Modeling of the Permeation of Thorium through Liquid Emulsion Membrane

Abstract

A general permeation model for the separation of thorium by liquid emulsion membrane (LEM), using theonyletrichloroacetone HTTA as a carrier is presented. The internal mass transfer in the W/O emulsion drop, the external mass transfer around the drop, the rates of formation, and the decomposition of the complex at the external aqueous‐organic interface were considered. Further, the leakage of the internal aqueous phase to the external phase due to the membrane break‐up is also taken into account. The batch extraction of thorium using HTTA as a carrier was carried out under various experimental conditions. It is found that the extraction rates can be satisfactorily simulated by the proposed model.     

支撑液膜萃取乳酸传质模型

本文对使用支撑液膜(Supported Liquid Membrane)从水溶液中革取乳酸(HL)的过程进行了理论分析,经过适当的简化,推导出支撑液膜革取乳酸的传质模型。对模型进行了实验验证,测得了膜的弯曲因子及过程的促进因子,模型计算值与实验值相吻合,同时得出膜内载体三烷基氧磷(TRPO)与乳酸形成的萃合物分子式为HL·TRPO。     

Selective Transport of Bismuth Ions through Supported Liquid Membrane

A new supported liquid membrane (SLM) system was prepared for the selective transport of bismuth ions from the aqueous feed into the aqueous permeate phase. The support of the SLM was a thin porous polypropylene or polyvinylidene fluoride membrane impregnated with diisooctyldithiophosphinic acid (Cyanex 301) as mobile carrier in 4‐chloroacetophenon as organic solvent. Cyanex 301 acts as a highly selective carrier for the uphill transport of bismuth ions through the SLM. In the presence of HNO₃ as a metal ion acceptor in the strip solution, the transport of bismuth ions into the strip side reached 70 % of the initial feed concentration after 3.5 hours. The selectivity and efficiency of bismuth transport from aqueous solutions containing different mixtures of cations were investigated. In the presence of P₂O₇^2– ions as suitable masking agent in the feed solution, the interfering effects of other cations were completely eliminated. The selective transport of bismuth through SLM is superior to liquid‐liquid extraction or through bulk liquid membranes. This is due to the high efficiency. The SLM reduces the solvent requirements, combines extraction and stripping operations in a single process and allows the use of highly selective extractants. The system may be applied to samples containing very low bismuth concentrations.     

Characterization of extracted complexes in liquid–liquid extraction of rhodium with Kelex 100 in the presence of SnCl2

Mixed Rh? Sn complexes found in aqueous and organic solutions involved in the liquid–liquid extraction of Rh(III) from chloride solutions, also containing SnCl₂, with 7-(4-ethyl-1-methyloctyl)-8-hydroxyquinoline (Kelex 100) were characterized through ¹¹⁹Sn NMR and Raman spectroscopy. At Sn: Rh molar ratios of 3:1 and 12:1, it was found that [Rh^IIICl₃(SnCl₃)₃]^3? and [Rh^I(SnCl₃)₅]^4?, respectively, are the dominant complexes in both the aqueous and organic solutions. These complexes can be quantitatively extracted from the aqueous solutions in less than 1 min contact time via ion-pair formation with the protonated 7-substituted 8-hydroxyquinoline reagent such that for both Sn:Rh ratios, the same Rh? Sn complex is found in the aqueous feed and in the fully loaded organic. In addition, it was found that [Rh^I(SnCl₃)₅]^4? is preferentially extracted over excess free Sn(II). Preliminary characterization of the complex stripped from the 12:1 loaded organic using 1·7 M H₂SO₄ shows an Rh? Sn complex having a ratio of 5:1 Sn:Rh.     

Acid Extraction from Liquid Phase Pyrolysis Oil Using Cyanex®923 and Subsequent Solvent Regeneration

Liquid phase pyrolysis (LPP) oil, an intermediate from biofuel production using second‐generation biomass, is a promising source of biobased platform chemicals like acetic acid, however, displaying a complex, multicomponent mixture. Reactive extraction with Cyanex®923 was investigated for selective recovery of acids and subsequent solvent regeneration in distillation at 200 mbar. In a three‐stage extraction 81 % of acids were removed from the LPP oil without loss of Cyanex®923 to the raffinate. Solvent regeneration efficiency of acids was up to 99.7 % with mainly acids and water in the distillate.     

Response Surface Modelling and Optimization of Mercury Extraction through Emulsion Liquid Membrane

Mercury(II) is a very harmful metal, highly toxic, and carcinogenic in nature. Experiments were carried out using the emulsion liquid membrane (ELM) technique in order to evaluate the maximum extraction of mercury(II) from aqueous solutions of mercuric chloride using 3³ factorial design. The ELM consisted of di-2-ethylhexylphosphoric acid as a carrier, toluene as an organic solvent, span 80 as a surfactant, and sulphuric acid with thiourea solution as stripping phase. The three factors for the factorial design were mercury(II) concentration in the aqueous solution, that is, feed phase concentration, carrier concentration in the membrane phase, and sulphuric acid concentration in the stripping phase. The study has also highlighted the effects of various other parameters, such as pH of the feed phase and thiourea concentration on mercury(II) extraction. The optimization of the factors to obtain maximum extraction were carried out by incorporating main effect plots, interaction plots, analysis of variance (ANOVA), normal probability plots, residual plots, surface plots, and contour plots. A reduced model developed by regression analysis was suggested in which the experimental data were fitted very well. The results showed that it is possible to extract mercury(II) up to 98% from aqueous solutions at the optimum conditions.     

液膜法处理H酸废水的多级萃取工艺研究

以Span-80、FSN-100为复合表面活性剂、三辛胺为流动载体,研究了三级逆流萃取时不同乳水比（Rcw）对废水COD去除率指标的影响,同时对逆流萃取后萃取相的破乳情况进行了考察,结果表明液膜法处理H酸废水的多级萃取工艺有较好的适应性。     

Solvent Extraction of Au(III) by the Chloride Salt of the Amine Alamine 304 and Its Application to a Solid Supported Liquid Membrane System

Abstract

The extraction of Au(III) by the chloride salt of the amine Alamine 304 (R₃NH⁺Cl^?) in xylene from hydrochloric acid solutions has been investigated. The analysis of metal distribution data by numerical calculations suggested the formation of the species R₃NH⁺AuCl₄ ^? in the organic phase with formation constant log K _ext = 5.44. The results obtained on Au(III) distribution have been implemented in a solid‐supported liquid membrane system, where in NaSCN solutions were found to be the most effective to strip the metal from the organic solution. Influence of membrane composition, metal concentration on gold transport, and the selectivity of the system have also been studied.     

支撑液膜法脱除氨氮的动力学

研究了以聚丙烯为支撑膜、以D2EHPA为载体脱除废水中的氨氮的支撑液膜体系。通过实验确定了料液pH值、载体浓度等与铵离子渗透系数之间的关系;建立了动力学方程。     

Extraction of Amino-J Acid from Waste-water by Emulsion Liquid Membrane

The emulsion liquid membrane technique was used to extract amino-J acid from industrial dye waste-water. The effects of stirring speed, ratio of the emulsion to water (Rew), ratio of the oil to internal phase (Roi) and membrane phase components on the extraction rate were investigated and optimized. The results showed that the extraction rate of amino-J acid approached 97% when the stirring speed was 300 r/min, Rew 1:6, Roi 1:1, trioctylamine (TOA) 3 mL/100 mL kerosene, and methyl-didecyle-alcohol-acrylate (LMA-2) 3 g/100 mL kerosene, respectively. The extraction rate had not changed with the oil phase reused for times.     

Effects of Membrane Parameters on Performance of Vapor Permeation through a Composite Supported Liquid Membrane

Abstract

Support liquid membranes have been used in air dehumidification due to their inherent high mass transfer rates. In this study, the effects of membrane structural parameters on vapor permeation through a LiCl solution based supported liquid membrane are investigated. To aid in the analysis, a mass transfer model has been proposed for moisture transfer through the membrane, which is composed of a supported liquid layer sandwiched by two hydrophobic protective layers. The model takes into account of the resistance in boundary layers, in the protective hydrophobic layers, and in the supported liquid layer. It is a transient model. It also reflects the distributed nature of moisture permeation through the membrane. The results found that the emission rate exhibits a non‐uniform distribution nature on the membrane surface. The structural parameters of the support and the protective layers, such as thickness, pore diameters, and porosity, have great effects on vapor permeation.     

Process Intensification via Liquid Emulsion Membrane Technique in Extraction and Enrichment of Rhodium (III) from Chloride Media

A liquid emulsion membrane (LEM) system as a tool for process intensification has been studied for rhodium recovery using di-2-ethylhexylphosphoric acid (D2EHPA) as a metal carrier and Monemul 80 as a surfactant, dissolved in liquid paraffin. The various process parameters affecting the LEM process, such as extractant, surfactant, and strip phase concentrations, the speed of agitation, the batch contact time, and the treat ratio have been experimentally investigated to get better insight into the process. Perchloric acid was found to be a better stripping agent in the LEM process. It was observed that the extraction of Rh (III) can be significantly more in the absence of a water repelling agent. The maximum enrichment of Rh (III) in the internal phase obtained was 4.3 times with feed phase pH adjusted to 6, perchloric acid (1.5 mol/dm³), and contact time of 15 min. A mass transfer model to predict the performance of the LEM system was used and found to fit well with the experimental data.     

Homogeneous Liquid-Liquid Extraction of Metal Ion Utilizing Upper Critical Solution Temperature of Propylene Carbonate

ABSTRACT

This study was undertaken to investigate the extraction of In³⁺ and Ga³⁺ by 7-(4-ethyl-1-methyloctyl)-8-hydroxy-quinoline (Kelex100), which has been found to be a slow extraction process. Homogeneous liquid-liquid extraction utilizing upper critical solution temperature of 4-methyl-1,3-dioxolan-2-one (propylene carbonate, abbreviated as PC) was used to eliminate the interface and speed up the extraction, since distribution between two phases was thought to be the rate-determining step. The effect of contact time on the percentage of metal extraction was examined at 80ºC using Kelex100 dissolved in toluene and PC solutions and the difference between two solvents was evaluated. The results clearly show that the use of homogeneous liquid-liquid extraction using PC with Kelex100 is faster than traditional two phase extraction.     

The Transport of Copper(II) through Hollow Fiber Renewal Liquid Membrane and Hollow Fiber Supported Liquid Membrane

Abstract

In this paper, hollow fiber renewal liquid membrane (HFRLM) and hollow fiber supported liquid membrane (HFSLM) were used to simultaneously remove and recover copper(II) from aqueous solutions, and the transport performance of these two techniques were compared under the similar conditions for the system of CuSO₄ +D2EHPA in kerosene +HCl. The results showed that the HFRLM process was more stable than the HFSLM process. The HFRLM process had a higher overall mass transfer coefficient than that of HFSLM process in single-pass experiments. These were because the renewal effect of the liquid membrane layer could reduce the mass transfer resistance of the lumen side and replenish the loss of the membrane liquid in the HFRLM process. The transport results were better in the HFRLM process than that in the HFSLM process with recycling experiments. Therefore, HFRLM technique is a promising method for simultaneous removal and recovery of heavy metal from aqueous solutions.     

Pilot-Scale Evaluation of Supported Liquid Membrane Extraction

Abstract

An evaluation of a solvent extraction system employing supported liquid membranes has recently been completed by Rockwell Hanford Operations. The focus was on a pilot-scale, tube and shell arrangement configured for continuous operation. The tube bundle consisted of 333 polypropylene-iiricroporous fibers with a total surface of 3.6 m².

Results are reported for the evaluation of operating parameters such as flow rates and corresponding aqueous pressure differences, solvent impregnation techniques, and test system durability. Chemical and physical test results, including permeability data, are also reported for the systems nitrate ion/nitric acid/tertiary amine and (nonradioactive) Group IA-IIA metal/nitric acid/ phosphoric acid extractant.     

Study and Optimization of Amino Acid Extraction by Emulsion Liquid Membrane

Abstract

A batch extraction of an essential amino acid, phenylalanine, from an aqueous solution of different concentrations by an Emulsion Liquid Membrane (ELM) was developed using D2EHPA as a cationic carrier, Span 80 as the surfactant, paraffin, and kerosene as the diluents, and HCl as the internal electrolyte. All effective parameters such as the initial pH of the aqueous external phase, the electrolyte concentration in the aqueous internal phase, carrier, and surfactant concentration in the emulsion, the volume ratio of the organic to aqueous internal phase (Roi), the volume ratio of the W/O emulsion to the aqueous external phase (Rew) and time were examined and optimized using the Taguchi method. Applying the Taguchi method to analyze the experimental results, the effects and contribution of each of the factors on the extraction efficiency were obtained. The results obtained from the experiments illustrated that with a stable emulsion, by optimizing all the effective parameters, a considerable amount of phenylalanine can be extracted in a short time with an acceptable ratio of swelling and breakage.     

液膜法提取绿原酸的实验研究

采用液膜法提取杜仲叶中绿原酸,通过正交实验对液膜制备工艺和绿原酸提取工艺进行了研究。结果表明,液膜制备的最佳工艺条件为:NaOH浓度4mol.L-1、吐温-20质量分数8%、搅拌速度350r.min-1;绿原酸提取的最佳工艺条件为:混合时间8min、乳水比1∶2、搅拌速度100r.min-1、油内比3∶1。液膜法实现了对绿原酸的提取和浓缩,为进一步开发利用绿原酸提供了依据。     

液膜分离技术在生化产品提取中的应用进展

介绍了液膜的基本概念、分类和分离机理。与传统的生化产品分离提纯技术相比,液膜分离技术具有简便、高效且成本低的特点。综述了液膜分离技术在抗生素和氨基酸提取中的应用进展,如青霉素、半合成青霉素、头孢菌素、麦白霉素、苯丙氨酸、亮氨酸和谷氨酸的提取,并指出其发展前景。     

PTFE中空纤维膜萃取烟酸工艺研究

以氢氧化钠溶液为萃取剂,采用PTFE中空纤维膜萃取料液中的烟酸,考察了料液相烟酸的初始浓度、料液相初始pH值、料液相与萃取相流量比、萃取剂的初始浓度对烟酸萃取率(η)的影响。结果表明,随着料液初始浓度增大,η增大,当烟酸浓度0.9 g/L时,η减小,但膜通量基本不变,即存在一个最大膜通量,此时烟酸浓度变化对传质无影响;烟酸料液存在一个最佳pH值为4~5;萃取相氢氧化钠浓度增大,η增大;存在一个最佳相流量比(Q料/Q萃)为2.1;温度升高有利于膜萃取。     

PTFE中空纤维膜萃取苯甲酸工艺研究

以氢氧化钠溶液为萃取剂,采用PTFE中空纤维膜萃取料液中的苯甲酸,考察了料液相苯甲酸的初始浓度、料液相初始pH、料液相与萃取相流量比、萃取剂的初始浓度对苯甲酸萃取率(η)的影响。结果表明,随着料液初始浓度增大,η增大,当苯甲酸浓度1 g/L时,η减小,但膜通量基本不变,即存在一个最大膜通量,此时苯甲酸浓度变化对传质无影响;料液的pH值下降,η增大;萃取相氢氧化钠浓度增大,η增大;存在一个最佳相流量比(Q料/Q萃)为1.8。另外,温度升高有利于膜萃取。