两相更新支撑液膜中金属二价镍的迁移行为研究(英文)

A novel disphase supplying supported liquid membrane(DSSLM),containing supplying feed phase and supplying stripping phase for transport behavior of Ni(II),have been studied.The supplying supported feed phase included feed solution and di(2-ethyhexyl) phosphoric acid(HDEHP) as the carrier in kerosene,and supplying stripping phase included HDEHP as the carrier in kerosene and HCl as the stripping agent.The effects of volume ratio of membrane solution to feed solution(O/F),pH,initial concentration of Ni(II) and ionic strength in the feed solution,volume ratio of membrane solution to stripping solution(O/S),concentration of H2SO4 solution,HDEHP concentration in the supplying stripping phase on transport of Ni(II),the advantages of DSSLM compared to the traditional supported liquid membrane(SLM),the system stability,the reuse of membrane solution and the reten-tion of membrane phase were studied.Experimental results indicated that the optimum transport of Ni(II) was ob-tained when H2SO4 concentration was 2.00 mol·L-1,HDEHP concentration was 0.120 mol·L-1,and O/S was 4:1 in the supplying stripping phase,O/F was 1︰10 and pH was 5.20 in the supplying feed phase.The ionic strength in supplying feed phase had no obvious effect on transport of Ni(II).When initial Ni(II) concentration was 2.00×10?4 mol/L,the transport percentage of Ni(II) was up to 93.1 % in 250 min.The kinetic equation was deduced in terms of the law of mass diffusion and the interface chemistry.     

La(III) Transport in Dispersion Supported Liquid Membrane Including PC-88A as the Carrier and HCl Solution as the Stripping Solution

The transport of La(III) through a dispersion supported liquid membrane with polyvinylidene fluoride membrane as the liquid membrane support and dispersion solution including HCl solution as the stripping solution and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC-88A) in kerosene as the membrane solution, was studied. As a result, the optimum transport conditions of La(III) were obtained as that concentration of HCl solution was 4.0 mol/L, concentration of PC-88A 0.16 mol/L, and volume ratio of membrane to stripping solution 30:30 in the dispersion phase, and pH value 4.0 in the feed phase. Ionic strength had no obvious effect on the transport of La(III). Under the optimum conditions, when initial concentration of La(III) was 0.8′10-4 mol/L, the transport rate was up to 96.3% during the transport time of 125 min. The kinetic equation was developed based on the law of mass diffusion and theory of interface chemistry. The diffusion coefficient of La(III) in the membrane and the thickness of diffusion layer between feed and membrane phases were obtained as 3.20′10-7 m2/s and 3.22′10-5 m, respectively. The calculated results were in good agreement with experimental results.     

Absorption of Low Concentration Sulfur Dioxide Using Liquid-containing Microporous Membrane

The absorption of low concentration SO2 in flue gas by using the module of liquid-containing microporous membrane which is made up of hollow fiber and citric acid-sodium citrate buffer solution was investigated. The absorption efficiency of hydrophilic and hydrophobic membranes by using the concept of dynamic contact angle was mainly studied. The influences on absorption efficiency from absorption time, flowrate of gas phase, SO2 concentration of gas phase, air pressure, citrate concentration, pH value of solution as well as the generation of sulfate radical in absorption solution were examined. The results indicate that the hydrophobic hollow fiber membrane is better than hydrophilic membrane, the absorption efficiency decreases with increasing absorption time, gas phase flowrate, gas phase SO2 concentration and air pressure, the absorption rate and capacity of SO2 can be improved by increasing the citrate concentration, the absorption efficiency can be improved by increasing the pH value of citrate solution, the concentration of SO42- in absorption solution increases linearly with the absorption time at a rate around 0.192 g/(L×h).     

苯酚体系支撑液膜不稳定性研究

The instability mechanisms of the supported liquid membrane using Celgard 2500 membranes as support and tributyl phosphate dissolved in kerosene as carrier for phenol transport was studied by electrochemical impedance spectroscopy. Emulsion formation is demonstrated to be one of the main causes for the instability of supported liquid membrane in the present system. The emulsion-facilitated conditions, such as higher membrane liquid concentration, faster stirring speed, lower salt concentration and higher HLB value, would accelerate the degradation of supported liquid membrane. Other mechanisms including solubility and os-motic pressure work together to increase the membrane liquid loss.     

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.     

P507溶于煤油作为载体的一种新型分散组合液膜对Eu3+的分离

The separation of Eu3+ is studied with a dispersion combined liquid membrane (DCLM), in which polyvinylidene fluoride membrane (PVDF) is used as the liquid membrane support, dispersion solution containing HCl solution as the stripping solution, and 2-ethyl hexyl phosphonic acid-mono-2-ethyl hexyl ester (P507) dissolved in kerosene as the membrane solution. The effects of pH value, initial concentration of Eu3+ and different ionic strength in the feed phase, volume ratio of membrane solution to stripping solution, concentration of HCl solution, concentration of carrier, different stripping agents in the dispersion phase on the separation are investigated. The optimum condition for separation of Eu3+ is that concentration of HCl solution is 4.0 mol•L1, concentration of carrier is 0.16 mol•L1, and volume ratio of membrane solution to stripping solution is 30︰30 in the dispersion phase, and pH value is 4.2 in the feed phase. The ionic strength has no significant effect on separation of Eu3+. Under the optimum condition, when the initial concentration of Eu3+ is 0.8×104 mol•L1, the separation percentage of Eu3+ is 95.3% during the separation time of 130 min. The kinetic equation is developed in terms of the law of mass diffusion and the theory of interface chemistry. The diffusion coefficient of Eu3+ in the membrane and the thickness of diffusion layer between feed phase and membrane phase are obtained and their values are 1.48×107 m2•s1 and 36.6 μm, respectively. The results obtained are in good agreement with literature data.     

Intensification of zirconium and hafnium separation through the hollow fiber renewal liquid membrane technique using synergistic mixture of TBP and Cyanex-272 as extractant

The novel synergistic mixture of TBP and Cyanex-272 is used as the extractant in the hollow fiber renewal liquid membrane(HFRLM) technique for Zr/Hf separation.The effects of the chemical and operational parameters such as HNO_3 concentration in the donor phase,NH4 F concentration in the acceptor phase,Cyanex-272 and TBP concentration in the liquid membrane phase,the lumen and shell side flow rates,and aqueous/organic volume ratio on the mass transfer and separation performance of HFRLM method were investigated.The obtained results reveal the intensification potential of proposed HFRLM technique for selective extraction of Zr over Hf with separation factor higher than 100.The HFRLM method provides two times higher mass transfer flux in comparison with hollow fiber supported liquid membrane(HFSLM).Also,the HFRLM method shows satisfactory stability for 700 min of continuous operation.The Zr ion transport through the LM phase follows the coupled co-transport mechanism and the diffusion in the renewal layer is recognized as the rate-controlling step in the HFRLM process.Moreover,the Zr mass transfer coefficient and molar flux in the HFRLM method are calculated in the range of 1×10~(-8)to 8.4×10~(-7) m·s~(-1) and 4.9×10~(-6) to 20.1×10~(-6) mol·m~(-2)·s~(-1),respectively.     

THE STUDY ON THE MASS TRANSFER MECHANISM OF EUROPIUM ION THROUGH LIQUID SURFACTANT MEMBRANES

The transfer of trivalent europium ion in a liquid surfactant membrane system is investigated in order toclarify the characteristics of liquid membrane separation process and the availability of this technique forrecovering trivalent lanthanides and actinides.A layered structure model for the emulsion globule is sug-gested.The equations describing the relationship among the effective membrane thickness,the time andother factors are derived and verified experimentally.Results show that under certain conditions the decreas-ing concentration of europium ion in the external phase is proportional to the square root of the time,the acidity of the internal phase and the carrier concentration in the membrane phase.The membrane phase consists of kerosene(solvent),Span-80(surfactant)and di-(2-ethylhexyl) phosphoricacid(HDEHP,carrier).The internal phase is dilute nitric acid and the external phase is aqueous solu-tion containing Eu(NO_3)_3.The mass transfer rate of europium in this system is high and the recovery ofeuropium may be more than 99%.     

The removal of Cr(Ⅵ) through polymeric supported liquid membrane by using calix[4]arene as a carrier

In this work, the transport and removal of Cr(Ⅵ) were achieved through supported liquid membrane(SLM) by using a 5,17, di-tert-butyl-11,23-bis[(1,4-dioxa-8-azaspiro [4,5]decanyl)methyl]-25,26,27,28-tetrahydroxy calix[4]arene carrier, dissolved in 2-nitrophenyl octyl ether dichloromethane.The studied parameters are the solvent effect in the membrane phase, the effect of carrier concentration, and the acid type in the donor phase.The Celgard 2500 was used as a membrane support.We used the Danesi mass transfer model to calculate the permeability coefficients for each studied parameter.In addition, AFM and SEM techniques were used to characterize the surface morphology of the prepared Celgard 2500 membrane that included the calix[4]arene carrier.     

THE SWELLING BEHAVIOR OF (W/O)/W LIQUID SURFACTANT MEMBRANE(Ⅰ)MODELING OF THE PERMEATION-SWELLING PROCESS

Water transfer through the organic phase of kerosene containing surfactant Span 80,L113B and certain carrier wasstudied theoretically and experimentally in(W/O)/W liquid surfactant membranes.The process of swelling owing to os-motic pressure can be pictured as solubilization of water in membrane phase caused by surfactant and certain carriers andthen diffusion of it through the membrane between the two aqueous phases due to the gradient of chemical potential.Amathematical model for estimating the permeation-swelling rate has been developed.This mathematical model does notcontain any adjustable parameters and the predicted values agree well with the experimental data of Fujinawa et al.,Xinsheng Ma and Yajun Shi and the authors.Using an apparatus developed for measuring the solubility of water in membrane phase,data for solubilization ofwater in oil caused by some surfactants and carrier were measured.     

Removal of Aniline from Wastewater Using Hollow Fiber Renewal Liquid Membrane

Hollow fiber renewal liquid membrane (HFRLM) method was proposed based on the surface renewal theory for removal of aniline from waste water. The system of aniline + D2EHPA in kerosene + HCl was used. Aqueous layer diffusion in the feed phase is the rate-control step, and the influence of lumen side flow rate on the mass transfer is more significant than that on the shell side. The resistance of overall mass transfer is greatly reduced because of the mass transfer intensification in the renewal of liquid membrane on the lumen side. The driving force of mass transfer can be considered as a function of distribution equilibrium, and the overall mass transfer coefficient increases with the increase of pH in the feed solution, HCl concentration and D2EHPA concentration, and decreases with the increase of initial aniline concentration. A mass transfer model is developed for HFRLM based on the surface renewal theory. The calculated results agree well with experimental results. The HFRLM process is a promising method for aniline wastewater treatment.     

Recovery of Copper Ions from Wastewater by Hollow Fiber Supported Emulsion Liquid Membrane

Recovery of copper ions from wastewater using a hollow fiber supported emulsion liquid membrane (HFSELM) was studied with LIX984N as carrier, kerosene as diluents, and sulfuric acid solution as strippi...     

Transport of cobalt(II) through a hollow fiber supported liquid membrane containing di-(2-ethylhexyl) phosphoric acid (D2EHPA) as the carrier

This work presents experimental, modeling and simulation studies for Co²⁺ ion extraction using hollow fiber supported liquid membrane (HFSLM) operated in a recycling mode. Extractant di-(2-ethylhexyl) phosphoric acid (D2EHPA) diluted with kerosene has been used as the membrane phase. The Co²⁺ ion concentration in the aqueous feed phase was varied in the range of 1–3 mM. Also, D2EHPA concentration was varied in the range of 10–30% (v/v). A mass transfer model has been developed considering the complexation and de-complexation reactions to be fast and at equilibrium. Equations for extractant mass balance and counter-ion (H⁺) transport have also been incorporated in the model. Extraction equilibrium constant (K_ex) for cobalt–D2EHPA system has been estimated from equilibration experiments and found to be 3.48 × 10⁻⁶. It was observed that the model results are in good agreement with the experimental data when diffusivity of metal-complex (D_m) through the membrane phase is 1.5 × 10⁻¹⁰ m²/s. Feed phase pH and strip phase acidity had negligible effect on the extraction profiles of Co²⁺ ions. An increase in D2EHPA concentration increased extraction rates of Co²⁺ ions. The membrane phase diffusion step was found to be the controlling resistance to mass transfer.     

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.     

A Reaction Flux Model for Extraction of Cu(II) with LIX84I in HFSLM

Hollow fiber supported liquid membrane (HFSLM) is a favorable method to extract both valuable compounds and heavy metal pollutants such as chromium, copper, and nickel at a very low concentration. In this work, the extraction of Cu(II) by LIX84I dissolved in kerosene was theoretically and experimentally investigated. A model to estimate the percentage of extraction of copper ions from synthetic water considering the effect of reaction flux in membrane phase of the HFSLM system was studied. H₂SO₄ solution was used as the stripping solution. The facilitated transport mechanism of the chemical reaction at the feed-membrane interface was taken into account in the model equations. The percentage of copper ion extraction was plotted against its initial concentration in feed and also feed flow rate. Subsequently, the separation time and separation cycle were determined in accordance with the simulated values of copper ion concentration and the feed flow rate from the model. The modeled results were in good agreement with the experimental data at the average percentage of deviation about 2%.     

New liquid membrane technology for simultaneous extraction and stripping of copper(II) from wastewater

In this paper, a new liquid membrane technique, hollow fiber renewal liquid membrane (HFRLM), is presented, which is based on the surface renewal theory, and integrates the advantages of fiber membrane extraction, liquid film permeation and other liquid membrane processes. The results from the system of CuSO₄+D2EHPA in kerosene+HCl show that the HFRLM process is very stable. The liquid membrane is renewed constantly during the process, the direct contact of organic droplets and aqueous phase provides large mass transfer area. These effects can significantly reduce the mass transfer resistance in the lumen side. Then the mixture of feed phase and organic phase flowing through the lumen side gives a higher mass transfer rate than that of stripping phase and organic phase, because the aqueous layer diffusion of feed phase is the rate-controlling step. The overall mass transfer coefficient increases with increasing flow rates and D2EHPA concentration in the organic phase, and with decreasing initial copper concentration in the feed phase. The overall mass transfer coefficient also increases with increasing pH in the feed phase, and reaches a maximum value at pH of 4.44, then decreases. Also, there is a favorable w/o volume ratio of 20:1 to 30:1 for this process. Compared with hollow fiber supported liquid membrane and hollow fiber membrane extraction processes, HFRLM process has a high mass transfer rate. Mathematical model for the HFRLM process based on the surface renewal theory is developed. The calculated results are in good agreement with experimental results under the conditions studied.     

LIX984N为载体的中空纤维更新液膜中铜的传递过程

以LIX984N为载体,煤油为稀释剂,H2SO4为反萃剂,研究了中空纤维更新液膜过程中铜的传递行为。考察了两相压差、铜离子浓度、两相流速、操作方式以及膜丝有效长度等对传质过程的影响。结果表明:膜丝两侧的操作压差对传质过程几乎没有影响;随着料液相中溶质Cu(Ⅱ)浓度的增大传质通量增大,而反萃相中的Cu(Ⅱ)浓度对传质过程几乎没有影响;传质通量会随着壳程料液流速的增大而增大,但管程侧反萃相的流速对传质过程影响很小;逆流和并流两种操作方式对传质过程的影响可以忽略,而膜丝有效长度的增加会导致单位面积平均传质通量的下降。     

ELM法提取磷酸中La3+的相界面反应-传质机理研究

在以(D2EHPA+TOPO)/ROSO3H/液体石蜡/煤油为膜相,HCl为内相,磷酸中La3+为外相的乳化液膜(ELM)体系中研究了不同相比A/O、膜相D2EHPA(H2A2)、TOPO、ROSO3H浓度、料液相H3PO4、H2PO4和H+浓度和内相HCl浓度对总分配比DT的影响。实验结果表明:随A/O的增加,DT显著下降;随膜相H2A2、TOPO、ROSO3H浓度的增加,DT先增加后基本不变;但料液相H3PO4和H+浓度的增加使DT降低,DT随H2PO4浓度增加而升高;DT随內相HCl浓度的增加而升高。通过斜率法对ELM各组分H2A2、TOPO、ROSO3H、H2PO4、H3PO4、H+的logc-logDT的线性拟合直线的斜率确定了其参与的摩尔数,得到了该ELM体系的相界面反应-传质机理,并计算出萃取、反萃反应平衡常数k1、k2分别为107.7237、104.8025。     

Separation of Zinc by a Non‐dispersion Solvent Extraction Process in a Hollow Fiber Contactor

Abstract

A process for recovery of zinc from acid solution with di(2‐ethyl hexyl phosphoric acid) (D2EHPA) dissolved in iso‐dodecane was carried out at 20°C in a countercurrent tubular membrane extractor using a hollow fiber as solid support. Experiments were performed at different aqueous metal concentrations (0.1–1.0 g/L), pH 0.1–2.1, and D2EHPA concentrations (2–8 v%). It was found that both the flux of metal and the extraction extent was highly influenced by the extractant concentration and the pH of the feed solution. Overall mass transfer coefficients were determined and related to the tube side, the membrane, and the shell side mass transfer by varying the aqueous flow rate (0.38–0.80 L/min) and organic flow rate (0.22–0.57 L/min) in countercurrent flow. The overall mass transfer coefficient for zinc extraction ranged from 6.2×10^?6 m/s to 25.3×10^?6 m/s. It was concluded that extraction kinetics were a major contributor to the overall resistance to mass transfer.