increasing interest in absorbents. We have developed a new approach to obtain high metal adsorption capacity by precipitating metal sulfides with sodium sulfide on the surface of bentonite and adhere them to the absorbent. This method allowed to remove approximately 90% of cadmium as CdS from 10(-4)-10(-6) M CdCl2 solutions. Additional reactions are related to the removal of excess sodium sulfide by the release of hydrogen sulfide and oxidation to sulfur using carbogen gas (5% CO2, 95% O2) followed by aeration.     

Enhanced removal of heavy metals in primary treatment using coagulation and flocculation.

The goal of this study was to determine the removal efficiencies of chromium, copper, lead, nickel, and zinc from raw wastewater by chemically enhanced primary treatment (CEPT) and to attain a total suspended solids removal goal of 80%. Operating parameters and chemical doses were optimized by bench-scale tests. Locally obtained raw wastewater samples were spiked with heavy metal solutions to obtain representative concentrations of metals in wastewater. Jar tests were conducted to compare the metals removal efficiencies of the chemical treatment options using ferric chloride, alum, and anionic polymer. The results obtained were compared with those from other studies. It was concluded that CEPT using ferric chloride and anionic polymer is more effective than CEPT using alum for metals removal. The CEPT dosing of 40 mg/L ferric chloride and 0.5 mg/L polymer enhanced heavy metals removal efficiencies by over 200% for chromium, copper, zinc, and nickel and 475% for lead, compared with traditional primary treatment. Efficient metals capture during CEPT can result in increased allowable headworks loadings or lower metal levels in the outfall.     

溴与铜协同还原法脱除污酸中的砷

针对高酸度的含砷废水处理难度大的问题,通过溴与铜的协同作用将高价态的砷还原为单质来实现脱砷,采用ICP测定、阴离子电极分析、XRF检测对反应前后的溶液滤渣进行了表征;研究了还原反应中各因素对反应的影响。结果表明：反应温度、反应时间、氢离子浓度、铜粉目数及搅拌速率的升高均有利于砷还原反应的发生;增加铜粉及溴化钠用量,有助于反应进行,铜粉与溴化钠过量则引起反应后溶液中铜、溴离子浓度升高。在最优条件下,反应后砷的去除率可达到99.5%以上,溶液中的铜离子为60 mg·L^-1以下,通过XRF分析反应后所得的滤渣发现,溶液中的砷均沉淀进入固体。通过溴与铜协同还原的方法,溶液中的高价砷还原为单质,实现了高酸度环境下砷的脱除。     

3种植物水浸提液对工业园区污水处理厂污泥中重金属的淋洗效果

为探讨植物材料淋洗去除工业园区污水污泥中重金属的可行性,选用马桑（Coriaria nepalensis）、枳椇子（Hovenia acerba）和乌药（Lindera aggregata）的水浸提液作为淋洗剂,采用振荡淋洗实验研究了不同淋洗剂浓度和pH、淋洗时间和温度对其去除供试污泥中重金属的影响,并确定淋洗的最佳参数。结果表明,当3种淋洗剂浓度从20 g·L-1上升到80 g·L-1或淋洗温度从15 ℃增至55 ℃时,重金属去除率均呈先升高后稳定的趋势。同时,淋洗效果还受淋洗剂pH和淋洗时间的影响。基于淋洗效果、技术应用和经济成本,枳椇子、乌药和马桑水浸提液淋洗的最佳参数分别为pH 7、80 g·L-1、25 ℃、180 min,pH 4、100 g·L-1、25 ℃、180 min和pH 4、80 g·L-1、25 ℃、180 min,此时各淋洗剂重金属去除率总体表现为Cd>Cu>Pb>Ni。其中枳椇子和乌药对Cd去除率较高,分别为73.12%和82.60%,但Ni去除率仅为23.34%和19.42%;与前2种植物材料相比,马桑对Pb（36.40%）和Ni（27.88%）的去除率高,但对Cd（30.11%）和Cu（30.38%）的去除率相对较低。淋洗后污泥中Cu和Pb含量均可达农用污泥A级标准（CJ/T 309-2009）,乌药淋洗后Cd及马桑淋洗后Ni含量可达到A级标准,其他淋洗剂情况下Cd和Ni含量可达到B级标准。此外,植物水浸提液淋洗污泥还能有效保留甚至增加其养分,降低可交换态、碳酸盐结合态和铁锰结合态重金属含量。研究表明,马桑、枳椇子和乌药在淋洗去除污泥中重金属和实现污泥土地应用上有一定潜力。     

Removal of heavy metal ions from water by complexation-assisted ultrafiltration

Toxic heavy metals in air, soil and water are global problems that are growing threat to the environment. Therefore, the removal and separation of toxic and environmentally relevant heavy metal ions are a technological challenge with respect to industrial and environmental application. A promising process for the removal of heavy metal ions from aqueous solutions involves bonding the metals to a bonding agent (such as macromolecular species), and then separating the loaded agents from wastewater by separation processes such as membrane filtration. The choice of water-soluble macroligands remains important for developing this technology. The effects of type of complexing agent, pH value and applied pressure on retention coefficients of Zn(II) and Cd(II) complexes were investigated. At best operating conditions (pH=9.0, p=300kPa) using diethylaminoethyl cellulose, the removal of Cd(2+) and Zn(2+) was more than 95% and 99%, respectively.     

Significance of design and operational variables in chemical phosphorus removal

Batch and continuous experiments using model and real wastewaters were conducted to investigate the effect of metal salt (ferric and alum) addition in wastewater treatment and the corresponding phosphate removal from a design and operational perspective. Key factors expected to influence the phosphorus removal efficiency, such as pH, alkalinity, metal dose, metal type, initial and residual phosphate concentration, mixing, reaction time, age of flocs, and organic content of wastewater, were investigated. The lowest achievable concentration of orthophosphate under optimal conditions (0.01 to 0.05 mg/L) was similar for both aluminum and iron salts, with a broad optimum pH range of 5.0 to 7.0. Thus, in the typical operating range of wastewater treatment plants, pH is not a sensitive indicator of phosphorus removal efficiency. The most significant effect for engineering practice, apart from the metal dose, is that of mixing intensity and slow kinetic removal of phosphorus in contact with the chemical sludge formed. Experiments show that significant savings in chemical cost could be achieved by vigorously mixing the added chemical at the point of dosage and, if conditions allow, providing a longer contact time between the metal hydroxide flocs and the phosphate content of the wastewater. These conditions promoted the achievement of less than 0.1 mg/L residual orthophosphate content, even at lower metal-to-phosphorus molar ratios. These observations are consistent with the surface complexation model presented in a companion paper (Smith et al., 2008).     

一种新型环境矿物材料在废水处理中的应用研究

实验研究表明 ,磷矿石作为一种新型环境矿物材料对重金属离子工业废水具有较好的处理效果 ,且自身具有显著的优点。采用分级处理的方法以及磷矿石的合适用量可以使处理后的工业废水达到排放标准甚至饮用标准 ,同时 ,由于磷矿石去除重金属离子速度快 ,在瞬间即可发生作用 ,使得利用动态法进行工业废水的连续处理成为可能 ,而且不会产生二次污染 ,具有工艺应用意义     

Characterization of primary precipitate composition formed during co-removal of Cr(VI) with Cu(II) in synthetic wastewater

BACKGROUND, AIMS AND SCOPE: Hexavalent chromium [Cr(VI)] cannot react with either carbonate or hydroxide to form chromium precipitates. However, by using a precipitation technology to treat plating wastewater containing Cr(VI), Cu(II), Ni(II) and Zn(II), approximately 78% of Cr(VI) (initial 60 mg/L) was co-removed with the precipitation of Cu(II), Ni(II) and Zn(II) (each 150 mg/L) by dosing with Na2CO3 (Sun 2003). Direct precipitation by forming Cu(II)-Cr(VI) precipitates followed by adsorption of Cr(VI) onto freshly formed Cu-precipitates was subsequently found to be the main mechanism(s) involved in Cr(VI) co-removal with Cu(II) precipitation by dosing Na2CO3 stepwise to various pH values (Sun et al. 2003). This study was. carried out to further characterize the formation of primary precipitates during the early stages of copper precipitation and simultaneous removal of Cr(VI) with Cu(II). METHODS: Test metal-solutions were prepared with industrial grade chemicals: CuCl2 x 2H2O, Na2SO4 and K2Cr2207. NaCO3 was added drop-wise to synthetic metal-solution to progressively increase pH. For each pH increment, removal of soluble metals was detected by atomic absorption spectrophotometer (AAS) and surface morphology of precipitates was analyzed by scanning electron microscope (SEM). To further characterize the formation of primary precipitates, a series of MINEQL+ thermodynamic calculations/analyses and equilibrium calculations/ analyses were conducted. RESULTS AND DISCUSSION: MINEQL+ thermodynamic calculation indicated that, for a system containing 150 mg/L Cu(II) and 60 mg/L Cr(VI) with gradual Na2CO3 dosing, if any precipitates can be formed at pH 5.0 or lower, it should be in the form of CuCrO4. Comparison tests using systems containing the same equivalent of Cu(II) plus Cr(VI) and Cu(II) plus SO4(2-) showed that the precipitation occurred at a pH of around 5.0 in the Cu(II)-Cr(VI) system and around 6.0 in the Cu(II)-SO4(2-) system. The discrepancy of the precipitation was indeed caused by the formation of Cu-Cr precipitates. The initiation of copper removal at pH around 5.0 for the Cu-Cr co-removal test was not attributable to the formation of Cu-CO3 precipitates, instead, it was most likely through the formation of insoluble Cu-Cr precipitates, such as CuCrO4 and CuCrO4 x 2Cu(OH)2. Experimental tests, equilibrium calculations, MINEQL+ thermodynamic calculations and surface morphologies for systems using higher concentrations of Cu(II) and Cr(VI) further verified the most probable composition of primary precipitates is copper-chromate. CONCLUSION: In the Cu-Cr co-removal test with Na2O3 dosing to increase pH and induce metal precipitation, copper-chromate precipitates are the primary precipitates produced and contribute to the initial simultaneous removal of copper and chromium.     

Metal ion and other key water quality constituent attenuation in soil columns

A set of soil columns was constructed to simulate discharge of disinfected tertiary treated wastewater to a river via nearby land application or indirect discharge. The system was primarily designed to observe the fate of metal ions and nutrients. The following three experiments were conducted: (1) flow through saturated soils only, which simulates indirect discharge where water is directly applied to groundwater; (2) flow through unsaturated soil followed by saturated flow, which simulates vadose then saturated zone transport; and (3) saturated flow only using ethylene diamine tetraacetic acid-metal chelates, which determined effects of metal organic complexes on metal mobility through the soil. Metal ion attenuation was substantial but not complete in experiments 1 and 2 (removal: 68% Cu2+, 43% Ni2+, 98% Pb2+, and 96% Hg2+), which was somewhat contrary to modeling results. Cyanide attenuation was also monitored (92% removal). In experiment 3, lead attenuation was somewhat reduced (92% removal) and delayed (requiring additional residence time); copper attenuation was significantly reduced (38% removal) and delayed; and nickel concentrations were higher in the 28-day sample (> 80 microg/L) than in the column feed water (58 microg/L). Near-complete denitrification and total phosphorus attenuation were observed. For the water quality constituents studied, unsaturated (vadose zone) transport did not appear to add additional benefit.     

Treatment of refectory oily wastewater by electro-coagulation process

Electro-coagulation was used to treat refectory wastewater with high oil and grease contents. Different operational conditions were examined, including pH, current density, reaction time, conductivity, electrode distance and inlet concentration. The optimum current density was 10-14 A m(-2) within 30 min depending on the wastewater properties tested. Conductivity had little effect on the treatment efficiency. Although the addition of extra salts (e.g., sodium chloride) to the wastewater did not help increase the pollutant removal efficiency, it could save the power consumption significantly. The COD(Cr) and oil removal efficiency descended with increasing electrode distance. The optimal electrode distance was determined to be 10 mm for this equipment in consideration of the treatment cost and efficiency together. The pH effect on the performance of the electro-coagulation process was not very significant in the range of 3-10. The removal efficiency of oil and COD(Cr) under normal condition exceeded 95% and 75%, respectively.     

微波法制备工业污泥含碳吸附剂及其除铬性能

为实现工业集中区污水处理厂的脱水污泥（简称工业污泥）的废物资源化,以工业污泥为原料,通过氯化锌浸渍微波辐射法制备污泥炭吸附剂,探讨了制备过程中不同制备条件对污泥炭吸附剂吸附性能的影响,并用于吸附重金属离子铬。实验结果表明,除了微波功率、辐照时间等主要影响因素外,过滤条件、搅拌时间和盛放介质等因素也会影响污泥炭吸附剂的吸附性能,确定了工业污泥炭吸附剂的最佳制备条件是微波功率490 W,辐照时间10.0 min,氯化锌溶液浓度40％,搅拌时间24 h等,并且再生前后活性炭对含铬废水均有较好的处理效果;活性炭的投加量为1.0 g/L,Cr（Ⅵ）初始浓度和振荡速率分别为50 mg/L和100 r/min时,最佳除铬条件为pH、温度和吸附时间分别为2、室温（25℃）和1.0 h,在此条件下,Cr（Ⅵ）的去除率为98.5%,TCr的去除率为86.1%,从而为工业污泥的资源化提供了一条新途径。