氯化铁浸出废金属回收海绵铜的工艺研究

采用氯化铁选择性浸出工艺对废金属进行综合利用,制备氯化铁及海绵铜。主要考察了废金属浸出、海绵铜洗涤工艺的可行性,并确定浸出工艺的最佳条件。结果表明:在搅拌速度150 r/min、氯化铁溶液质量分数29.91%、浸出剂量为理论量105%、反应温度60℃、反应时间1.0 h的条件下,铁浸出率为94.86%,铜浸出率为3.57%。浸出渣经盐酸溶液洗涤,能有效提高海绵铜的品质。     

三氯化铁蚀刻废液中铬离子去除的研究

研究磷酸盐沉淀法去除三氯化铁蚀刻废液中铬离子的工艺过程,实现三氯化铁再生利用。主要考察沉淀剂磷酸钠使用量、反应温度、溶液pH、搅拌速度等因素对溶液中铬去除率、铁损失率的影响。结果表明,该方法处理效果好,能有效降低溶液中的铬浓度,铬去除率为97.97%,铁损失率为7.25%。     

曝气混凝沉淀过滤技术在煤矿矿井废水处理中的运用

煤矿矿井水是一种具有行业特点的污染源,但又是一种水资源。将煤矿矿井水处理后作为煤矿工业用水或生活杂用水,不仅充分利用了矿井水水资源,而且避免了外排带来的严重污染,同时还可以解决某些矿区缺水的问题,具有明显的经济、环境和社会效益。针对贵州某些煤矿废水悬浮物、BOD、COD超标,铁、锰含量高,pH值低的特点,介绍中和、曝气...     

Arsenic removal by coagulation and filtration: comparison of groundwaters from the United States and Bangladesh

Arsenic contamination of drinking water is a concern in many parts of the world. In the United States, the Environmental Protection Agency recently reduced the maximum contaminant level of arsenic in drinking water from 50 to 10 μ/L (ppb). In Bangladesh the arsenic concentration in drinking water can be as high as hundreds of parts per billion while the maximum contaminant level is 50 ppb. Consequently, there is a great need for new cost-effective methods to remove arsenic from drinking water. Here arsenic removal by coagulation and filtration was investigated using groundwater from a city in southern Colorado in the United States and from Sonargaon in Bangladesh. The results of the bench-scale experiments conducted indicate that coagulation with ferric ions followed by filtration is effective in reducing arsenic concentration in the water tested. However, the actual efficiency of removal is highly dependent on the raw water quality. Further, addition of a polyelectrolyte coagulant aid may lead to improved permeate fluxes during tangential flow microfiltration but has little effect on the residual arsenic concentration.     

Process development of treatment plants for dyeing wastewater

A three‐step methodology that integrates experiments, modeling and synthesis has been developed for the systematic development of a plant for treating dyeing wastewater for discharge and/or reuse. First, wastewater characteristics, discharge water standards, and reuse water quality specifications, etc. are collected as input information. Heuristics developed in our industrial practice and gleaned from the literature are used to guide the designer to come up with preliminary flow sheet alternatives. Then, bench‐scale experiments and pilot plant tests for the relevant unit operations are performed. A computer code accepts the bench‐scale and pilot plant experimental data for regression of model parameters and determines the superior process configuration and equipment operating conditions through sensitivity analysis. The workflow among various stakeholders to reach the final design is presented. Possible extension of the methodology to other industrial wastewater treatment plants is discussed. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Predispersed solvent extraction of negatively complexed copper from water using colloidal liquid aphron containing a quaternary ammonium salt

Negatively complexed copper ion by complexing agent like EDTA (Ethylenediaminetetraacteic acid) was removed by predispered solvent extraction (PDSE) using colloidal liquid aphrons (CLAs) made out of Trioctylmetylammonium chloride (Aliquat 336) diluted with nonpolar kerosene. PDSE was found to have higher mass transfer rate than conventional solvent extraction under experimental conditions without mechanical mixing. The effect of type of water-soluble surfactants, phase volume ratio (PVR), concentration of anionic Sodium Dodecyl Benzene Sulfonate (SDBS) on PDSE was investigated. In addition, the effect of anionic SDBS on back extraction in PDSE was also studied. Under experimental conditions with enough mechanical mixing, the amount of copper transferred to Aliquat 336 core from the pregnant phase was compared in both PDSE by using anionic SDBS and conventional solvent extraction. It is concluded that PDSE using Aliquat 336 CLA can be used for treatment of negatively complexed copper without the influence of surfactant. To optimize CLAs-based process, stability of CLAs containing a quaternary ammonium salt Aliquat 336 diluted with kerosene in the continuous phase was investigated by measuring the volume released to surface. To destabilize CLAs, H⁺, OIL were added. Stability of CLAs was estimated by comparing the half-life obtained. Break-up of destabilization follows pseudo-first-order reaction kinetics at low ionic strength. But, pseudo-first-order model cannot be applied to a region of high ionic strength.     

三氯化铁催化合成乳酸异戊酯的研究

在乳酸0.1mol,异戊醇和六水三氯化铁用量一定条件下,回流分水合成乳酸异戊酯。探讨了催化剂和醇的用量对反应的影响,找出最佳配比。并用傅立叶变换红外光谱仪对产物结构和性能进行表征。结果表明:n(乳酸)∶n(异戊醇)∶n(六水三氯化铁)=1∶2∶0.027时,酯收率79.3%。     

Pilot plant investigation on petrochemical wastewater treatmentfor the removal of copper and chromium with the objective of reuse

There has been great demand for development of technologies that remove toxic heavy metal ions from wastewater. Chemical precipitation operation is known to remove heavy metal ions from water. In this study applicability of alkaline reagents such as Ca(OH)₂ (lime) and NaOH (caustic soda) in removing copper and chromium ions were evaluated. Separation of heavy metals such as chromium compounds from petrochemical industries' cooling water wastes was achieved by conversion of hexavalent chromium, Cr(VI), to trivalent chromium, Cr(III). Maximum conversion occurred in the pH range of 2.0 and 2.3, adjusted by ferrous sulfate and sulfuric acid. Maximum precipitation of Cr(III) occurred at pH 8.7 with addition of Ca(OH)₂, followed by mixing and 2-h sedimentation. At the end, the concentration of chromate was reduced from 30 ppm to 0.01 ppm. In the case of copper, which is found in the form of cupro-ammonia in ammonia plant wastes, it was observed that the presence of ammonia in wastewater prevents effective chemical precipitation. Therefore, the quantity of ammonia was reduced by aeration. The optimum aeration rate was determined to be 70 L/min, and it was found that ammonia concentration reached equilibrium after 5.0 h o f aeration. Furthermore, hydroxide and carbonate methods were evaluated with respect to precipitation of heavy metals at bench scale, and the former was selected as the method of choice. The results obtained in the Jar test were then applied to pilot scale, and it was determined that the optimum pH for maximum copper precipitation was about 12.0 for both lime and caustic soda used in the hydroxide precipitation method. Lime was preferred due to economics and its high speed of precipitation. Finally, using established methods described here, the concentration of copper followed by coagulation with lime, mixing, 2-h sedimentation and filtration through Whatman 0.45 Am filters was reduced from 48.51 mg/L to 0.694 mg/L, which is below the environmental standards for water resources.     

利用电镀酸铜废渣修复碱铜阳极的方法

以9 mol/L硫酸溶解某电镀公司废水处理所产生的酸铜渣(含铜35%~43%),将所得含铜溶液经过滤后作为电解液,采用电解法修复作为阴极的破损碱铜阳极,探讨了阳极类型,电流密度,镀液中硫酸和铜离子含量,以及温度对铜沉积速率的影响。分析了阳极修复前后的纯度和孔隙度,并通过赫尔槽试验对比了修复后的阳极与完好阳极的性能。结果表明,修复后的阳极虽然孔隙度分布不均,但是能够满足碱铜电镀的需要,为处置含铜浓废液、含铜泥渣提供了新的思路。     

Use of limestone obtained from waste of the mussel cannery industry for the production of mortars

Various types of cement−SiO₂−CaCO₃ mortar were prepared by replacing quarry limestone aggregate with limestone obtained as a by-product from waste of the mussel cannery industry. The CaCO₃ aggregate consists mainly of elongated prismatic particles less than 4 μm long rather than of the rounded particles of smaller size (2-6 μm) obtained with quarry limestone. The mechanical and structural properties of the mortars were found to be influenced by aggregate morphology. Setting of the different types of mortar after variable curing times was evaluated by scanning electron microscopy (SEM), thermogravimetric analysis (TG) and mercury intrusion porosimetry (MIP) techniques. Mortars with a high content in mussel shell limestone exhibited a more packed microstructure, which facilitates setting of cement and results in improved mortar strength. The enhanced mechanical properties of the new mortars allow the cement content in the final mortar composition to be decreased and production costs to be reduced as a result.     

Evaluation of cysteine as environmentally friendly corrosion inhibitor for copper in neutral and acidic chloride solutions

The efficiency of cysteine as a non-toxic corrosion inhibitor for copper metal in 0.6 M NaCl and 1.0 M HCl has been investigated by electrochemical studies. Potentiodynamic polarization measurements and electrochemical impedance spectroscopy “EIS” were used to study the effect of cysteine on the corrosion inhibition of copper. Inhibition efficiency of about 84% could be achieved in chloride solutions. The presence of Cu²⁺ ions increases the inhibition efficiency to 90%. Potentiodynamic polarization measurements showed that the presence of cysteine in acidic and neutral chloride solutions affects mainly the cathodic process and decreases the corrosion current to a great extent and shifts the corrosion potential towards more negative values. The experimental impedance data were analyzed according to a proposed equivalent circuit model for the electrode/electrolyte interface. Results obtained from potentiodynamic polarization and impedance measurements are in good agreement. Adsorption of cysteine on the surface of Cu, in neutral and acidic chloride solutions, follows the Langmuir adsorption isotherm. The adsorption free energy of cysteine on Cu (−25 kJ mol⁻¹) reveals a strong physical adsorption of the inhibitor on the metal surface.     

用冶金渣制备聚硅硫酸铁的研究

用钢渣和水渣制备出聚硅硫酸铁,分析了影响因素,制备的聚硅硫酸铁净水用量少、无毒、混凝效果好。     

Fundamental dewatering properties of wastewater treatment sludges from filtration and sedimentation testing

The prediction and optimisation of the performance of dewatering devices such as filters and thickeners requires the laboratory measurement of fundamental material characteristics. This work presents the application of recently developed methods for the extraction of meaningful phenomenological properties from filtration and sedimentation testing of wastewater sludges, which has previously been limited due to theoretical and experimental constraints. The results for a sample of digested wastewater treatment sludge described a material with weak network strength that was quite permeable at low solids concentrations and the gel point was about 1 v/v%. The sample compressed to high solids concentrations at moderate pressures (up to 40 v/v% at 400 kPa) but became extremely impermeable at these high concentrations. The solids concentration dependencies of the material characteristics had a form that was expected for highly compressible materials such as wastewater sludges, but had not been reported previously. The extracted material characteristics were then used to predict the test results to show that the characterisation was valid.     

Influence of the interaction between chloride and thiourea on copper electrodeposition

The interaction between chloride and thiourea in copper electrodeposition in a sulfate-plating bath was investigated. The sole addition of thiourea to the bath increased the polarization of the electrode potential during copper deposition, leading to very fine and smoothly structured deposit but with microscopic nodules distributed over the surface. When chloride was added to a plating solution containing thiourea, the copper deposition mechanism was changed, showing a depolarization of the electrode potential, and the copper deposits were found to have a relatively rougher microstructure, but without the formation of microscopic nodules. However, rough deposit surfaces having no distinct pattern were formed at the macroscopic scale. Observations of roughening evolution show that the rough surface was initiated from small holes formed across the deposit surface during the initial stage of deposition that eventually developed into visibly rough deposits. The copper deposition inside these holes and at other areas was expected to undergo different deposition mechanisms. Copper deposition in the areas that ultimately developed into holes was almost totally inhibited by the thiourea–Cu(I)–chloride complex film, not just in the grain growth process, but over practically the entire electrodeposition process. Conversely, copper deposition occurred in other areas under conditions where nucleation proceeded, but grain growth was inhibited to produce a fine, homogeneous microstructure. An uneven deposit surface that had different microscopic structures in different areas was then formed. The structure of the thiourea–Cu(I)–chloride film was strongly affected by the current density and appeared to break down completely if sufficiently high current density was applied to yield a fine and homogeneous microstructure that was also macroscopically smooth.     

Copper recovery and simultaneous COD removal from copper phthalocyanine dye effluent using bipolar disc reactor

Electrochemical treatment of real acidic effluent of copper phthalocyanine dye manufacturing plant with a view to explore the feasibility of the simultaneous removal of copper and phthalocyanine using a bipolar disc electrochemical reactor has been investigated. Experiments were conducted in a bipolar capillary gap disc stack electrochemical reactor under batch recirculation mode. Electrodes were RuO₂ and IrO₂ coated on titanium as anode and titanium as cathode. Effects of current density, electrolysis time and effluent flow rate on copper recovery and simultaneous COD removal and energy consumption were critically examined. The current density of 2.5 A dm⁻² and flow rate of 20 L h⁻¹ achieved 91.1% COD removal and 90.1% copper recovery with the energy consumption of 50.86 kWh kg⁻¹ for COD removal and simultaneous recovery of copper in a bipolar disc stack reactor.     

An oblique rotating barrel electrochemical reactor for removal of copper ions from wastewater

An experimental study was performed using an oblique rotating barrel cathode to recover copper from a simulated wastewater, which initially contained 100 parts per million (ppm) of cupric ions. The barrel was a perforated cylindrical polypropylene basket having several axial and circumferential fins on its exterior surface. It was partially filled with copper Raschig rings and was partially submerged in the wastewater at a tilted angle from the horizontal position. During the operation, the barrel was slowly rotating about its axis and the copper rings were made as the cathode by connecting them to a d.c. power supply through a dangler contact. The movement of exterior fins and tumbling motion of copper rings provided a high mass transfer rate and a large cathode area for copper electrodeposition reaction. The cupric ion concentration in the wastewater was reduced to less than 1.0 ppm, permitting discharge of the treated wastewater to the drain system. With an operating cell voltage of 2.5–5.0 V, the overall cathode current efficiency was 53–20%, and the electric energy requirement was 4 to 21 kWh per kilogram of copper recovered from the wastewater. An apparent first order reaction rate constant for copper electrodeposition reaction on the Raschig rings was measured as a function of process variables including cell voltage, barrel rotational speed, percentage barrel loading, barrel tilt angle and percent barrel immersion.     

Synthesis of LiFePO4/C cathode material from ferric oxide and organic lithium salts

LiFePO₄/C cathode material has been simply synthesized via a modified in situ solid-state reaction route using the raw materials of Fe₂O₃, NH₄H₂PO₄, Li₂C₂O₄ and lithium polyacrylate (PAALi). The sintering temperature of LiFePO₄/C precursor is studied by thermo-gravimetric (TG)/differential thermal analysis (DTA). The physical properties of LiFePO₄/C are then investigated through analysis using by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM) and the electrochemical properties are investigated by electrochemical impedance spectra (EIS), cyclic voltammogram (CV) and constant current charge/discharge test. The LiFePO₄/C composite with the particle size of ∼200 nm shows better discharge capacity (156.4 mAh g⁻¹) than bare LiFePO₄ (52.3 mAh g⁻¹) at 0.2 C due to the improved electronic conductivity which is demonstrated by EIS. The as-prepared LiFePO₄/C through this method also shows excellent high-rate characteristic and cycle performance. The initial discharge capacity of the sample is 120.5 mAh g⁻¹ and the capacity retention rate is 100.6% after 50 cycles at 5 C rate. The results prove that the using of organic lithium salts can obtain a high performance LiFePO₄/C composite.     

Role of membrane pore size in tertiary flocculation/adsorption/ultrafiltration treatment of municipal wastewater

Flocculation, adsorption onto powered activated carbon (PAC), and ultrafiltration (UF), alone and in combination, were tested for tertiary treatment of the secondary effluent from municipal wastewater treatment at the Ashkelon plant (in southern Israel). Encouraging and reliable results of total organic carbon (TOC) of <3 mg/l were achieved with a combination of 130 mg/l FeCl₃, 0.6 g/l PAC and UF. The relative contribution of the UF membrane to the reduction of TOC changed with the molecular weight cut-off (MWCO) of the membrane, from a negligible 2.9% for a 100-kDa-MWCO membrane to 17% for 10- and 2-kDa membranes. The latter membranes, however, developed significant fouling, with a 35% drop in flux during first 30 min of the filtration cycle. The flux drop for the 50- and 100-kDa membranes was in the low range of 3%. The optimal MWCO interval of 20- to 50-kDa in combination with flocculation/PAC pretreatment gave a significant reduction in organic content with minimal membrane fouling. Detailed GC–MS analysis showed that the combined treatment gave very efficient retention of organic compounds with molecular weights below 800 Da, with the consequent absence of harmful compounds in the tertiary effluent. It was therefore concluded that the recommended flocculation/adsorption protocol constitutes an effective pretreatment for UF and that the obtained tertiary effluent can be used for unrestricted irrigation.     

Effect of plating mode, thiourea and chloride on the morphology of copper deposits produced in acidic sulphate solutions

The influence of plating mode, chloride and thiourea (TU) on morphology of copper deposits has been studied. All experiments were conducted on disc electrodes rotating at 500 rpm and an average current density of 4 A dm⁻² to produce 10 μm thick deposits. In additive-free solutions, the use of pulsed current (PC) improved deposit morphology and brightness over DC plating. In the presence of thiourea (no Cl⁻), the deposits obtained by DC and PC plating were similar under most plating conditions. The presence of thiourea generally improved deposit quality over that obtained in additive-free solutions, but caused the formation of microscopic nodules and the deposits to appear slightly cloudy, resulting in lower reflectances than that of a polished uncoated copper surface. The addition of Cl⁻ to thiourea-containing solutions strongly influenced deposit morphology at both microscopic and macroscopic scales depending on chloride concentration and pulse conditions. It prevented nodule formation and created microscopically bright and reflective deposits, but caused extreme macroscopic roughness. Nevertheless, PC plating at 50 Hz in solutions containing appropriate amounts of thiourea and Cl⁻ was found to yield macroscopically and microscopically smooth deposits with reflectance similar to that of a polished uncoated copper substrate.