电镀废水处理工程设计实例

在实际工程中,采用何种方法处理电镀废水,需要根据具体条件加以考虑.讨论了含铬废水、含氰废水、酸碱重金属废水的处理方法和原理,结合西安某厂电镀废水处理的具体改造工程,设计了一套电镀废水的处理工艺流程,确定以化学还原法处理含铬废水,以碱性氯化法处理含氰废水,以碱性沉淀法处理酸碱重金属废水.整个工程处理设备较少、造价低、效果稳定,能承受大水量和高浓度负荷的冲击,出水水质达到国家污水综合排放标准.     

Small hazardous waste generators in developing countries: use of stabilization/solidification process as an economic tool for metal wastewater treatment and appropriate sludge disposal

The aim of this study was to propose a profitable destination for an industrial sludge that can cover the wastewater treatment costs of small waste generators. Optimized stabilization/solidification technology was used to treat hazardous waste from an electroplating industry that is currently released untreated to the environment. The stabilized/solidified (S/S) waste product was used as a raw material to build concrete blocks, to be sold as pavement blocks or used in roadbeds and/or parking lots. The quality of the blocks containing a mixture of cement, lime, clay and waste was evaluated by means of leaching and solubility tests according to the current Brazilian waste regulations. Results showed very low metal leachability and solubility of the block constituents, indicating a low environmental impact. Concerning economic benefits from the S/S process and reuse of the resultant product, the cost of untreated heavy metal-containing sludge disposal to landfill is usually on the order of US$ 150-200 per tonne of waste, while 1tonne of concrete roadbed blocks (with 25% of S/S waste constitution) has a value of around US$ 100. The results of this work showed that the cement, clay and lime-based process of stabilization/solidification of hazardous waste sludge is sufficiently effective and economically viable to stimulate the treatment of wastewater from small industrial waste generators.     

氰化滚镀铜工艺实践与探讨

氰化滚镀铜溶液中碳酸钠含量和主盐浓度不当,都会影响产品的质量.影响碳酸钠含量的因素较多,如溶液的pH值及NaOH浓度,槽电压等.对其具体影响进行了研究,提出措施:NaOH浓度在5.0～7.5 g/L可以将碳酸钠浓度控制在工艺范围内;降低镀槽电压和增加阳极面积有利于降低碳酸钠的浓度;较高的主盐浓度可以提高镀液的电流效率和均镀能力,有利于降低电镀成本.     

Recovery and reutilisation of copper from metal hydroxide sludges

Sludges generated from electroplating wastewaters contain high concentrations of metals. Studies have confirmed that the concentrations of several metals in the sludge exceed that of those found in natural ores. A very good example is in the case of copper. The natural copper ore contains less than 1% of copper, whereas copper precipitate sludges from the electroplating industry may have an average of 5–10% of copper. Thus, they are one of the largest sources of untapped metal-bearing secondary materials amenable to metals recovery. In Malaysia, most of these metal-bearing sludges are disposed in specially engineering landfills, as many of them do not have the proper incentives and recovery technology. Very less metal recovery is being carried out, and there seems to be a huge waste in these valuable metal resources. With regards to that, an experimental study was carried out to develop and optimise a method of copper recovery from metal hydroxide sludges. Sludge samples containing high concentrations of copper were obtained from a local electroplating plant for the study. A procedure based upon mineral acid leaching or solubilisation was carried out. Two different types of acids, hydrochloric acid (HCl) and sulphuric acid (H₂SO₄) were used to compare the extractability of copper. Experiments were conducted at various acid concentrations and temperatures to determine the maximum amount of copper recoverable. From the results obtained, maximum copper (95%) was solubilised using H₂SO₄ of 10 M at temperature 110°C, for a leaching period of 4 h. These copper concentrated solutions were then heated and crystallised to form CuSO₄ crystals. These crystals were then washed with water and purified. They can be then further treated and reutilised in the metallurgical industry. This study introduces a sustainable method of utilising an electroplating sludge containing valuable metals.     

Oxidation of cyanide in aqueous solution by chemical and photochemical process

Cyanide waste is found predominantly in industrial effluents generated from metallurgical operations. The toxicity of cyanide creates serious environmental problems. In this paper, oxidation of cyanide in aqueous solution was investigated using chemical and photochemical process. Chemical oxidation was studied at room temperature using H2O2 as oxidant and Cu2+ as catalyst. Photochemical oxidation was studied in an annular type batch photoreactor of 1l capacity using 25 W low-pressure (81.7% transmission at 254 nm wavelength) ultraviolet (UV) lamp along with H2O2 as oxidant. The effect of Cu2+ catalysis was also studied. It was observed that in absence of UV source, the degradation of cyanide by H2O2 alone was very slow, whereas copper ions accelerated the rate of reaction thereby acting as catalyst. Copper formed a complex with cyanide ion, i.e. tetracyanocuprate which had greater affinity for H2O2. Cyanate hydrolysis was also favoured by copper ions. As Cu2+ ion concentration was increased, rate of degradation also increased. Photochemical oxidation by H2O2 and Cu2+ was found to be the best system for cyanide degradation. CN- (100 mg/l) was degraded to non-detectable level in 9 min at pH 10.0 with optimum H2O2 dose of 35.5 mM and Cu2+ dose of 19 mg/l. Reaction kinetics of cyanide oxidation was found to be pseudo-first order and the rate constant has been determined for different processes.     

Integrated copper-containing wastewater treatment using xanthate process

Although, the xanthate process has been shown to be an effective method for heavy metal removal from contaminated water, a heavy metal contaminated residual sludge is produced by the treatment process and the metal-xanthate sludge must be handled in accordance with the Taiwan EPA's waste disposal requirements. This work employed potassium ethyl xanthate (KEX) to remove copper ions from wastewater. The toxicity characteristic leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) were used to determine the leaching potential and stability characteristics of the residual copper xanthate (Cu-EX) complexes. Results from metal removal experiments showed that KEX was suitable for the treatment of copper-containing wastewater over a wide copper concentration range (50, 100, 500, and 1000 mg/l) to the level that meets the Taiwan EPA's effluent regulations (3mg/l). The TCLP results of the residual Cu-EX complexes could meet the current regulations and thus the Cu-EX complexes could be treated as a non-hazardous material. Besides, the results of SDLT indicated that the complexes exhibited an excellent performance for stabilizing metals under acidic conditions, even slight chemical changes of the complexes occurred during extraction. The xanthate process, mixing KEX with copper-bearing solution to form Cu-EX precipitates, offered a comprehensive strategy for solving both copper-containing wastewater problems and subsequent sludge disposal requirements.     

液膜法从金矿贫液中除氰及回收氰化钠的小型工业化试验

本文提出了一种用乳化液膜法处理金矿含氰废水的新工艺,建立了规模为日处理量10～20m~3的一套小型工业化试验的液膜装置。研究了传质的影响因素及操作参数对除氰和回收氰化钠的影响。经运转操作证明,用该工艺流程能有效地从锌粉置换后的含氰贫液中将氰化钠浓缩回收并可重复使用,同时,使排放液中的游离氰根离子浓度低于0.5mg/L,达到国家排放标准。整个过程,氰的去除率达99％以上,氰化钠的回收率高于90％。经三个月的运转操作进行了经济估算,证明液膜法较其它方法优越。     

高压脉冲电凝系统治理电镀涂装废水

高压脉冲电凝系统（High Voltage Electrocagulation System)为当今世界新一代电化学水处理设备，对表面处理，涂装废水以及电镀混合废水中的铬、锌，镍 ，铜、镉、氰化物，磷，油等污染物有显著的治理效果，是较理想的表面处理综合废水治理新工艺。     

Activated sludge respirometry to assess solar detoxification of a metal finishing effluent

Inhibition of the respiration of activated sludge has been tested as a convenient method to estimate toxicity of aqueous solutions containing copper and cyanide, such as metal finishing effluents; according to this method, an EC50 of 0.5 mg/l was determined for CN(-) and 3.0 mg/l for copper. Solar detoxification of cyanide-containing solutions was studied using TiO2, but this process was unfavourable because of the inhibitory role that plays the copper ions present in real effluents on the oxidation of cyanide. On the other hand, the oxidative effect of hydrogen peroxide was greatly enhanced by Cu2+ and solar irradiation, as complete elimination of free and complexed cyanide could be accomplished, together with precipitation of copper, in experiments carried out at pilot plant scale with real metal finishing effluents. Under these conditions, total detoxification was achieved according to respirometric measurements although some remaining toxicity was determined by more sensitive Vibrio fischeri luminescent assay.     

Novel chitosan derivative for the removal of cadmium in the presence of cyanide from electroplating wastewater

Chitosan was chemically modified by introducing xanthate group onto its backbone using carbondisulfide under alkaline conditions. The chemically modified chitosan flakes (CMC) was used as an adsorbent for the removal of cadmium ions from electroplating waste effluent under laboratory conditions. CMC was found to be far more efficient than the conventionally used adsorbent activated carbon. The maximum uptake of cadmium by CMC in batch studies was found to be 357.14 mg/g at an optimum pH of 8.0 whereas for plain chitosan flakes it was 85.47 mg/g. Since electroplating wastewater contains cyanide in appreciable concentrations, interference of cyanide ions in cadmium adsorption was found to be very significant. This problem could be easily overcome by using higher doses of CMC, however, activated carbon was not found to be effective even at higher doses. Due to the high formation constant of cadmium with xanthate and adsorption was carried out at pH 8, cations like Pb(II), Cu(II), Ni(II) and Zn(II) did not interfere in the adsorption. Dynamics of the sorption process were studied and the values of rate constant of adsorption were calculated. Desorption of the bound cadmium from CMC was accomplished with 0.01 N H(2)SO(4). The data from regeneration efficiencies for 10 cycles evidenced the reusability of CMC in the treatment of cadmium-laden wastewater.     

浅析电镀行业的清洁生产措施

随着科学技术与生产的发展,电镀所涉及的领域越来越广。已经遍及人们生活的各个方面。但是电镀生产污染令人担忧,据统计,我国每年排出约4亿吨重金属废水,5万吨废渣。酸雾3000万立方米。更严重的是,一些重金属,如铅、隔、铬通过土壤吸收后进人庄稼内,人食用后会在人体内造成积累性中毒或致癌。因此电镀行业的清洁生产就成为当务之急,这也符合国家的节能减排政策,符合电镀工业的可持续发展。     

Ultrasonic recovery of copper and iron through the simultaneous utilization of Printed Circuit Boards (PCB) spent acid etching solution and PCB waste sludge

A method was developed to recover the copper and iron from Printed Circuit Boards (PCB) manufacturing generated spent acid etching solution and waste sludge with ultrasonic energy at laboratory scale. It demonstrated that copper-containing PCB spent etching solution could be utilized as a leaching solution to leach copper from copper contained PCB waste sludge. It also indicated that lime could be used as an alkaline precipitating agent in this method to precipitate iron from the mixture of acidic PCB spent etching solution and waste sludge. This method provided an effective technique for the recovery of copper and iron through simultaneous use of PCB spent acid solution and waste sludge. The leaching rates of copper and iron enhanced with ultrasound energy were reached at 93.76% and 2.07% respectively and effectively separated copper from iron. Followed by applying lime to precipitate copper from the mixture of leachate and rinsing water produced by the copper and iron separation, about 99.99% and 1.29% of soluble copper and calcium were settled as the solids respectively. Furthermore the settled copper could be made as commercial rate copper. The process performance parameters studied were pH, ultrasonic power, and temperature. This method provided a simple and reliable technique to recover copper and iron from waste streams generated by PCB manufacturing, and would significantly reduce the cost of chemicals used in the recovery.     

铜铁界面含氧层对镀层结合强度的影响

镀层与基体界面间含氧层的存在,影响电镀层与基体之间金属键的形成,进而影响镀层的结合强度.用氰化物和焦磷酸盐两种工艺在铁片上镀铜,对镀层进行恒电流极化,并以氩离子深度刻蚀和X射线光电子能谱相结合的方法进行检测.电沉积初始电位-时间曲线显示,两种镀铜工艺,结合强度好的出现了基体表面的还原活化电位平阶,结合强度差的焦酸盐镀铜未出现活化就发生了金属的电沉积,而且铜镀层与基体界面含氧量有增高的现象.铜镀层与铁基底界面间含氧层的存在是影响镀层结合强度的主要原因.通过控制金属电沉积初始电位可提高镀层的结合强度.     

The ultrasonically assisted metals recovery treatment of printed circuit board waste sludge by leaching separation

This paper provides a practical technique that realized industrial scale copper and iron separation from printed circuit board (PCB) waste sludge by ultrasonically assisted acid leaching in a low cost, low energy consumption and zero discharge of wastes manner. The separation efficiencies of copper and iron from acid leaching with assistance of ultrasound were compared with the one without assistance of ultrasound and the effects of the leaching procedure, pH value, and ultrasonic strength have been investigated in the paper. With the appropriate leaching procedure, a final pH of 3.0, an ultrasonic generator power of 160 W (in 1 l tank), leaching time of 60 min, leaching efficiencies of copper and iron had reached 97.83% and 1.23%, respectively. Therefore the separation of copper and iron in PCB waste sludge was virtually achieved. The lab results had been successfully applied to the industrial scaled applications in a heavy metal recovery plant in city of Huizhou, China for more than two years. It has great potentials to be used in even the broad metal recovery practices.     

Stabilization of Cu in acid-extracted industrial sludge using a microwave process

The leaching concentration of copper ions from the industrial sludge that has been extracted using sulfuric acid may still exceed 15 mg/L, which is the leaching standard of the toxicity characteristic leaching procedure (TCLP) for hazardous waste in Taiwan. Therefore, the acid-extracted industrial sludge is still an important source of hazardous waste. Usually, hazardous waste in Taiwan must be solidified and passed through the TCLP test before it is disposed in a landfill. The aim of this study is to develop a microwave process to stabilize copper ions in the sludge to replace the use of traditional solidification. In this study, two parameters--the reaction time of the microwave process and the additive reagents--were considered. The efficiency of stabilization of the microwave process was evaluated from the result of the TCLP test. The results showed that the stabilization efficiency of copper ions obtained using a microwave process without any added reagent depends highly on the property of the original acid-extracted sludge. Under some conditions, the leaching concentrations were much lower than those of the raw sludge. In additive reagent systems, the results showed that iron powder promoted the stabilization of copper ions more than the other additives such as sodium carbonate and sodium silicate. The leaching concentration of copper ions decreased dramatically from 179.4 to 6.5mg/L below in the iron additive system.     

槽边循环电解法回收电镀废水中Ni的研究

对槽边循环电解法回收电镀废水中Ni进行了分阶段实验研究,包括小型试验、扩大试验以及系统扩大试验。试验结果表明,适合工业生产中使用的操作条件如下:Ni离子浓度可在0.5～2.5g/L变化,电流密度40～80 A/m2,槽电压3～6 V,pH=4.5～5.5;当Ni离子浓度保持在1.0～2.5g/L,若连续操作电流密度采用100～150 A/m2,则电流效率仍大于40%;若从高浓度操作到低浓度,每次回收到0.5 g/L,电流密度应取40～80 A/m2,操作10次后,可回收到使浓度小于0.1 g/L,弃掉,则回收槽的回收率大于99%;由3类不同规模试验的对比中可以看出,在相同条件下,电流效率几乎相等。研究表明,采用槽边循环电解法回收电镀废水中的Ni是完全可行的,且可保证较高回收效率。     

镀铜废水中Cu2+含量的5,6-二氯-苯并噻唑偶氮苯甲酸显色光度法测定

利用5,6-二氯-苯并噻唑偶氮苯甲酸(5,6-diCl-BTAEB)与铜的显色反应,在pH值为5.0的NH4OAcHOAc缓冲溶液中,在乳化剂OP存在下,使5,6-diCl-BTAEB与Cu2+反应生成2:1稳定的配合物,可实现对Cu2+的测定.其最大吸收波长为650 nm,表观摩尔吸光系数为5.57×104L/(mo...     

Copper leaching from a sandy soil: mechanism and parameters affecting EDTA extraction

A series of 24h batch tests of copper extraction from a sandy soil were performed by washing the soil with aqueous solution of ethylenediaminetetraacetic acid, EDTA. EDTA versus copper molar ratio were in the range between 1 (equimolar tests) and 13.3. The tests were performed at three selected liquid/solid ratio, 5, 12.5 and 25. Results show that decreasing the pH of the washing solution an higher copper extraction yield was achieved: an almost complete copper extraction was achieved after 23 h of mixing at a L/S = 5, and after 5 h of mixing at an L/S = 12.5. The mechanism of copper extraction was found to involve two sequential processes: the former dissolution of metal salts, that lead to an initial high concentration of both copper and some competitive cations (essentially Ca(2+)), and the following EDTA exchange reaction between calcium and copper complexes, which corresponded an increase of pH in the washing solution. A negligible extraction of Fe(3+) was also observed at the investigated operative conditions.     

Heavy metal recovery from electroplating effluent using adsorption by jute waste-derived biochar for soil amendment and plant micro-fertilizer

Clean Technologies and Environmental Policy - Effluent from electroplating industries contains various toxic heavy metal ions such as chromium, nickel, lead, cadmium, copper and zinc. Recovery of...     

硫酸盐镀铜的研究进展

铜的性质决定了铜在工业应用中的重要性,特别是目前在微电子工业中的决定性作用,使铜的电沉积过程成为研究热点.结合铜在微电子工业中的应用,综述了硫酸盐镀铜中铜的电沉积机理、铜镀层微结构、添加剂对铜电沉积过程的影响以及铜电沉积初期行为方面的研究进展.指出了铜电沉积未来的研究方向.