Recovery of Copper（II） and Nickel（II） from Plating Wastewater by Solvent Extraction

The solvent extraction technology, was applied to recover Cu^2＋ and Ni^2＋ from plating wastewater.Lix984N was chosen as the extractant due to-its gooff extraction performance. The influence parame-ters were examlned. The results show that the separation of Cu^2＋ and Ni＂ from sulphate medium can be realized by adjusting pH value with the help of Lix984N. For extracting Cu^2＋ and Ni^2＋, the optimal pH values are 4 and 10.5, and the maximal extraction percentages are 92.9% and 93.0%, respectively .With recovered Cu^2＋ and Ni^2＋ stripped in 170g.L^ -1 and 200 g.L^-1 H2SO4 medium, the stripping percentages of Cu^2＋ and Ni^2＋ are 92.9% and 93.0%, respectively. This method is simple and can be used to recover Cu^2＋ and Ni^2＋ from plating wastewater. And a flow sheet for separation of Cu^2＋ and Ni^2＋ is presented.

Cascade sulfidation and separation of copper and arsenic from acidic wastewater via gas-liquid reaction

Copper and arsenic in acidic wastewater were separated by cascade sulfidation followed by replacement of arsenic in theprecipitates by copper in the solution which was realized by recycling precipitates obtained in the first stage into the initial solution.The effects of reaction time,temperature and H2S dosage on copper and arsenic removal efficiencies as well as the effects of solid-toliquidratio,time and temperature on the replacement of arsenic by copper were investigated.With20mmol/L H2S at50°C within0.5min,more than80%copper and nearly20%arsenic were precipitated.The separation efficiencies of copper and arsenic werehigher than99%by the replacement reaction between arsenic and copper ions when solid-to-liquid ratio was more than10%at20°Cwithin10min.CuS was the main phases in precipitate in which copper content was63.38%in mass fraction.

Recovery of copper sulfate after treating As-containing wastewater by precipitation method

The solid sodium hydroxide neutralized acidic As-containing wastewater till pH value was 6. Green copper arsenite was prepared after copper sulfate was added into the neutralized wastewater when the molar ratio of Cu to As was 2：1 and pH value of the neutralized wastewater was adjusted to 8.0 by sodium hydroxide. The arsenious acid solution and red residue were produced after copper arsenite mixed with water according to the ratio of liquid to solid of 4：1 and copper arsenite was reduced by SO2 at 60℃ for 1 h. The white powder was gained after the arsenious acid solution was evaporated and cooled. Copper sulfate solution was obtained after the red residue was leached by H2SO4 solution under the action of air. The results show that red residue is Cu3（SO3）2·2H2O and the white powder is As2O3. The leaching rate of Cu reaches 99.00% when the leaching time is 1.5 h, molar ratio of H2SO4 to Cu is 1.70, H2SO4 concentration is 24% and the leaching temperature is 80 ℃. The direct recovery rate of copper sulfate is 79.11% and the content of CuSOa·5H2O is up to 98.33% in the product after evaporating and cooling the copper sulfate solution.

Preparation of Granulated Adsorption Material of Water-quenched Slag/rectorite Composite for Removal of Cu(Ⅱ)Ions from Copper Smelter Wastewater

The preparation of granulated adsorption material of water-quenched slag/rectorite composite and the treatment of Cu （ Ⅱ ）-containing copper smelter wastewater with the adsorption material were studied. The experimental results showed that under the conditions with the mass ratio of water-quenched slag to rectorite of 1：1, 10% additive of industrial starch （IS）, and 50% water, and a calcination temperature of 400 ℃, the granulated adsorption material prepared had a density of 1.06 kg/m^3, a porosity of 62.29%, water absorption rate of 58.82%, and compressive strength of 2.22 MPa. The efficiency of wastewater treatment was the best, whereas the rate of spallation loss was low. Under the conditions of natural pH, with the addition of the granulated adsorption material of 0.05 g/mL, a reaction time of 40 minutes, and temperature of 25 ℃, the efficiency of the granulated adsorption material for the removal of Cu （ Ⅱ ） ions from the copper smelter wastewater attained 98.2%, and the quality indexes of the wastewater after treatment conformed with the first level of integrated wastewater discharge standard （GB8978-1996）. The reclamation of the used granulated adsorption material was carried out by de-sorption of the Cu （ Ⅱ） ions from the surface with 1 mol/L sodium chloride solution. The de-sorption rate was 96.4%, and the adsorption material can be reused many times to treat copper smelter wastewater.

Coordination configurations of cupric tartrate in electronic industry wastewater

The coordination structure of cupric tartrate(Cu−TA)complex was investigated by ultraviolet−visible(UV-Vis)and liquid chromatography/mass spectrometer(LC-MS)firstly;furthermore,effective coordination configurations and electronic properties of Cu−TA in aqueous solution were systematically revealed by density functional theory(DFT)calculations.Consistently,Job plots show the possible existence of[Cu(TA)]and[Cu(TA)_(2)]^(2-)at 230 and 255 nm based on UV-Vis results.LC-MS results confirm the existence of the single and high coordination complexes[Cu_(2)(TA)_(2)]^(+),[Cu(TA)_(2)]^(+)and[Cu_(2)(TA)_(3)(H_(2)O)_(2)(OH)_(2)]^(2+).DFT calculation results show that carboxylic oxygen and hydroxyl oxygen of tartaric acid(TA)are preferred sites for Cu(Ⅱ)coordination.[Cu(TA)](1H,3H sites O of TA coordinated with Cu(Ⅱ)),[Cu(TA)_(2)]^(2-)(two 1^(C),2^(H) sites O of TA coordinated with Cu(Ⅱ)),and[Cu(TA)_(3)]^(4-)(three 2H,3H sites O of TA coordinated with Cu(Ⅱ))should be dominant coordination configurations of Cu−TA.The corresponding Gibbs reaction energies are-170.1,-136.2,and-90.2 kJ/mol,respectively.

铝粉还原污酸中砷新工艺研究

由于硫化精矿中砷含量越来越高,致使烟气处理过程产生的污酸中砷含量也越来越高,同时污酸中含有铜、铁等有价金属。目前污酸除砷方法多以除砷为目的,形成的含砷渣属于危废,还需要二次处理。本研究研发了还原除砷新工艺,首先向污酸中加入硫化砷渣进行脱铜预处理并回收铜,然后用铝粉还原脱铜后液中的砷回收砷,最后向脱砷液中加入硫酸钾回收铝,还原后液回收还原剂后采用两段中和法处理。试验研究结果表明,在加入铜离子摩尔量1.1倍的硫化砷渣、反应温度85℃、反应时间3 h的条件下,污酸中的铜含量由2000 mg/L降至196 mg/L,硫化铜渣返熔炼配料系统;在还原温度70℃、还原时间2 h,还原剂用量1.8倍的条件下,砷的还原率大于96%,还原后液中的砷含量低于300 mg/L,得到的砷渣品位大于95%,可用于后续制备高品位单质砷;在硫酸钾用量1.1倍、反应温度常温、反应时间2 h的条件下,溶液含铝3.6 g/L,得到的明矾可达到《工业硫酸铝钾》(HG/T2565—2007)一等品标准。该方法除砷效果好,且能将污酸中的砷转变为具有经济价值的砷产品,还不会产生硫化氢气体,具有应用推广价值。

锂电三元前驱体工艺设计要点控制研究

锂电池材料分为正极材料、负极材料、隔膜、电解液等,正极材料是锂电池材料的关键性材料之一,三元前驱体是生产三元正极材料的重要上游材料。在三元前驱体工艺设计中,关注重点工艺控制条件、废水处理工艺设计、铜铁锌等异物引入的防护措施、工艺智能化设计,优化设计提升产品的竞争力,推动锂电池行业的发展。

基于分类处理-分质利用的电子电镀废水中金属离子资源化处理新技术研究进展

随着城市化、工业化以及农业现代化进程加快,电子信息行业快速发展的同时产生了大量电子电镀重金属废水。这类型废水成分复杂、赋存稳定、危害极大且具有一定资源属性,目前较流行的混凝沉淀法处理效果不佳,污泥量大,存在二次污染且无法资源化回收。基于此,归纳总结了电子电镀重金属废水的来源与危害,归纳分析了现行主要技术存在的不足,系统介绍了基于分类处理-分质利用的电子电镀废水中金属离子资源化处理的进展与最新研究成果,为电子信息行业清洁生产、重金属废水污染防治和资源化处理提供借鉴与技术支撑。

两级A/O+铁盐耦合沉淀组合工艺处理酞菁铜生产废水

经除铜预处理后的酞菁铜生产废水含有大量难生物降解的酞菁等含氮有机物,采用传统的“生物处理+深度处理”组合工艺处理该废水时,处理效果不稳定,且出水总氮(TN)难以达标。采用“两级A/O+铁盐耦合沉淀”组合工艺处理该废水,考察其处理效果,并利用荧光光谱、紫外光谱、腐殖质(HS)含量测定探究废水中污染物的去除机理。结果表明,“两级A/O+铁盐耦合沉淀”组合工艺处理酞菁铜生产废水,化学需氧量(COD)、氨氮、TN的去除率分别为96.5%、99.8%、93.2%;两级A/O可有效去除废水中绝大部分污染物,并使出水中HS含量提高,再利用对HS和有机氮具有高效去除作用的铁盐耦合沉淀技术处理两级A/O出水,使最终出水的COD、氨氮、TN分别为29、0.5、23.8 mg/L,实现了出水达标排放。

铜铝双金属材料对硝基苯废水的还原降解研究

以废旧铝箔为原料,采用化学镀铜的方式制备了铜铝双金属材料(Cu@Al^(0))并应用于硝基苯废水的还原降解。采用X射线衍射(XRD)、扫描电子显微镜(SEM)等手段对制备的材料进行表征,系统考察了镀铜率、初始pH、Cu@Al^(0)投加量、硝基苯初始浓度对硝基苯降解效果的影响,最后借助紫外可见吸收光谱(UV-Vis)和气相色谱(GC)进一步揭示了Cu@Al^(0)对硝基苯的还原降解机理。结果表明,金属铜可成功负载在铝箔表面,当铜负载率为3.43%,初始pH=3,Cu@Al^(0)投加量为0.50 g,硝基苯初始质量浓度为100 mg/L,反应时间为20 min时硝基苯的降解率可达88.4%,且Cu@Al^(0)具有良好的循环利用性能。Cu@Al^(0)对硝基苯的降解是从亚硝基苯到羟基苯胺再到苯胺的逐步还原过程,初始pH过高会影响中间产物亚硝苯进一步还原成最终产物苯胺。

铜选矿废水对碱激发粉煤灰/矿渣胶凝材料性能的影响

为加速铜选矿废水(CMw)的资源化利用,采用CMw作为拌合水制备碱激发粉煤灰/矿渣(AAFS)胶凝材料,研究了不同CMw掺量对AAFS凝结时间、水化特性、水化产物、孔结构和抗压强度的影响。结果表明:在AAFS中掺入CMw会略微延长其凝结过程,但略微促进AAFS的水化过程,这与CMw的酸性、有机药剂残留和金属离子有关。通过掺入不同量CMw, AAFS的凝胶孔不断增加,而过渡孔体积逐渐减小,抗压强度呈现出先增大后略微降低的趋势。当CMw掺量为50%时,AAFS的抗压强度提升幅度最大,分别为12.23%(3 d)、21.07%(7 d)、16.74%(28 d)。研究结果可为铜选矿废水的资源化利用提供新的思路和参考。

粉煤灰基沸石吸附废液中氨氮化物与铜离子的试验研究

开展了粉煤灰基沸石吸附电镀废液中氮氧化物和铜离子的试验研究。结果表明:粉煤灰基沸石吸附铜离子的适宜条件为:pH值8,溶液中铜离子初始质量浓度200 mg/L,吸附时间0.45 h,温度200℃;粉煤灰基沸石吸附氨氮化物的适宜条件为:粉煤灰基沸石投入量8 g/L,pH值8,吸附时间0.60 h,溶液中氨氮化物初始质量浓度150 mg/L;粉煤灰基沸石吸附铜离子的吸附过程为物理吸附过程,粉煤灰基沸石对氨氮化物的吸附是离子交换和物理吸附共同作用的结果。

沸石原位生物再生强化短程硝化处理高氨氮废水

为解决高浓度游离氨(FA)抑制氨氧化菌而造成高浓度氨氮废水无法进行生物处理的问题,采用添加天然沸石缓解FA的抑制影响。向SBR中添加天然斜发沸石并以短程硝化处理氨氮为2 210 mg/L的铜氨废水,在运行第86天时反应器在1.105 kg/(m^(3)·d)的氨氮负荷下达到98.5%的氨氮去除率。反应过程中原位生物再生保证了天然沸石的持续强化效果,沸石再生率为99.0%~106.3%。通过对污泥胞外聚合物(EPS)含量及成分分析发现进水氨氮的增加导致EPS含量升高,且在铜离子的胁迫下EPS中的蛋白质质量分数升高,促进了污泥颗粒化的形成。高通量测序结果显示亚硝化单胞菌属为主要氨氧化功能菌属,其相对丰度变化范围为10.3%~51.7%。丛毛单胞菌属(Comamonas)在高浓度氨氮环境下快速增长,其相对丰度从第22天的0.6%增长至第86天的29.9%。短程硝化在天然沸石的强化下实现了对铜氨废水的稳定高效处理。

酸性矿山废水中多种有价金属的高效分离

酸性矿山废水(AMD)中多种有价金属的高效分离回收,是重金属减排和资源化利用的关键。文章通过中和沉淀实验和静态吸附实验探究回收有价金属的最佳沉淀和吸附pH,成功开发了中和沉淀—离子交换—中和沉淀组合工艺,并应用于大宝山AMD的处理。结果表明,AMD在pH为3.00和9.80中和沉淀时,分别沉获64%的Fe_(2)O_(3)富铁渣和51%的Mn O富锰渣。采用离子交换树脂分别在pH 3.95和6.10条件下对AMD中的Cu和Zn进行吸附,得到质量浓度为Cu^(2+)11~26 g/L,Zn^(2+)10~20 g/L的两种解吸液。通过该组合工艺,AMD中的各金属Fe、Cu、Zn和Mn的回收率分别为:96%、81%、70%和60%,实现了有价金属的高效分离回收。若采用此工艺回收大宝山2000 m^(3)/d的AMD中的铜、锌、锰硫酸盐,每年的利润为119万元,经济效益非常显著。此处理工艺为酸性矿山废水的高效资源化利用提供了新路径。

山竹皮吸附剂对铜离子的吸附行为及其燃烧特性研究

以山竹果皮渣为原料,经过异丙醇脱色、碱性试剂活化制备出吸附材料,用于吸附溶液中的铜离子。实验结果表明,pH值升高有利于山竹皮吸附剂吸附铜离子,最大吸附容量达1.5 molCu^(2+)/kg,且30 min内可达到吸附平衡。负载铜离子数量对吸附剂燃烧热分解的特征温度有显著影响,铜离子浓度低于2 mmol/L时,负载的铜离子数量增加,其开始热分解以及剧烈燃烧分解的温度点显著降低;铜离子浓度高于2 mmol/L后,其热分解温度特征值不再发生明显变化。铜离子在燃烧过程中扮演催化剂的作用,能有效促进燃烧反应。

某金铜矿2种废水中和回收利用铜试验研究

针对某金铜矿含铜含氰废水和含铜酸性废水,开展了HCN挥发性试验、中和条件试验、铜资源回收试验、普鲁士蓝制备试验研究,考察了铁沉淀率、总氰化合物去除率和铜回收情况。结果表明:一段中和除氰除铁控制pH值为4.0,HCN挥发率为0.04%,铁沉淀率大于98%,总氰化合物去除率大于97%;二段过氧化氢破氰后,总氰化合物质量浓度小于5.0 mg/L。废水年处理量按87万m^(3)计算,经济效益高于4000万元。该研究为金精矿生物槽浸工艺除氰提供了思路,可大幅度降低破氰成本,同时为普鲁士蓝染料和电化学能源相关领域的电池前驱体材料制备提供参考。

PCB碱性蚀刻废液高效回收铜粉研究

针对PCB碱性蚀刻废液含铜量高、腐蚀性强等特点,在氮气气氛下采用水合肼液相还原制备高质量铜粉,同时实现蚀刻液再生。研究了液相还原气氛、肼与铜离子的摩尔比、反应温度和反应时间等对沉铜效率以及产物组成的影响。通过电感耦合等离子体质谱(ICP)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)和激光粒度分析仪(LDPA)等对蚀刻液成分、产物物相、形貌结构以及铜粉粒度分布进行表征。实验结果表明:空气气氛下液相还原过程中易产生一价铜,导致产物不纯且沉铜率较低;氮气气氛下肼还原效率显著提高,当肼与铜离子摩尔比≥0.64∶1.00、温度≥90℃时,沉铜率高达99.9%,还原产物以单质铜为主,伴有少量CuCl和Cu_(2)O杂质。经碱洗转化、氢还原后得到的铜粉产品纯度不低于99.9%,粒度均匀,满足工业质量标准。

含砷含镍高酸硫酸铜结晶母液的综合利用

针对硫酸铜结晶母液含砷、含镍、高酸的特点,根据正交试验法,采用pH调控法依次进行中和、沉铜、沉镍工业试验,探究了反应时间和终点pH对分离效果的影响。结果表明,采用液碱调控母液pH能有效回收铜、砷、镍元素。中和反应最佳参数为:终点pH=2.5~3.0、反应时间1.5 h、反应自然升温,能够以铜砷渣形式回收98%以上的砷,并与镍成功分离;沉铜反应终点pH=6.0~6.5、反应时间1.0 h、反应温度80~90℃,能实现铜沉淀率>93%;沉镍反应终点pH=10.0~10.5、反应时间2.0 h,在室温下压滤,镍沉淀率>98%。母液经处理后得到的沉镍后液含铜<50 mg/L,含砷<5 mg/L,含镍<100 mg/L,母液得到有效处理,实现铜回收率>96%,砷回收率>98%,镍回收率>84%。

咖啡渣活性炭的制备及其去除含铜废水中Cu(Ⅱ)的性能研究

研究了采用NaOH活化焙烧咖啡渣制备咖啡渣活性炭并用于吸附去除含铜废水中的Cu(Ⅱ)。通过SEM和EDS对咖啡渣活性炭进行表征,考察了废水初始pH、Cu(Ⅱ)初始质量浓度、吸附时间、吸附剂投加量对Cu(Ⅱ)去除率的影响。结果表明:针对质量浓度50 mg/L、pH=6的50 mL模拟含铜废水,在咖啡渣活性炭投加量10 mg、温度25℃,搅拌速率150 r/min条件下吸附9 h, Cu(Ⅱ)去除率可达94.12%;Langmuir等温吸附模型和准二级动力学模型能较好地描述吸附过程。该吸附材料对废水中Cu(Ⅱ)的吸附性能较好。

硅酸盐分子筛处理电镀含铜废水的研究

硅酸盐分子筛是一种具有吸附脱附、催化、离子交换等多用途材料。本文对硅酸盐分子筛处理电镀含铜废水进行研究,分析了硅酸盐分子筛加量、吸附时间、温度和p H四个因素对Cu离子去除率的影响。通过实验分析得出最佳处理条件:在电镀废水质量浓度为98.2 mg/L时,硅酸盐分子筛加量为4 g/100 m L,合理的吸附时间为30 min,温度的影响不显著,可以选择室温25℃作为处理温度,适宜的酸碱环境是p H为4~5,合理的搅拌速度为90 r/min。本文研究为实际电镀废水处理过程提供了理论依据。