Transport of Co(II) Ions through Di(2-ethylhexyl) Phosphoric Acid-CCl4 Supported Liquid Membranes

Abstract

A liquid membrane transport study of Co(II) using di(2-ethylhexyl) phosphoric acid (D2EPHA) as carrier and CCl₄, as diluent supported on polypropylene microporous film has been carried out. The carrier concentration in the membrane and HCl concentration in the stripping phase have been varied to see the effect on transport of Co(II) ions across the membrane. Maximum flux and permeability values of 1.23 × 10^?5 mol · m^?2 · s^?1 and 7.66 × 10^?11 m²/s, respectively, at a 0.87 mol/dm³ carrier concentration in the membrane have been found. At 1 mol/dm³ HCl concentration in the stripping phase the flux and permeability have maximum values of 1.4 mol · m^?2 · s^?1 and 5.27 × 10^?11 m²/s, respectively. The distribution coefficient of Co(II) ions into organic phase has been found to increase with increasing carrier concentration. The diffusion coefficient determined varies from 13.73 × 10^?11 to 0.83 × 10^?11 m²/s, which is the reverse order of the values of the distribution coefficient and explains the permeability of the Co(II) D2EPHA complex through the membrane.     

Transport of Europium(III) through Supported Liquid Membrane Containing Diisodecylphosphoric Acid

Abstract

Carrier mediated transport of europium has been investigated by the use of a flat-sheet membrane impregnated with diisodecylphosphoric acid (DIDPA). The addition of 1-octanol to the membrane improves the stripping process, and hence europium can be quantitatively transported from the feed solution of 0.1 M HNO₃ into the product solution of 5 M HNO₃. Its concentration in the feed solution decreases as [Eu] _f,t = [Eu] _f,0 exp (-k _obs t). The apparent rate constant (k _obs) increases with increasing carrier concentration and becomes nearly constant above 0.05 M DIDPA The europium flux is proportional to initial europium concentrations less than 10^?3 M, and becomes constant at high concentrations.     

Transport of Cadmium(II) Ion through a Supported Liquid Membrane Containing a Bathocuproine

Abstract

The active transport of cadmium ions across a supported liquid membrane (SLM) containing a ligand based on a driving force supplied by the concentration gradient of the chloride ion is described. The SLM used is a microporous polypropylene membrane impregnated with a bathocuproine (4,7-diphenyl-2.9-dimethyl-1,10-phenanthroline) solution in dibenzyl ether as a carrier. The characteristics of the cadmium ion transport system are examined under various experimental conditions. The active transport of cadmium ions through an SLM is dependent on the concentrations of the cadmium ion, ligand, and chloride ion. An equation for the permeation velocity of cadmium ions, consisting of three important factors for this transport system, is proposed.     

Transport of Eu3+ through a Bis(2-ethylhexyl)-phosphoric Acid,n-Dodecane Solid Supported Liquid Membrane

Abstract

The coupled transport of Eu³⁺ and H⁺ ions through a solid supported liquid membrane consisting of a porous polypropylene film immobilizing an HDEHP solution in n-dodecane has been studied as a function of the membrane area, stirring speed of the aqueous solutions, membrane composition, and acidity of the feed solution. The experimental results are in agreement with predictions derived from a theoretical permeability coefficient equation which assumes that membrane diffusion and aqueous film diffusion are the only rate-controlling factors.     

The Role of Feed Metal Concentration in the Coupled Transport of Zinc through a Bis-(2-ethylhexyl)phosphoric Acid Solid Supported Liquid Membrane from Aqueous Perchlorate Media

Abstract

The coupled transport of Zn(II) macroconcentrations (up to 100 mmol/dm³) and H⁺ through a solid supported liquid membrane (SSLM) consisting of bis-(2-ethylhexyl)phosphoric acid (HDEHP) dissolved in the aliphatic kerosene Isopar-H has been investigated as a function of the hydrodynamic characteristics and chemical composition of the system. The results were analyzed in terms of a model considering the aqueous and organic diffusion as well as chemical reaction rates in order to explain the observed zinc transfer rates. The analysis showed the importance of the carrier saturation phenomenon taking place as the metal concentration is increased and the subsequent minimization of the role of chemical reaction kinetics.     

Transport of Chromium(VI) through a Supported Liquid Membrane Containing Tri-n-octylphosphine Oxide

ABSTRACT

In this study the transport of chromium(VI) from aqueous solutions of pH 2–4 through a supported liquid membrane (SLM) with tri-n-octylphosphine oxide (TOPO) dissolved in kerosene as a mobile carrier was investigated. The transport flux of Cr(VI) increased with an increase in the concentrations of Cr(VI) in the feed phase and of TOPO in the membrane phase, but with a decrease in pH of the feed phase. Considering the equilibria of various Cr(VI) species in the aqueous phase and of the Cr(VI)—TOPO complexes formed in the membrane phase, a permeation model including the aqueous film diffusion of HCrO₄ ^? and Cr₂O₇ ^2? toward the membrane, the interfacial chemical reaction between them and TOPO, and the membrane diffusion of the Cr(VI)—TOPO complexes (H₂CrO₄(TOPO) and H₂Cr₂O₇(TOPO)₃) was proposed to describe the transport of Cr(VI) through the SLM. By best fitting the transport flux equations of Cr(VI) with the experimental data using the Rosenbrock method, the apparent mass-transfer coefficients of HCrO₄ ^? and Cr₂O_7^. across the aqueous film, and those of H₂CrO₄(TOPO) and H₂Cr₂O₇(TOPO)₃ across the membrane phase, were obtained. This work helps to clarify the transport mechanism of Cr(VI) through an SLM.     

二-(2-乙基己基)磷酸合成工艺研究

研究了合成二－（2－乙基己基）磷酸的工艺优化条件，通过加入无水AlCl3，严格控制反应温度，控制三氯氧磷加入量过量3％等措施，合成的二－（2－乙基己基）磷酸萃取稀土元素性能优于标准萃取剂。     

Extraction Equilibria of 4-Hydroxypyridine using Di (2-ethylhexyl) Phosphoric Acid

Extractions of 4-Hydroxpyridine (4HP) from aqueous solutions using Di(2-ethylhexyl)phosphoric acid (D2EHPA) as extractant in 1-octanol and kerosene were studied. The factors that affected the distribution coefficient (D), such as equilibrium pH, the concentration of D2EHPA, and the type of diluents were discussed. The interaction mechanism between 4HP and D2EHPA was validated by infrared spectroscopic analysis. D increased with the increase of the concentration of D2EHPA and peak values appeared at equilibrium pH = 3.6–5.0. D in the polar diluent (1-octanol) was much higher than those in the non-polar diluent (kerosene). The extraction reaction was found to be a proton-transfer process and D2EHPA mainly reacted through its –OH with –N– of 4HP. The apparent reactive extraction equilibrium constants K ₁₁ and K ₁₂ were obtained by fitting the experimental data of extraction equilibrium. By comparing calculated D values from the proposed model with the experimental ones, the accuracy of the proposed model was examined.     

Distribution Behavior of Amino Acid by Extraction with Di(2-ethylhexyl) Phosphoric Acid

Abstract

The distribution equilibrium of l-tryptophan (l-Trp) by extraction with di(2-ethylhexyl) phosphoric acid (D2EHPA) dissolved in n-hexane was studied. The effects of L-Trp and D2EHPA concentrations, pH, and ionic strength, particularly of L-Trp loading in the organic phase, on extraction equilibrium were examined in detail. When the amino acid loading ratio (the molar concentration ratio of the equilibrium amino acid in the organic phase to the initial dimeric D2EHPA) was less than 3 × 10^?3, one L-Trp molecule was extracted by forming a complex with four monomeric D2EHPA molecules, and the extraction equilibrium constant (K _e) was determined to be 0.045 dm³/mol. Above this loading ratio the equilibrium formula did not hold, and the apparent equilibrium constant (K _a) increased significantly with increasing loading ratio. The phenomenon was explained by taking into account two parallel reactions in which fewer D2EHPA molecules, two and one respectively, were needed to extract one l-Trp molecule.     

Transport of Europium through Supported Liquid Membrane Containing Dihexyl-N,N-diethylcarbamoylmethylphosphonate

Abstract

The transport of europium has been studied through a supported liquid membrane (SLM) impregnated with dihexy-N,N-diethylcarbamoylmethylphosphonate (CMP). Europium was effectively extracted from the perchlorate solution into SLM, but was insufficiently stripped to a dilute acid solution. The addition of 1-decanol improved the stripping process, and quantitative transport of europium was achieved. By the combination of two SLM systems consisting of diiso-decylphosphoric acid and CMP, europium was transported from the feed solution (0.1 M HNO₃) through the intermediate solution (1 M HclO₄ + 4 M NaClO₄) to the product solution (0.1 M HNO₃) and effectively concentrated by a factor of about 20.     

Cu2+在支撑液膜中的传质过程

研究了以疏水性多孔聚丙烯膜(Celgard 2500)为支撑体和LIX984的煤油溶液为膜液的支撑液膜体系萃取Cu2+的传质过程. 采用双膜理论描述Cu2+通过平板支撑液膜的传质过程,建立了其在稳态下的传质动力学方程,且当反萃取侧酸浓度大于2 mol/L时,反萃取侧的传质阻力可以忽略;利用膜内分传质系数km表征支撑液膜膜液的流失行为,在传质过程中,km先增大而后逐渐减小,且载体的流失速率大于稀释剂煤油的流失速率. 考察了操作条件对传质和膜液流失速率的影响,结果表明,Cu2+初始传质通量随载体初始浓度、料液初始pH值和料液初始Cu2+浓度的增大而增大;载体初始浓度越大,膜液流失越快;料液初始Cu2+浓度增大,膜液流失越慢;料液相pH值的改变对膜液流失速率没有影响.     

Synergic Extraction of Folic Acid with Di(2-ethylhexyl) Phosphoric Acid and Amberlite LA-2

The influences of extractants concentrations and solvent polarity on the efficiency of folic acid separation by synergic extraction with Amberlite LA-2 and di(2-ethylhexyl) phosphoric acid (D2EHPA) mixture have been analyzed. The results indicated the formation of an interfacial compound which includes one molecule of folic acid and one of D2EHPA, the hydrophobicity of this compound being increased by solvation with Amberlite LA-2 molecules. The number of aminic molecules participating in the interfacial complex formation is controlled by solvent polarity and D2EHPA concentration, decreasing from 3 to 1 with the increase of these two parameters. The results indicated that the most important synergic effect corresponds to the extractants mixture dissolved n-heptane, at low D2EHPA concentration in the organic phase (5 g/l).     

Separation of Carrier Free 90Y from 90Sr by Hollow Fiber Supported Liquid Membrane Containing Bis(2-ethylhexyl) Phosphonic Acid

The present article gives a comparative account of the efficiency of carrier-free ⁹⁰Y separation from ⁹⁰Sr by solvent extraction, flat sheet-supported liquid membrane (FSSLM) and hollow fiber-supported liquid membrane (HFSLM) methods using bis(2-ethylhexyl) phosphonic acid (PC88A) as the carrier extractant. The major focus of this work has been to develop the HFSLM method for the separation of Y(III) on a relatively large scale. The feed and receiver phase conditions were optimized by carrying out batch solvent-extraction studies. The extraction of Sr(II) by PC88A was negligible in the acidity range of 0.01–3 M HNO₃, whereas the extraction of Y(III) was significantly large at lower acidity (≤0.1 M HNO₃) with a separation factor (SF = D_Y/D_Sr) of 8.5 × 10⁴. HFSLM studies suggested selective and efficient transport of Y(III) into 3 M HNO₃ from a feed solution containing a mixture of Y(III) and Sr(II) at 0.1 M HNO₃. On the other hand, transport of Sr(II) was negligible in the receiver phase. The purity of the separated ⁹⁰Y was ascertained by paper chromatography and by half-life measurement. The radiation stability of the carrier was excellent as studied up to 1000 KGy dose.     

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.     

Study of Mono-(2-ethylhexyl) Phosphoric Acid and Neutral Organophosphorus Synergists for Extraction of Uranium from Phosphoric Acid Solution

Abstract

The distribution of uranium(IV) and uranium(VI) between phosphoric acid solution and mono-(2-ethylhexyl) phosphoric acid (H₂MEHP)-trioctyl phosphine oxide (TOPO), and mono-(2-ethylhexyl) phosphoric acid-dibutyl butyl phosphonate (DBBP) in kerosene diluent has been investigated. The effects of extractant composition, phosphoric acid concentration, temperature, uranium concentration, and shaking time on the uranium extraction have been examined. Reductive extraction and oxidative stripping processes for the separation and concentration of uranium from phosphoric acid solution with synergic systems of H₂MEHP-TOPO and H₂MEHP-DBBP are proposed and discussed.     

Transport of Palladium(II) through Trioctylamine Liquid Membrane

Abstract

The permeation behavior of palladium(II) through a supported liquid membrane (SLM) impregnated with trioctylamine (TOA) in kerosene has been investigated. By selecting perchloric or nitric acid as a stripping agent, Pd(II) was transported through the SLM containing 0.5 M TOA and 20% 1-octanol without remaining in the liquid membrane. The permeation rate (k _{f. obs}) of Pd(II) for HNO₃ was faster than that for HClO₄. Palladium(II) was concentrated across the SLM from the 0.5 M CHI solution into the HClO₄ or HNO₃ solution.     

Modeling of Facilitated Transport of Phenylalanine by Emulsion Liquid Membranes with Di(2-ethylhexyl)phosphoric Acid as a Carrier

ABSTRACT

A mathematical model is developed in this paper to simulate the facilitated transport of phenylalanine (Phe) in emulsion liquid membrane (ELM) systems with di(2-ethylhexyl)phosphoric acid as a carrier. The model takes into account the mass transfer in both the external aqueous phase and the organic membrane phase interfacial reaction as well as membrane breakage during agitation. The model is tested by comparing theoretical predications with experimental results using Phe extraction by ELM processes. It is found that the model is valid for simulating the facilitated transport of Phe with ELM under various experimental conditions.     

Selective Transport of Copper(I,II), Cadmium(II), and Zinc(II) Ions through a Supported Liquid Membrane Containing Bathocuproine,Neocuproine, or Bathophenanthroline

Abstract

Some selective transport systems for heavy metallic ions through a supported liquid membrane (SLM) containing a 2,2′-dipyridyl derivative ligand, 4,7-diphenyl-2,9-dimethyl-1,10-phenanthroline (bathocuproine), 2,9-dimethyl-1,10-phenanthro-line (neocuproine), or 4,7-diphenyl-1,10-phenanthroline (bathophenanthroline), were investigated. The transport of copper(I, II), cadmium(II), zinc(II), lead(II), and cobalt(II) ions was accomplished with a halogen ion such as chloride, bromide, or iodide ion as a pairing ion species for any SLM. The ranking of the permeability of the metallic ions was Cu^+,2+, Zn²⁺, Cd²⁺ ? Pb²⁺, Co²⁺. When the oxidation-reduction potential gradient was used as a driving force for metallic ions, the transport of Cu⁺ ion was higher than those of Cd²⁺ and Zn²⁺ ions for any SLM containing bathocuproine, neocuproine, or bathophenanthroline. On the other hand, in the transport system which used the concentration gradient of pairing ion species, the permeability of the Cu²⁺ ion decreased whereas that of the Cd²⁺ ion increased. Moreover, it was found that the different selectivity for the transport of metallic ions is produced by using various pairing ion species.     

中空纤维支撑液膜技术处理含铜废水

重金属废水的处理在环境保护和重金属资源综合利用方面都受到广泛的关注.采用中空纤维支撑液膜技术,用CuSO4水溶液模拟工业含Cu(Ⅱ)废水,二(2-乙基己基)磷酸(D2EHPA)/煤油为液膜相,盐酸为接受相,研究了液膜相组成、两相流速、流动方式等因素对中空纤维支撑液膜过程传质性能的影响.结果表明,料液相在管程流动时的传质通量大于料液相在壳程流动时的传质通量,传质通量随着管、壳程两相流速的增大及液膜相中载体浓度的增加而增大.模拟实验结果表明,中空纤维支撑液膜技术可同时实现废水中Cu(Ⅱ)的去除与浓缩,处理效果好.废水中Cu(Ⅱ)的去除率达97%以上,富集液中Cu(Ⅱ)浓缩倍数达5倍以上.