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.     

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.     

Emulsion liquid membrane for selective extraction of Bi(III)

Di(2-ethylhexyl)phosphoric acid was used as extractant of bismuth ions from nitrate medium by emulsion liquid membrane, with Triton X-100 as the biodegradable surfactant in n-pentanol bulk membrane. The novelties and innovative points of this work are the application of emulsion liquid membrane for selective and efficient extraction of bismuth ions as wel as the relevant optimization procedures. The extraction of bismuth ions was evaluated by the yield of extraction. The experimental parameters were evaluated and optimized, including the ratio of di(2-ethylhexyl)phosphoric acid mass concentration to Triton X-100 (1.0%:0.5%), nature of diluent (n-pentanol), nature and concentration of stripping solution (sulfuric acid, 0.5 mol·L?1), stirring speed (1800 r·min?1) and equilibrium time of extraction (20 min), initial feed solution of bismuth (350 mg·L?1) and the volume ratio of internal stripping phase to membrane phase (14). The experimental parameters of kinetic extraction reveal that the bismuth ions can be extracted by 100%.     

中空纤维支撑液膜萃取Cu(II)的传递性能

The transport of Cu(II) from aqueous solutions containing buffer media through hollow fiber supported liquid membrane (HFSLM) using di(2-ethylhexyl) phosphoric acid (D2EHPA) dissolved in kerosene as membrane phase and hydrochloric acid as striping phase was investigated. A set of factors were studied, including tube side velocity, shell side velocity, pH of the feed phase, Cu(II) concentration in the feed phase, buffer media concentration and D2EHPA concentration in the membrane phase. Experimental results indicate that the mass transfer coefficient increases with increasing both carrier concentration in the organic phase and flow rates on the tube side and shell side, and decreases with increasing initial Cu(II) concentration in the feed phase. With increasing pH value and acetate concentration in the feed phase, the mass transfer coefficient reaches a maximum value then decreases. The optimal operating conditions are obtained at pH value of 4.44 and 0.1 mol&;#8226;L－1 acetic ion concentration in feed phase, and carrier volume fraction of around 10% in kerosene as organic phase. A mathematical model of the transport mechanism through HFSLM is devel-oped. The modeled results agree well with the experimental ones.     

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.     

乳状液膜中1,3-桥连杯[4]芳烃/冠醚对碱金属离子的选择性萃取(英文)

Nano-assisted inclusion separation of alkali metals from basic solutions was reported by inclu sion-facilitated emulsion liquid membrane process. The novelty of this study is application of nano-baskets of calixcrown in the selective and efficient separation of alkali metals as both the carrier and the surfactant. For this aim, four derivatives of diacid calix[4]-1,3-crowns-4,5 were synthesized, and their inclusion-extraction parameters were optimized including the calixcrown scaffold （4.4%, by mass） as the carrier/demulsifier, the commercial kero sene as diluent in membrane, sulphonic acid （0.2 mol.L-1） and ammonium carbonate （0.4 mol.L-1） as the strip and the feed phases, the phase and the treat ratios of 0.8 and 0.3, mixing speed （300 r.min-1）, and initial solute concentration （100 mg.L-1）. The selectivity of membrane over more than ten interfering cations was examined and the re sults reveled that under the optimized operating condition, the degree of inclusion-extraction of alkali metals was as high as 98%-99%.     

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.     

Osmotic concentration of succinic acid by forward osmosis: Influence of feed solution pH and evaluation of seawater as draw solution

In this study, we investigated the essential role of feed solution pH so as to gain insights into the transport mechanisms of succinic acid concentration by osmotically-driven forward osmosis(FO) process. FO performances including water flux and bidirectional transport of succinate and chloride anions were systematically examined using cellulose triacetate-based FO membrane. Additionally, real seawater was explored as draw solution. Experimental results revealed that the p H-dependent speciation of succinic acid can affect the FO performances. Ionization of succinic acid at higher solution p H enhanced the osmotic pressure of feed solution, thus leading to lower water flux performance. A strong effect was pointed out on the succinate rejection for which nearly 100% rejections were achieved at p H above its pK_(a2) value. The rejection of succinate increased in the following order of chemical form: C_2H_4 C_2O_4H_2 C_2H_4C_2O_4H~ˉ C_2H_4C_2O_4~(2-).With real seawater as the draw solution, low to moderate water fluxes(4 L·m~(-2)·h~(-1)) were observed.The divalent succinate anion was highly retained in the feed side despite differences in the succinic acid feed concentration at p H of approximately 6.90.     

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.     

旋转填充床内高黏介质脱挥过程的传质模型(英文)

A mass transfer model for devolatilization process of highly viscous media in rotating packed bed(RPB) was developed based on penetration theory and mass conservation.Before establishing the model,some mass transfer experiments of thin film were conducted in a designed diffusion cell including vacuum and feeding system. In this study,acetone was used as the volatile organic compound(VOC) and syrup as the highly viscous media.The thickness of thin film was changed by using different liquid distributor.It was found that bubbling played an important role in the devolatilization.The correlation of diffusion coefficient of acetone in highly viscous dilute solution was proposed.The relative error between predicted and experimental data was within the range of ± 30% for diffusion coefficient of acetone in syrup.A comparison of experimental data of RPB with model indicated that the relative error was within ± 30% for efficiency of acetone removal.     

分散支撑液膜中四价铈的传输分离

研究了以聚偏氟乙烯膜(PVDF)为液膜支撑体,煤油为膜溶剂,2-乙基己基磷酸-单-2-乙基己基酯(PC-88A)为流动载体,煤油和PC-88A的混合溶液作为膜溶液,膜溶液和HCl溶液组成分散相的分散支撑液膜(DSLM)中Ce(IV)的传输行为;考察了料液相酸度、Ce(IV)起始浓度、HCl浓度、膜溶液与HCl溶液体积比、解析剂及载体浓度对Ce(IV)传输的影响,得出其最优传输分离条件为：HCl浓度4.0 mol/L,膜溶液与HCl溶液体积比2:1,载体浓度0.16 mol/L,料液相中HCl浓度0.1 mol/L. 在最优条件下,料液相中Ce(IV)的初始浓度为0.7′10-4 mol/L时,迁移75 min,其迁移率达到96.3%. 提出了Ce(IV)在DSLM中的传质动力学方程,得出Ce(IV)在膜中的扩散系数为6.69′10-8 m2/s,料液-膜边界层厚度为19.3 mm. 对模拟样品Ce(IV)的分离结果表明,在一定条件下,125 min内模拟煤粉灰中Ce(IV)迁移率达到92.8%;105 min内模拟冶金熔渣中其迁移率可达92.6%;215 min内Ce(IV)与Eu(III)的混合液中Ce(IV)迁移率达到83%,其他元素迁移率极低.     

Separation of yttrium from europium using a hollow fiber-supported liquid membrane with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester as an extractant

The separation of Y(III) from Eu(III) using a hollow fiber-supported liquid membrane with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (EHPNA) as an extractant was studied. The effects of HCl and metal concentrations in the feed solution, the EHPNA concentration in the membrane, and the HCl concentration in the stripping solution on the initial fluxes of the two metals and the separation factor were investigated. The optimum conditions for selective recovery of Y(III) from an equimolar solution of Y(III) and Eu(III) chlorides (0.001?mol?L^?1 each) were as follows: HCl concentration in the feed solution, 0.1?mol?L^?1; EHPNA dimer concentration in the organic phase in the membrane, 0.1?mol?L^?1; and HCl concentration in the stripping solution, 4?mol?L^?1. Under these conditions, complete Y(III) extraction was achieved after 1 ks of operation, and the Y(III) purity in the stripping solution was 84%.     

PC-88A为载体的大块液膜体系Cu(II)传输动力学

采用以2-乙基己基膦酸-2-乙基己基单酯(PC-88A)为载体、CHCl3为膜溶剂的大块液膜分离体系,研究了搅拌速度、载体浓度、体系温度对铜离子迁移的影响. 获得了不同反应温度下的表观反应速率常数,萃取与反萃取表观反应活化能分别为41.97和8.59 kJ/mol. 铜离子的迁移过程可用2个串联的准一级不可逆过程描述,萃取过程化学反应为控速步骤,反萃取过程扩散为控速步骤.     

以D2EHPA-TOPO为载体的乳化液膜体系萃取磷酸中La（Ⅲ）的工艺及传质机理研究

通过以二（2-乙基己基）磷酸酯／氧化三辛基膦（D2EHPA／TOPO）为流动载体,磺化聚丁二烯（LYF）为表面活性剂,液体石蜡为膜增溶剂,煤油为稀释剂,盐酸为内水相的W／O型乳液,与含La（Ⅲ）的磷酸的外水相进行萃取的过程,制备了W／O／W的双重乳化液膜体系,用单因素法考察了载体浓度,表面活性剂浓度,内相酸度,水乳比等对液膜提取率的影响,确定了最佳工艺条件,迁移率达94．21％以上。并以单浓度递变斜率法研究了载体浓度,表面活性剂浓度,磷酸浓度,H2PO4^-浓度,水相平衡H^＋浓度对分配比的影响,推导出了该乳化液膜的传质机理所经历的步骤。传质机理中包括萃取-反萃表达式,和协萃物组成La（H2PO4）L2（HL）2·（H3PO4）·2TOPO。     

Analysis of the mechanism of rare earth metal permeation through a liquid membrane with a chelating agent in the

The effect of adding a water-soluble chelating agent, diethylenetriaminepentaacetic acid (DTPA), to the feed phase was studied on the selective permeation of rare earth metal ions (Ln³⁺) through a supported liquid membrane (SLM) containing 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (PC-88A). High selectivity of Pr to Nd was observed at a pH of 2.0 in the stripping phase, and selective permeation of La was observed at higher pH values. The permeation mechanism of the Ln³⁺ was analyzed, and the above results were explained by the change in the concentrations of free Ln³⁺ in the feed phase and Ln³⁺/PC-88A complexes in the SLM with pH.     

乳状液膜法去除湿法磷酸中Mg(Ⅱ)的研究

采用乳化液膜技术对湿法磷酸进行脱镁净化是一种净化湿法磷酸的新途径。以-(2-乙基己基)磷酸酯为流动载体乳状液膜体系,系统研究了油水体积比(Roi)、膜试剂、增稠剂(石蜡量)、外水相pH值等因素对Mg(Ⅱ)的迁移行为。得出了乳化液膜法去除湿法磷酸中镁离子的最佳工艺条件：表面活性剂：L113A,膜试剂：环己烷;反萃取剂：HCl3mol／L,增稠剂：石蜡量0．5mL。     

Transport of mercury(II) ion through a supported liquid membrane containing a triisobutylphosphine sulfide (Cyanex 471X) as a mobile carrier

Carrier‐facilitated transport of mercury(II) against its concentration gradient from aqueous 0.1 mol dm^?3 hydrochloric acid solution across a flat‐sheet supported liquid membrane (SLM) containing triisobutylphosphine sulfide (Cyanex 471X) as the mobile carrier in kerosene as diluent has been investigated. Dilute sodium thiocyanate solution (0.11 mol dm^?3) was the most efficient stripping agent among several aqueous reagents tested. Various parameters such as stirring rate, concentration of HCl in the feed solution, concentration of NaSCN in the strippant, concentration of Cyanex 471X in the membrane, and contact time were investigated. Under optimum conditions the transport of Hg(II) across the liquid membrane is about 100% after 6 h. The carrier, Cyanex 471X, selectively and efficiently transported Hg(II) ions in the presence of other associated metal ions. The method has been demonstrated to recover selectively mercury from waste samples and mercurochrome solution. © 2002 Society of Chemical Industry