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.     

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.     

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.     

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.     

Extraction of rare earths using mixtures of sec-octylphenoxy acetic acid and organophosphorus acids

The extraction of rare earths from nitrate medium using three organophosphorus acids, 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HEHEHP), di-(2-ethylhexyl) phosphoric acid (D2EHPA), bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex272), and their mixtures with sec-octylphenoxy acetic acid (CA12) has been studied in detail. The mixtures have different extraction effects on various rare earths. Synergistic extraction effects are only found when light rare earths and yttrium (III) are extracted with mixtures of D2EHPA and CA12. The possibilities of separating the rare earths with these mixtures are investigated according to the extractabilities. It is feasible and advantageous to separate yttrium (III) from the lanthanoids (III) with HEHEHP + CA12 and D2EHPA+CA12 mixtures at proper extractant ratios. The separation of yttrium (III) from heavy rare earths is also possible with mixtures of Cyanex272 and CA12.     

Recovery of nickel,cobalt, copper and zinc in sulphate and chloride solutions using synergistic solvent extraction

A number of synergistic solvent extraction (SSX) systems have been developed to recover nickel, cobalt, zinc and copper from sulphuric and chloride leach solutions by the solvent extraction team of CSIRO, Australia. These in-clude (1) Versatic 10/CLX50 system for the separation of Ni from Ca in sulphate solutions, (2) Versatic 10/4PC system for the separation of Ni and Co from Mn/Mg/Ca in sulphate solutions, (3) Cyanex 471X/HRJ-4277 system for the separation of Zn from Cd in sulphate solutions, (4) Versatic 10/LIX63 system for the separation of Co from Mn/Mg/Ca in sulphate solutions, (5) Versatic 10/LIX63/TBP system for separation of Ni and Co from Mn/Mg/Ca in sulphate solutions, (6) Versatic 10/LIX63 system for the separation of cobalt from nickel in sulphate solutions by difference in kinetics, (7) Cyanex 272/LIX84 system for the separation of Cu/Fe/Zn from Ni/Co in sulphate solutions, (8) Versatic 10/LIX63/TBP system to recover Cu/Ni from strong chloride solutions, and (9) Versatic 10/LIX63 system to separate Cu from Fe in strong chloride solutions. The synergistic effect on metal separation and efficiency is presented and possible industrial applications are demonstrated. The chemical stability of selected SSX systems is also reported.     

Removal of Zinc(II) and Manganese(II) from Crude Phosphoric Media by Bis(2,4,4‐Trimethylpentyl) Phosphinic Acid (Cyanex‐272)

Purification of commercial phosphoric acid produced by the wet process from toxic heavy metals such as zinc and manganese is considered to be a very important environmental and economical process. The commercial bis(2,4,4‐trimethylpentyl)‐ phosphinic acid (Cyanex‐272) is proposed as an extractant for the efficient removal of Zn(II) and Mn(II) from crude phosphoric acid samples of concentrations of 25% and 45%. Various parameters affecting the extraction rate of Zn(II) and Mn(II) were investigated. The results were assessed to obtain the optimum conditions for the fast and efficient removal of both cations from crude phosphoric acid using Cyanex‐272 as an extractant in various diluents. The selectivity sequence of different diluents for Zn(II) and Mn(II) extraction were: kerosene > n‐hexane > cyclohexane > toluene > benzene > chloroform. The stripping of the investigated metal ions is efficiently performed with ammonium thiocyanate which has been selected as a suitable stripping agent.     

Separation of cobalt and zinc from concentrated nickel sulfate solutions with Cyanex 272

BACKGROUND: Removal of cobalt and zinc from concentrated nickel solutions separately using two Cyanex 272 circuits has been practised in the nickel industry. However, no detailed study has been conducted and data are scarce for further improvement. This study aims to optimise the operating conditions and to simplify the process flowsheet. RESULTS: With a synthetic solution containing 100 g L^?1 Ni, 1.4 g L^?1 Co and 0.8 g L^?1 Zn and the organic solution containing Cyanex 272 and TBP in Shellsol D70, the operating conditions of extraction, scrubbing and stripping were optimised. McCabe–Thiele diagrams were constructed to determine the theoretical extraction and stripping stages and a flowsheet to separate cobalt and zinc from nickel was proposed. With this flowsheet, more than 99% cobalt and zinc could be separated, resulting in a pure nickel solution with less than 10 mg L^?1 of cobalt and zinc. CONCLUSIONS: The current study shows that Cyanex 272 can be used to separate cobalt and zinc in one Cyanex 272 circuit effectively from concentrated nickel solutions to obtain very pure nickel solutions suitable for nickel electrowinning or hydrogen reduction. The cobalt and zinc in the loaded strip liquor were concentrated over 10 times and can be separated readily in another much smaller solvent extraction circuit. Copyright © 2010 Society of Chemical Industry     

Solvent extraction of praseodymium using different extractants – a synergistic study

The extraction of praseodymium was investigated from chloride media using different extractants such as D2EHPA, PC88A, Cyanex 272, Cyanex 921, Cyanex 923, Cyanex 301, Cyanex 302, LIX 84I, LIX 622N, Alamine 336, Aliquat 336 and their mixtures. The synergistic effect of Cyanex 272, Cyanex 921, Cyanex 923, Cyanex 301 and Cyanex 302 were studied with each other. Among all the combinations, the mixtures of Cyanex 921-Cyanex 301 and Cyanex 923-Cyanex 301 showed the synergistic effect on the extraction of praseodymium. Solvent extraction of Pr was carried out with the mixture of 0.5 M Cyanex 301 and 0.5 M Cyanex 923. The McCabe-Thiele diagram indicated the quantitative extraction of Pr in two counter-current stages at an A:O phase ratio of 1:2. The two-stage counter-current simulation study showed 94% of extraction efficiency.     

Process for the Recovery of Cobalt and Nickel from Sulphate Leach Liquors with Saponified Cyanex 272 and D2EHPA

Abstract

In this paper, a process is reported for the recovery of cobalt and nickel from copper raffinate solutions using partially saponified Cyanex 272 and D2EHPA as the extractants. The aqueous feed contains 1.65 g/L cobalt and 16.42 g/L nickel. More than 99.9% cobalt separation was achieved with 0.13 M Cyanex 272 (60% neutralized with alkali) in two counter‐current stages at an aqueous to organic phase ratio of 1.1:1. Co‐extraction of nickel was 0.18% only. Stripping of cobalt from a loaded organic phase was carried out with synthetic spent electrolyte solution at an organic to aqueous phase ratio of 2.5 in two counter‐current stages to generate a pregnant electrolyte solution to produce cobalt metal by electrowinning. Similarly, optimum conditions for nickel extraction with 60% neutralized 1 M D2EHPA at O/A ratio of 1.4 in 2 two stages and stripping of metal with synthetic spent electrolyte at O/A ratio of 1.6 in two stages were standardized. Extraction and stripping efficiencies were >99% and the flowsheet of the process is demonstrated.     

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.     

Separation and recovery of heavy metals from concentrated smelting wastewater by synergistic solvent extraction using a mixture of 2-hydroxy-5-nonylacetophenone oxime and bis(2,4,4-trimethylpentyl) -phosphinic acid

Extraction and separation of copper, zinc, nickel, and cadmium from calcium and magnesium in concentrated smelting wastewater by synergistic solvent extraction using a mixture of 2-hydroxy-5-nonylacetophenone oxime (Mextral 84H) and bis(2,4,4 -trimethylpentyl)-phosphinic acid (Cyanex 272) in an aliphatic diluent (DT-100) was studied. The effects of extractant concentrations, equilibrium pH, organic-to-aqueous phase ratios, system temperature, and extraction and stripping efficiencies on the extraction performance of the heavy metals were investigated. Extraction of pH isotherms showed that addition of Cyanex 272 to Mextral 84H causes obvious synergistic shifts for zinc and cadmium and a slightly antagonistic shift for nickel. The separation factor of cadmium over magnesium was 155.7 and the ΔpH₅₀ values between the metals were over 1.00 pH units. Semi-continuous tests for the metals extraction, scrubbing, and stripping were conducted in a continuous extraction apparatus with conditions further optimized for separation of the metals. Nearly 100% of the copper and nickel and over 98% of the zinc and cadmium were recovered with less than 0.1 mg/L copper and nickel, 26 mg/L of zinc, and 10 mg/L of cadmium remaining in the raffinate. A process in which all valuable metals are extracted simultaneously and stripped selectively at optimal conditions is proposed that is entirely feasible for the separation of copper, zinc, nickel, and cadmium from calcium and magnesium in concentrated smelting wastewater. The study determines the fundamental parameters for the treatment of smelting wastewater by solvent extraction.     

Production of high purity rare earth mixture from iron-rich spent fluid catalytic cracking (FCC) catalyst using acid leaching and two-step solvent extraction process

Acid leaching and a two-step solvent extraction procedure were developed to produce high purity mixture of La and Ce from iron-rich spent FCC catalyst discharged from Dzung Quat refinery (Vietnam). Acid leaching of the spent catalyst with 2M HNO₃ and a solid-to-liquid ratio of 1/3 at 80 °C in 1 h dissolved almost 90% of La while 12% of Al and 25% of Fe were transferred to the leachate. The extraction of RE metals and main impurities such as Al and Fe by a mixture of di-2-ethylhexyl phosphoric acid (D2EHPA) and tributyl phosphate (TBP) was investigated. Experiments showed that it was necessary to remove Fe before extracting RE and the optimum extraction conditions for a high recovery of RE while 0% of Al extraction were pH-1, contact time=10min, and D2EHPA/TBP volume ratio= 4: 1. At these conditions, the extraction yields of La(III) and Ce(III) were 72% and 89%, respectively. A two-step solvent extraction was developed to achieve a high purity of RE mixture, which included (1) the removal of impurity Fe by 25% (v/v) diisooctyl phosphinic acid (DiOPA) in n-octane for 140 min, (2) the extraction of rare earths by a mixture of di-2-ethylhexyl phosphoric acid (D2EHPA) and tributyl phosphate (TBP) in n-octane for 10 min without the need for adjusting the pH of the leaching solution.     

Zinc and Copper Separation through an Emulsion Liquid Membrane Containing Di‐(2‐Ethylhexyl) Phosphoric Acid as a Carrier

The separation of zinc and copper ions from sulfuric acid solutions by an emulsion liquid membrane (ELM), using di‐(2‐ethylhexyl) phosphoric acid (D2EHPA) as a carrier, has been investigated. The batch extraction of zinc and copper was carried out while varying a selection of experimental conditions, i.e., stirring speed, treatment ratio, concentrations of metal ions in the feed phase, carrier and Span 80 concentration in the membrane, and internal phase concentration. The results obtained demonstrate the effectiveness of D2EHPA as a carrier for the separation of zinc and copper from sulfuric acid media using an ELM. An increase of the D2EHPA concentration beyond 2 vol.‐% does not result in the improved extraction of zinc because the viscosities of the membrane and emulsion have a trend to increase for higher carrier concentrations. It was found that the extraction rate of copper was affected by the carrier concentration in the liquid membrane and by the pH and metal content in the external phase. A 3 vol.‐% concentration of surfactant in the organic phase was required to stabilize the emulsion. The number of stages required for the extraction of zinc and copper by an ELM was determined from McCabe‐Thiele plots.     

Solvent Extraction Studies for Separation of Zn(II) and Mn(II) from Spent Batteries Leach Solutions

This study aims at assessing the possibility of using solvent extraction processes for separating Zn(II) and Mn(II) dissolved in aqueous solutions obtained by acid bioleaching of spent alkaline and Zn-C batteries. In this context, Cyanex 272 and DEHPA were tested as extractant agents, and the former was shown to have better performance. Hence, the effect of four factors (equilibrium pH, extractant concentration, A/O ratio, and temperature) into three response variables (extraction efficiency of Zn, Y_Zn; extraction efficiency of Mn, Y_Mn; separation factor, β) were tested according to a full factorial design (2⁴) with two replicated center points. Our study revealed that Y_Zn depends mainly on the extractant concentration, Y_Mn on the equilibrium pH and β on the equilibrium pH, extractant concentration, and A/O ratio as well as on second and third order interactions. One extraction step is sufficient to reach high extraction of zinc in synthetic solutions, but two stages were required for real leaching liquor. The extraction kinetics is fast (less than 15 min) for both metals, even when real liquor was tested. The organic solvent can be efficiently recovered using a stripping solution of H₂SO₄ 1 M and thus the process can be considered environmentally sustainable.     

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.     

Thermodynamical and catalytic aspects of zinc separation from aqueous solution

The present research work examines extraction mechanism of zinc by D2EHPA (Di-2-ethyl hexyl phosphoric acid) and comprehensively studies the main effective parameters on the process. Results of thermodynamic experiments showed that zinc extraction by D2EHPA was endothermic and spontaneous, and thermodynamic parameters including entropy and enthalpy were+27.37 J·mol^-1·K^-1 and 25.21 kJ·mol^-1, respectively. Gibbs free energy was varied between -7.21 kJ·mol^-1 and -8.41 kJ·mol^-1 with the variation of temperature from 20℃ to 70℃. Solution ionic strength was increased by addition of potassium and lithium sulfate solution while addition of calcium sulfate decreased ionic strength whereby zinc extraction efficiency was also decreased. TBP showed positive synergism at concentration of 5% (v/v) and negative synergism effect at concentrations of 2% and 10%. Simultaneous addition of both TBP and salt caused extraction efficiency to drop significantly and lower both TBP and ionic strength efficiency. Results showed that a continuous addition of TBP tends to effectively improve the zinc extraction efficiency. Experiments in the presence of catalyst Ni-Raney demonstrated that zinc extraction kinetic increases remarkably and due to easy recycling of the catalyst, we can propose a novel idea in solvent extraction field.     

Synergistic separation of yttrium ions in lanthanide series from rare earths mixture via hollow fiber supported liquid membrane

Separation of yttrium ions from the mixture of rare earths in lanthanide series has been examined by a microporous hydrophobic hollow fiber supported liquid membrane. Cyanex 272 and TBP in kerosene are used separately as an extractant. Nitric acid solution is used as a stripping solution. Increasing the concentration of Cyanex 272 increases the percentages of extraction and stripping of yttrium from rare earths but slightly percentages are obtained by TBP. Interestingly, when TBP is added with Cyanex 272, the percentages of extraction and stripping increases. This is due to the synergistic effect of the extractants. Moreover, yttrium can be selectively extracted and stripped more than other lanthanide ions because the equilibrium constant decreases with an increase in atomic number or decreases with the ionic radius of the lanthanides. In other words, yttrium is separated selectively due to the smallest ionic radius while other lanthanides are separated with a decrease in ionic radius or an increase in atomic number.     

Separation and Recovery of Light Rare-Earths from Chloride Solutions using Organophosphorus based Extractants

In this paper, separation possibilities of light rare-earths (LREs), Ce, La, Nd, and Pr with three acidic organophosphorus extractants such as TOPS 99 (an equivalent of di-2-ethylhexyl phosphoric acid, D2EHPA), PC 88A(2-ethylhexylphosphonic acid mono-2-ethylhexyl ester), and Cyanex 272 (Bis(2,4,4-trimethylpentyl)phosphinic acid) from synthetic chloride solutions of monazite at three initial pH values has been investigated. The composition of synthetic leach liquor is Ce ? 5.4 g/L, La ? 3.12 g/L, Nd ?1.35 g/L, and Pr ? 0.475 g/L at pH 2.0. Using sodium hypochlorite and sodium hydroxide, cerium was precipitated as ceric hydroxide quantitatively. Among the three investigated extractants, TOPS 99 showed better separation factors towards LREs. Therefore, 0.7 mol/L TOPS 99 has been employed for the separation of Nd, and Pr from La in 3-stages at an aqueous to organic phase ratio of 4:1 and pH 2.0. Raffinate contains 2120 mg/L La, 41 mg/L of Nd, and 17 mg/L of Pr corresponding to an extraction efficiency of 32.1%, 96.4%, and 96.2%, respectively. La from loaded organic phase was scrubbed with 9182 mg/L Nd solution and achieved a scrubbing efficiency of 98.2%. 1 mol/L HCl is used for quantitative stripping. A process flowsheet for the separation and recovery of LREs was presented.     

THE EXTRACTION OF SOME BASE METAL IONS BY CYANEX 30L CYANEX 302 AND THEIR BINARY EXTRACTANT MIXTURES WITH ALIQUAT 336

ABSTRACT

The extraction behaviour of Cyanex 301, Cyanex 302 and their binary extractant mixtures with Aliquat 33b towards copper(II), zinc(II), iron(III), iron(II), cobalt(II), nickel(II) and manganese(Il) is indicated. The extraction data were collected from sulphate solutions with acidities ranging from pH 10 to 8 mol/dm³ sulphuric acid. Cyanex 301 is a more efficient extractant than Cyanex 302 and is able to effect extraction at greater acidities. In combination with the organic base Aliquat 336 the extraction power of these extractants is lowered and in some cases the extraction is suppressed appreciably. However, the suppression of extraction can be useful in metal separation and affords greater control over the back-extraction. The suppression is ascribed to the high stability of the acid-base couple which must dissociate in order to effect extraction.