Cobalt removal from waste‐water by means of supported liquid membranes

BACKGROUND: Supported liquid membranes (SLM) are an alternative technique to remove and recover metals from diluted process solutions and waste‐water. In the present work, the removal of Co(II) from a synthetic CoSO₄ solution containing initial amounts of cobalt(II) in the range 100–200 ppm (0.1–0.2 g dm^?3) has been studied on a pilot scale. By performing batch equilibrium experiments, the optimal settings, i.e. the composition of the organic phase, the pH of the feed, the type and concentration of the stripping agent were determined. RESULTS: It is shown that the equilibrium characteristics of a synergistic extractant mixture containing di‐2‐ethyl‐hexylphosphoric acid (D2EHPA) and 5‐dodecylsalicylaldoxime (LIX 860‐I) are superior to D2EHPA. Both hydrochloric acid and sulfuric acid have been evaluated as stripping solutions in liquid–liquid extraction tests and as the receiving phase in a SLM configuration. Although equilibrium tests showed no difference in stripping characteristics between both chemicals, it was observed that in a SLM configuration the stability of the system when hydrochloric acid is used is poor. With a commercially available SLM module (Liqui‐Cel Extra‐Flow 4 × 28) having a surface area of 19 m², a steady Co(II) flux of 0.140 gm^?2h^?1 has been obtained at influent concentrations of cobalt between 100 and 200 ppm with 3 mol dm^?3 sulfuric acid as stripping phase. CONCLUSIONS: The results obtained show that a supported liquid membrane containing a synergistic mixture of LIX 860‐I and D2EHPA gives the possibility of recovering cobalt from dilute solutions. Copyright © 2008 Society of Chemical Industry     

Solvent Extractive Separation of Zirconium and Hafnium from Hydrochloric Acid Solutions by Organophosphorous Extractants and Their Mixtures with Other Types of Extractants

From 1 to 4 M HCl medium, zirconium was selectively extracted over hafnium by organophosphorous extractants (D2EHPA, PC88A, Cyanex 272). In order to increase the separation factor Zr/Hf, mixtures of organophosphorous extractants with amines (Alamine 336, Aliquat 336) or cationic extractants (Versatic acid 10, LIX 63) were employed in 1–4 M HCl medium. Mixtures with Versatic acid 10 and LIX 63 led to depression in the extraction percentages. But the mixture with LIX 63 was found to be the most effective in separating the two metals among the extractant systems tested in this study. The highest separation factor of around 9.5 was obtained with a mixture of 0.01 M LIX 63 + 0.05 M Cyanex 272 at HCl concentration of 2–4 M. The Zr and Hf were effectively stripped from the loaded mixture of LIX 63 + Cyanex 272 by sulfuric acid solution.     

二（2-乙基己基）磷酸/磷酸三丁酯复合萃取剂协萃对氨基苯甲酸

为强化两性官能团化合物的萃取分离性能,以对氨基苯甲酸（PABA）为被分离溶质,二（2-乙基己基）磷酸（D2EHPA）/磷酸三丁酯（TBP）/正庚烷的混合物为萃取剂进行了萃取平衡特性的研究,考察了溶液的pH值、D2EHPA浓度、TBP浓度对于萃取平衡的影响,建立了复合萃取剂协同萃取PABA的萃取平衡分配系数的表达式.结果表明,D2EHPA/TBP/正庚烷复合萃取剂萃取PABA具有明显的协萃效应,协萃机理为D2EHPA及TBP分别与PABA的Lewis碱性官能团（—NH2）和Lewis酸性官能团（—COOH）缔合形成亲油性更强的萃合物,且D2EHPA与TBP的浓度差异越小,协萃效应越明显.根据萃取平衡分配系数表达式拟合求取了表观萃取平衡常数,复合萃取剂的值远大于D2EHPA、TBP单独作为萃取剂的值,进一步证明了本文提出的协萃机理.     

Synergistic effect of various neutral donors in D2EHPA for selective neodymium separation from lanthanide series via HFSLM

The separation of Nd(III) from lanthanide series via hollow fiber supported liquid membrane (HFSLM) using synergistic extractant was investigated. Optimum extraction and stripping obtained were 94.5% and 85.1% using D2EHPA and TOPO mixtures (0.5:0.5 M/M) as the synergistic extractant. Reaction order for both extraction and stripping were first-order with rate constants of 1.444 and 1.338 min⁻¹, respectively. The experimental results were used to correlate with the models. Results showed that the concentration of Nd(III) from the experiment fitted in well with the model results. The average deviation was 1.95% and 2.18% for predictions in both feed and stripping sides, respectively.     

Extraction and recovery of rhodamine B,methyl violet and methylene blue from industrial wastewater using D2EHPA as an extractant

The extraction behavior of cationic dyes namely rhodamine B (RB), methyl violet (MV) and methylene blue (MB) from industrial wastewater has been investigated using di-(2-ethylhexyl) phosphoric acid (D2EHPA) in hexane as a carrier. The extraction of cationic dyes increases with decreasing feed phase pH and increasing D2EHPA concentration in organic phase. The stripping percentage of dyes using acetic acid as the stripping agent from loaded D2EHPA was found to increase with increasing acid concentration. 98% stripping efficiency of dyes was achieved with 8.5 mol/L acetic acid solution at an organic:aqueous phase ratio (O/A) of 2:1. Parameters examined include D2EHPA concentration, effect of diluents, effect of pH, effect of initial dye concentration, equilibration time, and various stripping agents, aqueous to organic phase ratio in extraction and organic to aqueous phase ratio in stripping.     

Structure of the Extracted Complex in the Ni(II)‐LIX84I System and the Effect of D2EHPA Addition

Abstract

The structure of the Ni(II) complex extracted with the commercial hydroxyoxime, LIX84I, and the effect of adding bis(2‐ethylhexyl) phosphoric acid (D2EHPA) to LIX84I on the extraction rate and the coordination of Ni(II) were investigated by solvent extraction and XAFS methods. The XANES spectrum and the curve fits of the EXAFS spectrum of the Ni‐LIX84I complex showed that the complex is four‐coordinate square‐planar with a 1:2 stoichiometry. In the Ni(II)–D2EHPA–LIX84I system, the coordination geometry changes from square‐planar to six‐coordinate octahedral with an increase in the D2EHPA concentration. Although the rate of Ni(II) extraction from the model spent electroless nickel plating bath with LIX84I is significantly accelerated by adding a small amount of D2EHPA ([LIX84I]: 0.5 M, [D2EHPA]: 0.05 M), most of the Ni(II) complexes extracted with this organic solution remain square‐planar. This indicates that the increase in the extraction rate does not depend on the change in the coordination structure of the extracted complex.     

Solvent extraction with LIX 973N for the selective separation of copper and nickel

LIX 973N diluted with Iberfluid was used to co‐extract copper and nickel from ammoniacal/ammonium carbonate aqueous media. The influence of equilibration time, temperature, equilibrium pH and extractant concentration on the extraction of both metals has been studied. It was observed that neither copper nor nickel extraction is sensitive to temperature and equilibrium pH, however nickel extraction equilibrium is reached at a longer contact time (20 min) than that of copper (5 min), in addition nickel extraction depends greatly on the extractant concentration in the organic phase. For a solution containing 3 g dm⁻³ each of copper and nickel and 60 g dm⁻³ ammonium carbonate, conditions were established for the co‐extraction of both metals, ammonia scrubbing and selective stripping (with H₂SO₄) of nickel and copper. Using the appropriate extractant concentration the yield (extraction stage) for both metals is near 100%, whereas the percentage of nickel and copper stripping is also almost quantitative. © 1999 Society of Chemical Industry     

草酸强化三价铁离子的反萃性能

二(2-乙基己基)磷酸(P204)常作为溶液净化除铁的萃取剂，P204-磺化煤油体系中Fe³⁺与有机相形成络合能力较强的萃合物，使得Fe³⁺反萃比较困难，需采用较高浓度的酸作为反萃剂，但高浓度的酸会破坏有机分子的结构，影响萃取剂循环利用。针对P204-磺化煤油负铁有机相反萃困难的问题，提出利用草酸为反萃剂对负载1g/L铁的P204-磺化煤油有机相的反萃行为进行研究，考察了反萃转速、草酸浓度、反萃温度、反萃时间和相比对Fe³⁺反萃率的影响。结果表明：以反萃转速200r/min，草酸0.4mol/L，反萃时间10min，反萃温度40℃，反萃相比1∶1，采用二级逆流萃取方式，铁的反萃率可以达到99%以上；Fe³⁺反萃过程是吸热反应，其反应的焓变为81.58kJ/mol，反萃过程符合准一级反应动力学方程，对应活化能为49.5kJ/mol。进一步研究了反萃后P204-磺化煤油有机相对Fe³⁺的萃取性能。结果表明：经5次草酸反萃后的P204-磺化煤油有机相萃铁性能几乎不变，对比于高浓度的酸反萃，草酸反萃简化了反萃流程，降低了萃取剂的消耗。     

萃取法制备工业级磷酸二氢铵-萃取剂的反萃取研究

本课题以高效的2-乙基己基磷酸(D2EHPA)为萃取剂,采用溶剂萃取法来提取MAP溶液中的Mg2++杂质,从而实现生产高品质MAP的目的;但是实现其产业化的难点之一,就是反萃取剂的选择,而在选择反萃取剂时关键是实现络合物D2EHPA-Fe3+的有效分离,因为络合物D2EHPA-Fe3+是非常稳定的,而且Fe3+的富集能使萃取剂老化.因此,选择有效的反萃取剂来实现D2EHPA的循环回收利用是非常有必要的.以H2SO4+添加剂A为反萃取剂,通过考察反萃取剂浓度,相比,反应温度,反应时间,搅拌速度等对反萃取Fe3+反萃取率的影响,求得最佳工艺条件为H2SO4浓度:4mol· L-1,反应温度45℃,相比为1∶1,搅拌速度550r· min-1,搅拌时间0.5h.     

Extraction and Stripping Behavior of Iron (III) from Phosphoric Acid Medium by D2EHPA Alone and Its Mixtures with TBP/TOPO

In the present study an attempt has been made to understand the extraction and stripping behavior of iron (III) with D2EHPA alone and its mixture with TBP or TOPO in phosphoric acid medium. Effect of variables such as concentrations of iron (III), phosphoric acid, and phosphate in the aqueous phase, D2EHPA, TBP, and TOPO concentrations in the organic phase and temperature on the extraction process has been studied. The extraction of iron (III) decreased with increase in phosphoric acid concentration. The increase in D2EHPA concentration increased the extraction of iron (III). The presence of TOPO or TBP with D2EHPA showed antagonism. The increase in temperature decreased the extraction of iron (III) with D2EHPA alone and its mixture with either TOPO or TBP showing the exothermic nature of the extraction reaction. The stripping of iron (III) by various reagents followed the order: oxalic acid > phosphoric acid > hydrochloric acid > sulphuric acid > mixture of sulphuric and hydrofluoric acids > ascorbic acid > citric acid irrespective of extraction systems. Higher temperature favors the stripping. The effect of diluents on iron (III) extraction has also been studied. The mechanism of extraction has been explained in the light of the results obtained.     

Sulfonic Acids: Catalysts for the Liquid-Liquid Extraction of Metals

Abstract

Three sulfonic acid extractants, dinonylnaphthalene sulfonic acid (HDNNS), didodecylnaphthalene sulfonic acid (HDDNS) and di-(2-ethyl-hexyl) sodium sulfosuccinate (Aerosol OT, AOT) are compared as to their effects on the extraction of nickel with LIX63. The acidic extractants interact synergistically with the oxime. Interfacial tension results are presented which demonstrate that the sulfonates form reversed micelles in non-polar organic solvents. It is proposed that the reversed micelles catalyze the extraction by specific solubilization of both the metal and the extractant, resulting in an increase in the interfacial concentration of the reacting species. The ability of LIX63 to chelate with nickel without deprotonating permits the synergism to occur at low pH.     

Extraction of strontium ion from sea water by contained liquid membrane permeator

To develop a liquid membrane permeator that extracts strontium ion from sea water effectively and continuously, we investigated the extraction of strontium ion from artificial and natural sea water in a contained liquid membrane permeator. The permeator consists of a liquid membrane and two cells for aqueous solutions. The liquid membrane containing D₂EHPA(di-2-ethylhexyl-phosphoric acid) and DCH18C6(dicyclohexano-18-crown-6) is trapped between two hydrophobic microporous polyethylene films and separates sea water and the 0.2 M H₂SO₄ aqueous stripping solution. The effects of various operating parameters on the extraction of strontium ion were experimentally examined. The extractant of DCH18C6 -D₂EHPA mixture in kerosene had a synergistic effect on the extraction of strontium ion. The permeator extracted strontium ion from sea water effectively and continuously with long membrane lifetime.     

三烷基氧膦与二(2-乙基己基)磷酸协萃对氨基苯酚的研究和应用

为考察复合萃取剂萃取两性官能团溶质的协萃机理,以对氨基苯酚(PAP)为分离溶质,三烷基氧膦(TRPO)+二(2 乙基己基)磷酸(D2EHPA)+庚烷为萃取剂进行了萃取平衡特性的研究。结果表明,该萃取剂萃取PAP时,具有明显的协萃效应。协萃机理为TRPO与PAP的中性分子以及D2EPHPA与PAP的中性分子和阳离子反应生成(HP)2·NH2—C6H4—OH·TRPO或者P·NH3—C6H4—OH·TRPO萃合物;萃取剂中D2EHPA与TRPO的适宜协萃比为1∶3;pH是影响萃取能力的关键因素,起始pH值条件下PAP分子形态摩尔分数较大的pH值区域(6—8),分配系数出现极大值;采用适宜的萃取剂组成对PAP的工业生产废水进行处理,可有效去除废水中的PAP和苯胺。     

采用不同载体的中空纤维更新液膜Cu(Ⅱ)传质的研究(英文)

The extraction ability of organophosphorus extractant D2EHPA (di-2-ethylhexyl phosphoric acid) and hydroximic extractant Lix984N are investigated by the extraction equilibrium experiments. Effects of carrier concentration and organic/aqueous volume ratio on the mass transfer of hollow fiber renewal liquid membrane (HFRLM) are studied. Results show that, in the extracting process, kerosene and n-heptane are more suitable than methyl-isobutyl ketone, butylacetate and benzene as the diluents of D2EHPA or Lix984N. The favorable feed pH is 4.4 for D2EHPA and 2.6 for Lix984N. The mass transfer flux of HFRLM increases with carrier concentration and finally reaches a plateau. The mass transfer flux and the overall transfer coefficient increase with the or-ganic/aqueous volume ratio, reach the maximum and then decrease.     

Synergistic extraction and separation of Fe(III) and Zn(II) using TBP and D2EHPA

Waste chloride pickle liquors from hot-dip galvanizing plants, steel plants and flue dust contain reasonable amounts of heavy metals such as Zn, Cr, Ni, etc. Iron is invariably associated with most of these materials and comes into solution during leaching. Thus, the synergistic extraction of zinc(II) and iron(III) from leach solutions in tri-n-butyl phosphate (TBP)–di(2-ethylhexyl) phosphoric acid (D2EHPA) system diluted in kerosene was investigated. The Zn and Fe concentrations in the leach liquor used in the present study were 2 g/L. Experiments were carried out in the pH range of 0.5–4.0, temperature of 25°C, using sole D2EHPA, sole TBP and D2EHPA–TBP mixtures at different ratios. Results showed that the co-extraction of zinc(II) and iron(III) increased with increasing equilibrium pH using D2EHPA. It is demonstrated that the mixtures of TBP and D2EHPA are more efficient and selective than D2EHPA alone. At low pH values, the separation factor is low when pure D2EHPA is used as an extractant; however, using TBP as a synergist, the separation factor increases and results in a better separation of zinc from iron. Increasing TBP to D2EHPA ratios in the organic phase caused a slight shift to the right in the extraction isotherm of iron and a marked shift to the right in the extraction isotherm of zinc, and the maximum separation factor of 13.3 × 10³ was achieved at a TBP to D2EHPA volume ratio of 4:1 (0.58 M TBP: 0.12 M D2EHPA). Furthermore, the effect of equilibrium pH, organic to aqueous phase ratio and Cl^? concentration on the selective extraction was investigated. Using two extraction stages at the O/A ratio of 2:1 and pH_e (equilibrium pH) of 3 and 1 for zinc and iron, respectively, 99% of zinc(II) and 96.25% of iron(III) were extracted.     

THE SELECTIVITY OF NICKEL OVER IRON IN THE LIX63-HDNNS SOLVENT EXTRACTION SYSTEM

ABSTRACT

The effects of the aqueous phase pH and the organic phase HDNNS concentration on the distribution coefficients of Ni and Fe in pure HDNNS or mixed LIX63-HDNNS systems have been investigated. With the mixed extractants, there is antagonistic extraction of iron below pH 1.4 whereas synergistic extraction occurs above this pH. At pH 2.5 and a fixed LIX63 concentration, iron distribution increases markedly in comparison with the oxime-free system and goes through a maximum with increase in HDNNS concentration. A similar behavior is shown by nickel at both pH 1.0 and 2.5. The log D_Feversus pH plot gives a curve with a slope of two for the LIX63-HDNNS mixed system, which suggests that iron is extracted in the form of a species with an ionic charge of 2, probably Fe(OH)²⁺. The extracted complexes are proposed as Ni(H₂L)₃D₂where all three oxime molecules function as bidentate ligands, and Fe(OH) (H₂L) ₃D₂where one of the oxime molecules functions as a monodentate ligand. The Ni/Fe selectivity is high at low pH and changes mainly as a result of variations in the nickel distribution coefficient, but it is low at high pH because of the synergistic extraction of iron.     

THE KINETICS OF ZINC,COBALT AND NICKEL EXTRACTION IN THE D2EHPA-HEPTANE-HC104 SYSTEM USING THE ROTATING DIFFUSION CELL TECHNIQUE

The kinetics of the extraction of zinc, cobalt and nickel from perchlorate solutions using di 2-ethyl-hexyl phosphoric acid (D2EHPA) dissolved in heptane were studied using the Rotating Diffusion Cell technique. The extraction of each metal was investigated individually over a wide range of metal concentration, extractant concentration, pH and temperature conditions.

The data were analysed in terms of a mass transfer with chemical reaction (MTWCR) mechanism. Hughes and Rod'/s generalized MTWCR model was used to fit the cobalt data using kinetic and equilibrium parameters. The zinc and nickel data were quantitatively described within the framework of the MTWCR model. The zinc extraction rate was so fast that mass transfer alone was rate controlling. The nickel extraction experiments were so slow that the metal-ligand complex formation was incomplete in the aqueous film. Some reaction was determined to be occurring in the aqueous bulk solution as well.     

Investigating the Synergistic Effect of D2EHPA and Cyanex 302 on Zinc and Manganese Separation

The synergistic effect of Cyanex 302 on the extraction of zinc and manganese with D2EHPA in sulfate media was investigated. Experiments were carried out in the pH range of 1.0–5.0, temperature of 23, 40, and 60°C with sole D2EHPA and Cyanex 302 as extractant and D2EHPA to Cyanex 302 ratios of 1:3, 1:1, and 3:1. The experimental results showed that the co-extraction of zinc and manganese increased with increasing equilibrium pH and temperature. Increasing the D2EHPA to Cyanex 302 ratio in the organic phase, caused a left shifting of the extraction isotherm of zinc and a right shifting of the extraction isotherm of manganese. Thus, a better separation of zinc over manganese was achieved. At low pHs, the separation factor is low when pure D2EHPA is used as an extractant; however, using Cyanex 302 as a synergist, the separation factor increases and results in a better separation of zinc from manganese. Stoichiometric coefficient of zinc for single D2EHPA and Cyanex 302 and their mixture was calculated to be close to 6.     

Liquid Emulsion Membrane (LEM) Process for Vanadium (IV) Enrichment: Process Intensification

Abstract

A liquid emulsion membrane (LEM) system for vanadium (IV) transport has been designed using di‐2‐ethylhexyl phosphoric acid (D2EHPA), dissolved in n‐dodecane as carrier. The selection of extractant, D2EHPA, was made on the basis of conventional liquid‐liquid extraction studies. The work has been undertaken by first carrying out liquid‐liquid extraction studies for vanadium (IV) to get stoichiometric constant (n), and equilibrium constant (K_ex), which are important for process design.

Transport experiments were carried out at low vanadium (IV) concentration (ppm level). The studies on liquid emulsion membrane included i) the influence of process parameters i.e. feed phase pH, speed of agitation, treat ratio, residence time and ii) emulsion preparation study i.e., organic solvent, extractant concentration, surfactant concentration, internal strip phase concentration. When the strip phase concentration was 2 mol/dm³ (H₂SO₄) and feed phase pH 3 better extraction of vanadium was obtained. Higher V_m/V₁ gave higher extraction of vanadium (IV). A simplified, design engineer friendly model was developed.     

Separation and Recovery of Cadmium from Acidic Leach Liquors of Spent Ni-Cd Batteries using Molten Paraffin Wax Solvent Extraction

Separation and recovery of cadmium from sulphate leach liquors of spent Ni-Cd batteries using TBP, HDEHP (D2EHPA), EHEHPA (PC 88A or Ionquest 801 or P507) have been investigated in a laboratory scale. Cadmium can be extracted into paraffin waxes from acidic solutions in the temperature range of 55–75°C using different extractants. The influence of various parameters on extraction and stripping were studied in detail. The feasibility of separation of cadmium from nickel using these extractants and their combination was studied. The mixture extractant of EHEHPA and TBP was found to be the best for the separation of Cd and Ni. A three-stage counter-current extraction simulation test for cadmium extraction was carried out at an A/O phase ratio of 4:1 and pH 2.5. More than 99.97% Cd²⁺ was extracted with the organic phase containing 0.7 mol L^?1 EHEHPA and 0.5 mol L^?1 TBP, while more than 99.97% nickel was left in the raffinate. The cadmium loaded organic phase was stripped with 2 mol L^?1 hydrochloric acid in the stripping stage. The present method can be applied to the separation and recovery of cadmium from acidic leach liquor of spent Ni-Cd batteries or related waste liquor.