酸浸—萃取—沉淀法回收废锂离子电池中的钴

采用酸浸—萃取—沉淀法回收废锂离子电池中的钴。实验结果表明:废锂离子电池在600℃下煅烧5 h可将正极材料上的有机黏结剂与正极活性物质分离;正极活性物质在Na OH溶液浓度为2.0 mol/L、n(Na OH)∶n(铝)=2.5、碱浸温度为20℃的条件下碱浸反应1 h后,铝浸出率达99.7%;已除铝的正极活性物质在硫酸浓度为2.5 mol/L、H_2O_2质量浓度为7.25 g/L、液固比为10、酸浸温度为85℃的条件下酸浸反应120 min,钴浸出率高达98.0%;酸浸液在p H为3.5、萃取剂P507与Cyanex272体积比为1∶1的条件下,经2级萃取,钴萃取率为95.5%;采用H_2SO_4溶液反萃后在硫化钠质量浓度为8 g/L、反萃液p H为4的条件下沉淀反应10 min,钴沉淀率达99.9%。     

苯甲酸生产残液中锰、钴和镍的提取及分离

探讨了苯甲酸生产残液中锰、钴和镍的提取及分离方法。首先采用酸溶液提取残液中的金属元素;然后通过氨水沉淀法分离锰;最后使用p507萃取剂分离钴和镍。实验结果表明:当苯甲酸生产残液中锰、钴和镍的质量分数分别为0.085 0%,0.307 1%,0.015 5%时,在硫酸浓度为2.0 mol/L、过氧化氢溶液质量分数为25%的条件下,锰、钴和镍的提取率分别为88.59%,87.77%,86.50%;当氨水浓度为2 mol/L时,锰的沉淀率达94.24%;在平衡水相p H为4、p507萃取剂皂化率为60%、油相中p507萃取剂的体积分数为15%的条件下,钴萃取率达87.53%,镍萃取率仅为8.46%,钴镍分离系数为68.70。     

Vanadium recovery from oil fly ash by leaching, precipitation and solvent extraction processes

In order to reduce the environmental impact due to land disposal of oil fly ash from power plants and to valorize this waste material, the removal of vanadium was investigated using leaching processes (acidic and alkaline treatments), followed by a second step of metal recovery from leachates involving either solvent extraction or selective precipitation. Despite a lower leaching efficiency (compared to sulfuric acid), sodium hydroxide was selected for vanadium leaching since it is more selective for vanadium (versus other transition metals). Precipitation was preferred to solvent extraction for the second step in the treatment since: (a) it is more selective; enabling complete recovery of vanadate from the leachate in the form of pure ammonium vanadate; and (b) stripping of the loaded organic phase (in the solvent extraction process) was not efficient. Precipitation was performed in a two-step procedure: (a) aluminum was first precipitated at pH 8; (b) then ammonium chloride was added at pH 5 to bring about vanadium precipitation.     

Recovery of copper from contaminated soil by flushing

In this work the development of a process for the recovery of copper from contaminated industrial soils is presented. Experimental tests on a standard soil contaminated with a solution of copper chloride were carried out. The metal was extracted from the contaminated soil by flushing with a 0.1 M aqueous solution of an ethylenediaminetetraacetic acid (EDTA) sodium salt. A maximum copper extraction efficiency of about 60% was observed. Copper was then separated from the extracted solution by precipitation with sodium hydroxide after addition of ferric sulfate.     

Combination of three-stage sink-float method and selective flotation technique for separation of mixed post-consumer plastic waste

The aim of this research was to separate the different plastics of a mixed post-consumer plastic waste by the combination of a three-stage sink-float method and selective flotation. By using the three-stage sink-float method, six mixed-plastic wastes, belonging to the 0.3-0.5 cm size class and including high density polyethylene (HDPE), polypropylene (PP), polyvinylchloride (PVC), polystyrene (PS), polyethylene terephthalate (PET) and acrylonitrile-butadiene-styrene copolymers (ABS) were separated into two groups, i.e., a low density plastic group (HDPE and PP) and a high density plastic group (PET, PVC, PS and ABS) by tap water. Plastic whose density is less than that of the medium solution floats to the surface, while the one whose density is greater than that of the medium solution sinks to the bottom. The experimental results elucidated that complete separation of HDPE from PP was achieved by the three-stage sink-float method with 50% v/v ethyl alcohol. To succeed in the separation of a PS/ABS mixture from a PET/PVC mixture by the three-stage sink-float method, a 30% w/v calcium chloride solution was employed. To further separate post-consumer PET/PVC and PS/ABS based on plastic type, selective flotation was carried out. In order to succeed in selective flotation separation, it is necessary to render hydrophilic the surface of one or more species while the others are kept in a hydrophobic state. In flotation studies, the effects of wetting agent, frother, pH of solution and electrolyte on separation were determined. The selective flotation results showed that when using 500 mg l(-1) calcium lignosulfonate, 0.01 ppm MIBC, and 0.1 mg l(-1) CaCl2 at pH 11, PET could be separated from PVC. To separate ABS from PS, 200 mg l(-1) calcium lignosulfonate and 0.1 mg l(-1) CaCl2 at pH 7 were used as a flotation solution. Wettability of plastic increases when adding CaCl2 and corresponds to a decrease in its contact angles and to a reduction in the recovery of plastic in the floated product.     

Cobalt separation from waste mobile phone batteries using selective precipitation and chelating resin

Separation of cobalt from mixed-waste mobile phone batteries containing LiCoO₂ cathodic active material was investigated using selective precipitation and chelating resin. Cobalt was recovered from the active powder materials containing 47 % Co oxide together with Mn, Cu, Li, Al, Fe, and Ni oxides. The metal ions were leached sufficiently using 4 M HCl. The metal ions detected spectrophotometrically were removed from the leaching solution by selective precipitation at pH 5.5, with cobalt loss of 27.5 %. Conditions for achieving a recovery of Co in the filtrate by chelating resin were determined experimentally by varying the pH and time of the reaction, as well as the initial resin-to-liquid ratio. The cobalt was efficiently determined by absorption spectrometry at λ _max 510 nm. Chelating polyamidoxime resin was synthesized by polymerization of acrylonitrile and followed by amidoximation reaction. Physically cross-linked gel of polyacrylonitrile was made by a cooling technique.     

有机磷阻燃剂生产废水预处理工艺研究

采用液膜萃取—酸析沉降—络合萃取组合工艺对有机磷阻燃剂生产废水进行预处理.最佳工艺条件为:液膜萃取时,液膜油相(表面活性剂与煤油的混合液)与内水相(H2SO4溶液)的体积比2∶1、乳化液膜与废水的体积比1∶8、废水pH 13.0,硫酸体积分数10％、煤油中表面活性剂质量浓度30 g/L、液膜萃取时间 15 min;酸析沉降时,废水pH l.0,酸析沉降时间30 min;络合萃取时,络合萃取剂(烷基叔胺N235与煤油的混合液)中烷基叔胺N235体积分数30％,络合萃取剂与废水的体积比1∶4,废水pH l.0,络合萃取时间30 min.在此最佳处理条件下,废水COD总去除率可达93％,吡啶去除率达99.9％以上,总磷去除率可达97％,BOD5/COD提高至0.32,有利于后续生化处理.     

萃取法分离回收不锈钢酸洗污泥硫酸浸出液中的重金属

采用非皂化P204和皂化P204萃取剂对不锈钢酸洗污泥的硫酸浸出液进行萃取。在浸出液pH为0.80、非皂化P204体积分数为25%、萃取剂与浸出液体积比为1∶2、萃取时间为5 min的条件下,Fe~(3+)萃取率达99.64%,Cr~(3+)和Ni~(2+)萃取率为3.98%和6.99%,一次萃余液pH为0.64。采用皂化P204对除Fe~(3+)后的一次萃余液进行萃取,在P204体积分数为25%、萃取剂与浸出液体积比为1∶2、萃取剂皂化率为60%、一次萃余液pH为1.50、萃取时间为5 min的条件下,Ni~(2+)萃取率为93.12%,Cr~(3+)萃取率为20.69%,二次萃余液pH为2.63。     

Recovery of yttrium from fluorescent powder of cathode ray tube,CRT: Zn removal by sulphide precipitation

This work is focused on the recovery of yttrium and zinc from fluorescent powder of cathode ray tube (CRT). Metals are extracted by sulphuric acid in the presence of hydrogen peroxide. Leaching tests are carried out according to a 2² full factorial plan and the highest extraction yields for yttrium and zinc equal to 100% are observed under the following conditions: 3 M of sulphuric acid, 10% v/v of H₂O₂ concentrated solution at 30% v/v, 10% w/w pulp density, 70 °C and 3 h of reaction.Two series of precipitation tests for zinc are carried out: a 2² full factorial design and a completely randomized factorial design. In these series the factors investigated are pH of solution during the precipitation and the amount of sodium sulphide added to precipitate zinc sulphide. The data of these tests are used to describe two empirical mathematical models for zinc and yttrium precipitation yields by regression analysis. The highest precipitation yields for zinc are obtained under the following conditions: pH equal to 2–2.5% and 10–12% v/v of Na₂S concentrated solution at 10% w/v. In these conditions the coprecipitation of yttrium is of 15–20%.Finally further yttrium precipitation experiments by oxalic acid on the residual solutions, after removing of zinc, show that yttrium could be recovered and calcined to obtain the final product as yttrium oxide. The achieved results allow to propose a CRT recycling process based on leaching of fluorescent powder from cathode ray tube and recovery of yttrium oxide after removing of zinc by precipitation. The final recovery of yttrium is 75–80%.     

酸析与超声波-超重力-臭氧氧化法联合预处理二硝基甲苯废水

将二硝基甲苯废水(简称废水)酸析后进行超声波-超重力-臭氧氧化处理,考察了酸的种类及废水pH对酸析效果的影响.实验结果表明:加入质量分数98％的H2SO4溶液调节废水pH为1.0时,酸析效果较好,酸析后废水COD去除率为38.50％,硝基化合物的去除率为45.26％,酸析析出物为一硝基甲苯磺酸；酸析后废水经超声波-超重...     

Study concerning the recovery of zinc and manganese from spent batteries by hydrometallurgical processes

Used batteries contain numerous metals in high concentrations and if not disposed of with proper care, they can negatively affect our environment. These metals represent 83% of all spent batteries and therefore it is important to recover metals such as Zn and Mn, and reuse them for the production of new batteries. The recovery of Zn and Mn from used batteries, in particular from Zn–C and alkaline ones has been researched using hydrometallurgical methods. After comminution and classification of elemental components, the electrode paste resulting from these processes was treated by chemical leaching. Prior to the leaching process the electrode paste has been subjected to two washing steps, in order to remove the potassium, which is an inconvenient element in this type of processes. To simultaneously extract Zn and Mn from this paste, the leaching method in alkaline medium (NaOH solution) and acid medium (sulphuric acid solution) was used. Also, to determine the efficiency of extraction of Zn and Mn from used batteries, the following variables were studied: reagents concentration, S/L ratio, temperature, time. The best results for extraction yield of Zn and Mn were obtained under acid leaching conditions (2 M H₂SO₄, 1 h, 80 °C).     

二壬基萘磺酸反胶团萃取模拟废水中的铅

以二壬基萘磺酸（DNNSA）反胶团煤油溶液萃取模拟含铅废水中的铅。在萃取前水相中铅离子浓度为3×10-4 mol/L、DNNSA浓度为0.010 mol/L、油水比为1∶20、模拟含铅废水pH为6、萃取温度为303 K、萃取时间为40 min的条件下，萃取后水相中铅离子浓度为0.845×10-4 mol/L，有机相中铅离子浓度为4.517×10-3 mol/L，铅萃取率为71.83%。DNNSA反胶团萃取铅离子萃取容量为1 188.62 mg/g，热力学焓变为2.595 kJ/mol。     

黄钠铁矾法氧化去除废锂电池硫酸浸出液中的铁

废锂电池中含有的Co、Ni和Cu等金属具有回收价值,Fe的存在降低了有价金属的回收效率。为去除废锂电池硫酸浸出液中的Fe,采用黄钠铁矾法分别以氯酸钠和过氧化氢作为氧化剂氧化除Fe,并优化了过氧化氢作为氧化剂的除Fe工艺参数。实验结果表明:过氧化氢作为氧化剂的除Fe效果好于氯酸钠;在n(H2O2)∶n(Fe)=0.5、初始溶液pH为1.8、终点pH为2.5、反应时间为2.0 h、搅拌速率为500 r/min的最佳工艺条件下,初始ρ(Fe)为0.212g/L的硫酸浸出液经除Fe处理后ρ(Fe)小于0.004 g/L,Fe去除率达98.0%,Co、Ni和Cu的损失率分别为1.04%、2.17%和1.41%。     

Adsorption characteristics of Cu2+ and Zn2+ from aqueous solution using carbonized food waste

The aim of the present study was to analytically provide adsorption characteristics of Cu²⁺ and Zn²⁺ using carbonized food waste (CFW); more specifically, batch tests were conducted using various concentrations of metal ions, contact times, and initial pH levels in an attempt to understand the adsorption removal of heavy metal ions in aqueous solution at concentrations ranging between 50 and 800 mg/l. The results confirmed that the adsorption equilibrium was established within a maximum of 80 min, and the maximum concentrations for adsorption of Cu²⁺ and Zn²⁺ were 28.3 and 23.5 mg/g, respectively. These adsorption levels indicate that CFW has better performance than many other adsorbents. In experiments using different pH conditions, the applicability to acid wastewater was found to be high, and an excellent adsorption removal ratio of 75%–90% was observed under acid conditions at pH 2–4. Furthermore, as the adsorption time increased, the calcium component in the CFW began to leach into the aqueous solution and raise the pH, accordingly causing the removal of heavy metal ions partially as a result of precipitation. When our results were analyzed using the Langmuir model and the Freundlich model for isothermal adsorptivity, the activity of CFW in this study was shown to be more consistent with the former; the adsorption speed of Cu²⁺ and Zn²⁺ according to a pseudosecond-order reaction model was found to be very fast for an initial concentration of not more than 100 mg/l. In a test in which an attempt was made to compare adsorption capacity values obtained from the experiments in this study with the aforementioned three models, the pseudosecond-order reaction model was found to provide results closest to the actual values.     

液液萃取—气相色谱-质谱法测定丙傲来、烯酸生产废水中的特征污染物

建立了液液萃取—气相色谱-质谱法快速测定丙烯酸生产废水中苯系物、酯类、醇类、醛类和酮类等12种半挥发性有机物的分析方法。液液萃取条件为：以二氯甲烷为萃取剂,废水pH 7,分散剂甲醇加入量10 mL/L,盐析剂NaCl加入量300 g/L。各组分的工作曲线的线性关系良好。各组分的加标回收率为95.2%~116.0%,各组分的方法检出限为0.001~0.179 μg/L,相对标准偏差均小于3.5%。该方法可用于丙烯酸生产废水中主要特征有机物的快速定量检测。     

The Effect of Extraction Conditions on the Chemical Characteristics of Pectin from Opuntia ficus indica Cladode Flour

Pectin from the cladode flour of Opuntia ficus indica was extracted at different ethylenediaminetetraacetate concentrations (10 or 20 %), temperatures (40 or 80 °C), pH values (2 or 11), and times (10, 20, 30 40, 50 or 60 min). The effects of the extraction conditions on the yield, purity, and chemical composition of pectin were assessed. The highest pectin yield was observed for pectin obtained under alkaline conditions and 20 % of EDTA. However, pectin produced from alkaline extractions had a lower content of GalA than pectin produced from acid extractions. Higher temperatures favored the extraction of pectin under acid conditions, but these conditions diminished the arabinose content of pectins in a time-dependent manner. The tested extraction conditions caused only slight changes in the molecular weight of the extracted pectin as a function of time.     

Laboratory study on the leaching potential of spent alkaline batteries using a MSW landfill leachate

Two leaching tests were carried out, one with whole batteries and another with cross-cut batteries. In both cases, NEN 7343 (a Nederland’s Standard) procedure was followed using a municipal solid waste (MSW) landfill leachate as extraction solution. Seven fractions were collected corresponding to cumulative liquid/solid (L/S) ratio from 0.1 to 10.0. Those fractions were separately characterized in terms of pH, conductivity, redox potential, density, sulphate, chloride, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn. Results showed that the influence of the alkaline batteries in the landfill leachate composition varies with their physical integrity and with the L/S ratio, and several variations were observed throughout the tests. The leachate pH and redox potential increased as result of the contact with batteries, particularly pH in the test with the cross-cut batteries. The leachate density and conductivity did not change significantly with the whole batteries, in contrast with the test with cross-cut batteries.     

Characterization and leaching of NiCd and NiMH spent batteries for the recovery of metals

Since NiMH and NiCd batteries are still used in the electronic devices market, a treatment and recycling plant has many advantages both from the environmental and the economic points of view. Unfortunately, there is no relationship between shape, size and chemical composition of spent batteries, consequently the characterization and the leaching method of the starting material becomes an important step of the overall treatment process in choosing the best conditions for the selective separation of the metals by hydrometallurgy. Leaching at 20 degrees C with H(2)SO(4) 2M for about 2h seems to be a good solution in terms of cost and efficiency for both battery types. The hydroxide compounds can be readily leached while Ni present as metallic form requires more aggressive conditions due to kinetic constraints. In this paper, the characterization of NiMH and NiCd spent batteries and the results of leaching tests in different conditions are reported.     

催化裂化钠碱脱硫液中钙镁离子的去除

研究了化学沉淀法和氨基膦酸型螯合树脂吸附法对催化裂化钠碱脱硫液中Ca~(2+)和Mg~(2+)的去除效果。实验结果表明:NaOH沉淀法可有效去除钠碱脱硫液中的Mg~(2+),当溶液pH为12、反应时间为15 min时,Mg~(2+)去除率达91.6%;NaOH-Na_2CO_3联合沉淀法无法去除钠碱脱硫液中的Ca~(2+);经过NaOH溶液有效除Mg~(2+)后的脱硫液再采用氨基膦酸型螯合树脂吸附柱去除其中的Ca~(2+)和Mg~(2+),可使出水硬度小于2 mg/L。提高进水pH、降低进水流量、降低进水硬度均可提高单位体积树脂的处理水量。     

Phosphate fertilizer from sewage sludge ash (SSA)

Ashes from sewage sludge incineration are rich in phosphorus content, ranging between 4% and 9%. Due to the current methods of disposal used for these ashes, phosphorus, which is a valuable plant nutrient, is removed from biological cycling. This article proposes the possible three-stage processing of SSA, whereby more than 90% of phosphorus can be extracted to make an adequate phosphate fertilizer. SSA from two Swiss sewage sludge incinerators was used for laboratory investigations. In an initial step, SSA was leached with sulfuric acid using a liquid-to-solid ratio of 2. The leaching time and pH required for high phosphorus dissolution were determined. Inevitably, dissolution of heavy metals takes place that would contaminate the fertilizer. Thus in a second step, leach solution has to be purified by having the heavy metals removed. Both ion exchange using chelating resins and sulfide precipitation turned out to be suitable for removing critical Cu, Ni and Cd. Thirdly, phosphates were precipitated as calcium phosphates with lime water. The resulting phosphate sludge was dewatered, dried and ground to get a powdery fertilizer whose efficacy was demonstrated by plant tests in a greenhouse. By measuring the weight of plants after 6 weeks of growth, fertilized in part with conventional phosphate fertilizer, fertilizer made from SSA was proven to be equal in its plant uptake efficiency.