Separation of cobalt and nickel from acidic sulfate solutions using mixtures of di(2‐ethylhexyl)phosphoric acid (DP‐8R) and hydroxyoxime (ACORGA M5640)

DP‐8R and ACORGA M5640 extractants diluted in Exxsol D100 were used to co‐extract cobalt and nickel from aqueous acidic sulfate media. The influences of equilibration time, temperature, equilibrium pH and reagent concentrations on the extraction of both metals have been studied. It was observed that both cobalt and nickel extraction are slightly sensitive to temperature but are pH dependent. Metal extraction equilibria are reached within about 5 min contact time. In addition, cobalt extraction depends on the extractant concentration in the organic phase. For a solution containing 0.5 g dm^?3 each of cobalt and nickel and an initial pH of 4.1, conditions were established for the co‐extraction of both metals and selective stripping (with H₂SO₄) of cobalt and nickel. Using the appropriate reagent concentrations the yield (extraction stage) for both metals exceeded 90%, and stripping of cobalt and nickel was almost quantitative. Copyright © 2004 Society of Chemical Industry     

Extraction of molybdenum(VI) from sulfate solutions by LIX 622

The application of LIX 622 (oxime derivative) as an extraction reagent of molybdenum (VI) from sulfate media was studied. The extraction system was studied as a function of contact time, temperature, aqueous pH, diluent of the organic phase and metal and extractant concentrations. The extraction is exothermic and it is dependent on the organic diluent, aqueous pH and reagent concentration. The data have been analysed numerically to determine the stoichiometry of extracted species and their equilibrium constants. It was found that molybdenum was extracted into the organic phase by a complex mechanism which involves the formation of three species (MoO₂L₂, MoO₄H₃HL⁺HSO₄⁻ and MoO₄H₂HL, where L represents the extractant). Molybdenum stripping by acidic and ammonium hydroxide solutions was also studied. © 2000 Society of Chemical Industry     

用M5640从锌氨溶液中萃取锌

以M5640为萃取剂,在CO2协同作用下,从氨?硫酸铵溶液中萃取锌,考察了萃取剂浓度、总氨浓度、相比、温度、加入CO2等因素对锌萃取率的影响. 结果表明,M5640在氨性溶液中对锌有一定的萃取能力,溶液pH值和总氨浓度对锌的萃取率影响较大,向溶液中加入CO2可明显提高M5640对锌离子的萃取能力. 在温度25℃及M5640加入量35vol%、相比O/A=2、锌离子浓度18.02 g/L、总氨浓度3 mol/L、加入CO2的条件下,锌的单级萃取率由不加CO2时的65.1%提升至97%以上,两级错流萃取锌萃取率达99.9%. 萃取得到的有机相不含氨,表明加入CO2可避免氨的共萃.     

Modeling of the Extraction Equilibrium of Copper from Sulfate Solutions with Acorga M5640

The extraction equilibrium of copper from sulfate media with the aldoxime Acorga M5640 in ShellSol D70 has been investigated. The distribution results were interpreted by taking into account the nonideality of the aqueous phase. The activity of copper and hydrogen ions in the target systems CuSO₄/H₂SO₄/Na₂SO₄ and CuSO₄/H₂SO₄/Fe₂(SO₄)₃/ZnSO₄ were calculated through the speciation of the aqueous solutions and by applying the Pitzer model. The experimental pH values were found in good agreement with the predicted pH values. A model considering the dimerization of the aldoxime extractant was proposed to predict the distribution ratio and the copper loading isotherms. The extraction constant at infinite dilution and the apparent dimerization constant were evaluated from the experimental data and were found to be 10^{3.06 ± 0.07} and 51 ± 9 M^?1, respectively, at 25°C.     

用磷酸三丁酯萃取分离硫酸铵母液中的HCN

研究了磷酸三丁酯(TBP)-磺化煤油体系从重庆某企业甘氨酸生产副产物硫酸铵母液中萃取分离HCN的工艺,考察了萃取体系、TBP体积分数、母液初始pH值、相比(Vorg∶Vaq)对萃取HCN的影响以及氢氧化钠浓度、相比(Vaq∶Vorg)和平衡pH值对HCN反萃的影响。结果表明:选用TBP作为萃取剂能够对硫酸铵母液中的HCN进行快速有效的萃取;TBP体积分数、母液初始pH值及相比对HCN萃取率影响显著;以含体积分数35%TBP的有机相作萃取剂,在相比(Vorg∶Vaq)为2∶1的条件下,pH值为2.92的含氰1.71 g/L的硫酸铵母液经3级错流萃取,萃余液中含氰低于0.5 mg/L,氰的萃取率接近100%;在相比(Vaq∶Vorg)为1∶1条件下,以0.6 mol/L的氢氧化钠为反萃液,控制反萃液平衡pH值大于13.0,氰的单级反萃率大于96%;含氰0.78 g/L的有机相在相比为1∶1条件下,经过2级错流反萃,氰基本上被反萃完全,贫有机相不经过处理可循环使用。     

Recovery of vanadium from ash-leaching solutions by solvent extraction

One of the principal problems during vanadium recovery from combustion residues is its purification, mainly from iron and nickel. This can be achieved by selective solvent extraction of V from liquors obtained by ash-leaching. The use of solvents also makes feasible the recovery of V from boiler washing water and leaching ponds. In the present work, leach liquors from two fouling-ashes were extracted at various pH levels with secondary, tertiary and quaternary amines, with di-(2-ethylhexyl) phosphoric acid (DEHPA), and with DEHPA-tributylphosphate mixtures. Various concentrations of the solvents in kerosene were used. Both DEHPA and amines (secondary and tertiary) are good and selective extractants for V leached from ash. However, amines always require V oxidation and partial neutralization of the leach liquors; DEHPA seems more interesting because it does not need any preliminary V reduction nor partial neutralization, provided that ash leaching is carried out with water and not with acid.     

Separation of Simulated Mixed Mo(VI) and V(V) From HNO3 and HCl Solutions by Selective Extraction and Stripping with Tri-N-Butyl Phosphate as Extractant

Equilibrium study was carried out to determine the optimum conditions required for Mo(VI) extraction from HNO₃ solutions and subsequently, simulated mixed Mo(VI), and V(V) were extracted from HNO₃ (pH = 1.0) and 6.0 mol L^?1 HCl solutions with TBP dissolved in n-hexane. The variation of pH (selective extraction) and selective stripping were investigated as methods of separation of Mo(VI) and V(V). The latter method was found inefficient for separations from HNO₃ solutions (pH = 1.0) except supplemented with selective stripping (back-extraction with 2.0 mol L^?1 H₂SO₄/14.5 mol L^?1 NH₄OH). While from 6.0 mol L^?1 HCl, selective stripping was adequate to quantitatively strip in turns the Mo(VI) and V(V) co-extracted into the TBP phase. About 100% of the co-extracted V(V) from the HCl medium was stripped in a two-stage process, in contrast to a single-stage required for Mo(VI) of the same result. The selective stripping method was found to be better because an initial appreciable co-extraction had occurred prior to stripping separation. Based on analytical and spectra data, the extracted complexes from HNO₃ and HCl media were formulated as ((MoO₂)_7–8n(VO₂)_2n · (NO₃)₁₆) ^(16–18)n- · m TBP (where n>m) and (MoO₂Cl₂ · VO₂ Cl) · xTBP, respectively.     

Extraction of zinc from ammoniacal/ammonium sulphate solutions by LIX 54

The extraction of zinc from ammoniacal/ammonium sulphate aqueous media using LIX 54 has been studied. The metal extraction rate has been examined and also the effect of temperature on the extraction of zinc (ΔH° = −8·8 kJ mol⁻¹). The effect of the aqueous pH, and therefore zinc ammine complex formation, on the extraction of zinc was studied. Stripping of the metal from loaded organic phases was carried out at various rates, temperatures (ΔH° = 3·2 kJ mol⁻¹) and sulphuric acid concentrations. The results obtained were compared with others obtained from the literature wherein different extractants were used. © 1998 SCI.     

利用失效钒电解液回收钒制备偏钒酸铵工艺

为了提取失效钒电解液中有价钒元素,对全钒氧化还原液流电池失效钒电解液的回收利用进行了研究。在常温常压条件下,以氯酸钠作氧化剂对失效钒电解液进行深度氧化,使低价钒全部转变成五价钒,然后通过浓缩、沉钒、干燥等工艺过程,得到具有高附加值的偏钒酸铵。分析了回收过程的工艺原理,探讨了回收工艺的工艺条件。结果表明：NaClO₃对失效钒电解液的氧化是影响钒回收率的关键工艺过程,V⁴⁺：NaClO₃的最佳摩尔比为1：0.2,V³⁺：NaClO₃的最佳摩尔比为1：0.4;沉钒的最佳工艺条件为：钒液浓度为25～30g/L,pH为8.0～8.5,沉钒温度为50～60℃,加铵系数K为1.0～1.2,沉钒时间为80～120min。该工艺具有钒回收率高、成本低、操作简便、对环境友好等优点,在最佳工艺条件下钒的回收率可高达99%左右,为全钒液流电池失效钒电解液的回收利用提供了一条新途径。     

Separation and recovery of copper from waste printed circuit boards leach solution using solvent extraction with Acorga M5640 as extractant

Waste printed circuit boards (WPCBs) have received extensive attention in recent years because of its harmfulness and resource. In this work, two-step leaching process was carried out by using steel pickling waste liquor (SPWL) as the leaching agent. The leaching solution contains a variety of metals, especially iron, which will have an effect on the recovery of copper. Acorga M5640 (M5640) extractant with a kerosene diluent was used to recover copper from WPCBs leach solution, and the separation factor is adopted to analyze the effects of these metal ions. The effect of different parameters such as pH of aqueous phase, phase ratio (O/A), M5640 concentration, contact time as well as the concentration of H₂SO₄ as stripping reagent were investigated. Over 90.0% copper was extracted with pH 1.1, phase ratio (O/A) 1/1, M5640 concentration 16%, contact time 3 min at room temperature. For the stripping process, the 60 s contact time and 2.5 mol/L H₂SO₄ concentration are suitable with 90.0% stripping percentage of copper. Copper extraction isotherm accords with Langmuir isotherm equation and the results show that iron is the most influential metal ion for copper extraction, which will reduce the theoretical saturation of the extractant. The extractant M5640 has excellent reuse performance and can be recycled more than 10 times, which demonstrated M5640 has the industrial application value in the extraction of copper from WPCBs leach solution.     

Separation of Copper and Nickel from Ammoniacal/Ammonium Carbonate Solutions Using ACORGA PT5050

ABSTRACT

ACORGA PT5050 diluted with iberfluid (kerosene-type diluent, mostly aliphatic) was used to coextract copper and nickel from ammoniacal carbonate solutions. The influence of kinetics, temperature, equilibrium pH, and extractant concentration on the extraction of both metals has been studied. It was observed that nickel extraction is very sensitive to aqueous pH and that the extraction falls beyond an equilibrium pH of 9. For a typical solution containing near 3 g/L each of copper and nickel and 60 g/L ammonium carbonate, conditions were established for the coextraction and selective stripping of nickel and copper.     

逆向浸取法制取硫酸镁、氢氧化镁及氧化镁

介绍了以硫酸铵、白云石为原料制备硫酸镁、氢氧化镁、轻质氧化镁的实验条件及工艺过程。讨论了实验条件对产品质量、性能的影响。与白云石的开发利用其它工艺比较，该方法具有原料来源方便、生产成本较低等优点，无三废污染，废渣可加工成CaSO4产品，所排氨气也可回收利用。     

制钒废水中钒铬渣制备碱式硫酸铬的工艺研究

以钒制品厂含钒废水中回收的含钒铬废渣为原料,以HG/T 2678-2007工业碱式硫酸铬为检测标准,研究制备碱式硫酸铬的工艺。该工艺是将提钒后的铬渣进行浓酸熟化、浸取废渣中的铬后,再将浸取液除铁和纯化,制备达到纯度要求的氢氧化铬,最后按产品要求,与一定比例硫酸反应制成碱式硫酸铬。该工艺铬回收率达到89.61%,产品符合HG/T 2678-2007的要求,其中三氧化二铬质量分数可以达到31%。     

Three-liquid-phase extraction and separation of V(V) and Cr(VI) from acidic leach solutions of high-chromium vanadium–titanium magnetite

A new method by liquid–liquid–liquid three phase system, consisting of acidified primary amine N1923(abbreviated as A-N1923), poly(ethylene glycol)(PEG) and (NH_4)_2SO_4 aqueous solution, was suggested for the separation and simultaneous extraction of V(V) and Cr(VI) from the acidic leach solutions of highchromium vanadium–titanium magnetite. Experimental results indicated that V(V) and Cr(VI) could be selectively enriched into the A-N1923 organic top phase and PEG-rich middle phase, respectively, while Al(III)and other co-existing impurity ions, such as Si(IV), Fe(III), Ti(IV), Mg(II) and Ca(II) in acidic leach solutions,could be enriched in the(NH_4)_2SO_4 bottom aqueous phase. During the process for extraction and separation of V(V) and Cr(VI), almost all of impurity ions could be removed. The separation factors between V(V) and Cr(VI) could reach 630 and 908, respectively in the organic top phase and PEG middle phase, and yields of recovered V(V) and Cr(VI) in the top phase and middle phase respectively were all above 90%.Various effects including aqueous p H, A-N1923 concentration, PEG added amount and(NH_4)_2SO_4 concentration on three-phase partitioning of V(V) and Cr(VI) were discussed. It was found that the partition of Cr(VI) into the PEG-rich middle phase was driven by hydrophobic interaction, while extraction of V(V) by A-N1923 resulted of anion exchange between NO_3~- and H_2V_(10)O_(28)~(-4). Stripping of V(V) and Cr(VI) from the top organic phase and the middle PEG-rich phase were achieved by mixing respectively with NaNO_3 aqueous solutions and Na OH-((NH_4)_2SO_4 solutions. The present work highlights a new approach for the extraction and purification of V and Cr from the complex multi-metal co-existing acidic leach solutions of high-chromium vanadium–titanium magnetite.     

由硫酸铵溶剂萃取法制备硫酸钾工艺研究

通过在反应体系中加入难溶于水的有机溶剂,对硫酸铵和氯化钾制备硫酸钾的溶剂萃取工艺进行了研究。以氧化钾收率为评价指标,确定其工艺条件为:反应时间120 m in,反应温度45℃,萃取剂用量以不超过90%(质量分数)为宜,固液比22%左右,配料比1.85左右。对硫酸钾产品进行质量分析,表明其达到农用一级品标准。     

钙化提钒溶液沉钒的影响因素及沉钒动力学

用(NH4)2SO4对钒渣钙化焙烧、稀酸浸取、化学沉淀净化后的酸性含钒溶液进行沉淀富集,考察了钒浓度、初始pH值、加铵系数(NH3/V摩尔比)、沉钒温度和时间对沉钒率及V2O5含量的影响,研究了沉钒动力学,对沉钒产物进行了表征. 结果表明,在初始pH为2.00?0.05、加铵系数1.5、温度大于95℃、沉钒时间120 min、钒液中V浓度大于20 g/L的条件下,沉钒率超过96%,产品中V2O5含量大于98%,杂质含量符合98级氧化钒的国家标准. 75~99℃下的沉钒过程可由Avrami动力学方程描述,表观活化能Ea=93.23 kJ/mol,指前因子A=9.14×1011 min?1. 铵盐沉钒产物为(NH4)2V6O16?1.5H2O,高温煅烧所得V2O5晶体为柱状,平均粒径1.25 ?m,主要杂质Mn以MnV2O6形式存在.     

Photoinitiation of polymerization of styrene by oxotris(dimethyl dithiocarbamato) vanadium(V)

Oxotris(dimethyl dithiocarbamato) vanadium(V) [VO(S₂CN(CH₃)₂)₃] sensitizes the polymerization of styrene when irradiated by light of λ = 365 nm at 25°C. Under the experimental conditions employed, no retardation occurs, and the rate of initiation is independent of monomer concentration. The mean values of the quantum yield of iniiation (?_i) and polymerization (?_o) are 2.85 × 10^?3 and 6.72 respectively. Spectroscopic analysis shows that initiation occurs predominatly through scission of the N,N-dimethyl dithiocarbamate ligand (—SC(S)N(CH₃)₂) with reduction of vanadium(V) to (IV), and VO (S₂CN(CH₃)₂)₂ is the final photolytic product. A reaction mechanism is proposed based on an intramolecular photoredox reaction which leads to the primary formation of SC(S)N(CH₃)₂ radicals and a vanadium(IV) chelate complex. The rellevant kinetic parameters are evaluated. The polystyrene produced shows a photoactivity when irradiated with UV-light.     

硫酸铵法硝酸磷肥生产高品质硫酸钙工艺研究

研究了昆阳磷矿的硝酸酸解液与硫酸铵反应制备硫酸钙的工艺条件,分别研究了硫酸铵用量、硫酸铵质量分数、温度、加料时间、反应时间对晶体大小和共晶磷含量的影响。确定了结晶过程适宜的工艺条件：硫酸铵用量为理论用量的110%、硫酸铵质量分数为30%、反应温度为90 ℃、加料时间为20 min、反应时间为2 h。在此工艺条件下得到磷质量分数为0.179%、氟质量分数为0.06%的半水和二水混合晶型的硫酸钙结晶,该硫酸钙具有晶体粗大整齐、过滤强度高的优点。     

利用乙磷铝废液生产硫酸铝铵工艺研究

测定了乙磷铝废液中各成分含量。利用乙磷铝废液中铵态氮代替固体硫酸铵生产硫酸铝铵,液固质量比为(1.5 ~4.0)∶1。最佳的工艺路线是先进行固体铝盐的制备,然后再加入经过处理的乙磷铝废液,混合反应后结晶、脱水制得成品。制造工艺简单,而且在生产的过程中充分利用了乙磷铝杀菌剂的生产废液,在降低工业硫酸铝铵生产成本的同时,也减少了乙磷铝杀菌剂的生产废液处理成本。     

Extraction equilibrium of m-cresol by tri-n-octylamine sulfate salts

The influence of the extraction conditions on the distribution coefficient of m-cresol were investigated. The equilibria of m-cresol extraction from an aqueous solution by the tri-n-octylamine sulfate salts (TOA salts) in an organic solvent were examined. Sulfuric acid first reacted with tri-n-octylamine (TOA) to form TOA salts; then m-cresol was extracted into the organic phase from the aqueous phase by the TOA salts. The model of the equilibrium of the chemical reaction of TOA and sulfuric acid to form the TOA salts was constructed by modifying the Wilson model (Wilson, 1967). The predictions of the developed model were fairly consistent with the experimental data, and it was applied to the reaction systems in benzene at various temperatures to predict the extraction of m-cresol. The number of water molecules associated with the various TOA salts, which reflect the extraction capability of m-cresol, was determined.