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。     

膜接触器中乳化液膜脱除Ni2+的研究

研究了以D2EHPA/煤油/HC1形成的微乳液体系在中空纤维膜接触器中萃取NiCl2水溶液中Ni2的过程,考察了D2EHPA和Ni2+浓度、水溶液酸度、两相流速对溶液中Ni2+的萃取率和传质性能的影响.结果表明,用D2EHPA/煤油/HCl形成的微乳液体系能有效萃取NiCl2水溶液中的微量Ni2+,增大微乳液中载体D2EHPA浓度和料液pH都能提高Ni2的萃取率和过程的总质系数,增加料液流速能显著提高Ni2+的萃取率和过程的总质系数,表明过程的传质阻力主要在水溶液相.     

用P507从硫酸体系中萃取分离镓与铁锌离子

采用P507萃取剂对硫酸体系中的Ga3+与Fe2+, Zn2+进行萃取分离,考察了料液酸度、萃取剂浓度、时间、温度对萃取的影响,绘制萃取等温线;通过比较负载有机相中3种离子用不同浓度HCl和H2SO4反萃的效果及规律,提出用HCl洗脱Fe2+和Zn2+后,再用H2SO4反萃Ga3+的分离方案,并绘制反萃等温线. 结果表明,以40%(j) P507+磺化煤油为有机相,在相比O/A=1:1、温度25℃、时间20 min条件下,经过4级逆流萃取,Ga3+萃取率可达98.48%,同时19.56%的Fe2+和38.42%的Zn2+共萃进入有机相. 负载有机相用6 mol/L HCl洗涤3次可完全洗脱Fe2+和Zn2+而不损失Ga3+,除Fe2+和Zn2+后的负载有机相用100 g/L H2SO4按O/A=4:1、25℃、10 min,经过4级逆流反萃,Ga3+反萃率达97.64%.     

D2EHPA对高浓度盐酸介质中钛的萃取

研究了D2EHPA对盐酸介质中钛的萃取和反萃性能。研究结果表明:萃取液中钛以TiOCl2.2D2EHPA的形式存在。钛萃取率随无机相中氯离子浓度和有机相中萃取剂浓度的增加而增加。D2EHPA对钛的饱和承载量为8.98 g/100 g D2EHPA。红外光谱研究进一步表明了Ti-D2EHPA螯合物的性质。在0.5～12 mol/dm3的盐酸介质中,D2EHPA对钛的萃取率随盐酸介质浓度的增加而增加,而对铁、铝、钙、镁无萃取性能。以7%H2O2+3 mol/dm3H2SO4为反萃剂,有机相中的钛可实现一次完全反萃。     

乳化萃取法脱除Mg2+制备工业级磷酸二氢钠的研究

本文以高效的二(2-乙基己基磷酸)(D2EHPA)为萃取剂,采用乳化萃取技术来提取NaH2PO4溶液中的Mg2+杂质,通过考察萃取剂浓度,水相溶液pH值,相比(水相:有机相),乳化速度等对萃取Mg2+萃取率的影响,求得适宜工艺条件:D2EHPA体积分数:75%,相比(A/O):2∶1,起始NaH2PO4溶液pH值为4,搅拌速度:3000r.min-1;实验结果表明,在适宜工艺条件下,经过三级萃取,可制取工业级NaH2PO4。     

微乳液的增溶、相态及微乳液/中空纤维膜萃取钕

通过考察非离子型微乳液体系（OP-4+OP-7）/ 苯甲醇/D2EHPA/煤油/盐酸中的混合表面活性剂OP-4［壬基酚聚氧乙烯（4）醚］和OP-7［壬基酚聚氧乙烯（7）醚］配比、盐酸浓度、温度和NaCl对盐酸增溶量的影响以及D2EHPA［二（2-乙基己基）磷酸］和盐酸浓度对体系相态的影响，制备了适合作为液膜分离介质的微乳液体系，同时提出了新的膜萃取过程：微乳液/中空纤维膜萃取，并用于稀土钕的萃取.结果表明，微乳液中盐酸的增溶量随混合表面活性剂HLB值以及盐酸浓度的增大而增大，随温度的升高、NaCl浓度的增大而减小;D2EHPA的加入有利于WinsorⅡ体系的形成;盐酸浓度小于6 mol•dm^-3时也可形成WinsorⅡ体系，而盐酸浓度为7 mol•dm^-3和8 mol•dm^-3时则分别形成WinsorⅢ体系或WinsorⅠ体系;将W/O非离子型微乳液通过中空纤维膜从浓度为300 mg•dm^-3的料液中萃取钕时，采用3个中空纤维膜器串连一次萃取即可使萃取率达95.3%，内相富集倍数18.1.该新膜萃取体系同时具有液膜与固膜萃取的优点，不需进行反萃操作.     

硫酸介质中D2EHPA萃取In~(3+)与Fe~(3+)的动力学

采用恒界面池法研究了从硫酸介质中萃取In3+和Fe3+的动力学,考察了搅拌速度、界面面积、温度、萃取剂浓度、氢离子活度及硫酸根浓度对In3+,Fe3+萃取速率的影响.结果表明,在温度25℃、搅拌转速70～240 r/min条件下,In3+以三价离子形式被萃取,萃取活化能为17.54 k J/mol,萃取过程为扩散控制;Fe3+以Fe SO4+形式被萃取,萃取活化能为52.87 k J/mol,萃取过程为界面化学反应控制.增加D2EHPA浓度可增大正向反应动力,提高萃取速率.萃取过程为阳离子交换,氢离子活度增加会导致萃取速率降低,硫酸根与金属离子的络合效应会降低萃取速率.通过动力学研究得到In3+萃取的正向速率方程为-d CIn3+/dt=10-0.378[In3+](aq)[H+](aq)-0.376[H2A2](org)0.158,Fe3+萃取的正向速率方程为-d CFe3+/dt=10-2.413[Fe3+](aq)[H+](aq)-1.526[H2A2](org)0.600.     

重型卡车车架磷化工艺

重型卡车的车架材质主要由热轧板组成,其表面疏松、多孔,车架表面在脱脂、水洗、表调等工序中极易发黄、生锈.本文对前处理剂进行改进,使之适应热轧板的特性.研究了磷化液中Zn2+、Mn2+及Ni2+质量浓度对磷化膜表面形貌、膜重、P比(即Zn2Fe(PO4)2·4H2O与Zn3(PO4)2·4H2O之比)的影响,得出这几种离...     

合金钢黑色磷化膜研制及耐蚀性研究

通过单因素实验和正交试验确定了一种合金钢的黑色磷化液的组成和操作条件,并用中性盐雾试验和电化学测试表征了黑色磷化膜的耐腐蚀性。结果表明,最优黑色磷化液的成分为:30 g/L马日夫盐,20 g/L Zn(H2PO4)2·2H2O,8 g/L Zn(NO3)2·6H2O,10 g/L Mn(NO3)2。在最优磷化液中得到的黑色磷化膜耐中性盐雾试验6h未见腐蚀。通过X-射线衍射分析,黑色磷化膜由Mn2Zn(PO4)2·4H2O、Zn2Fe(PO4)2·4H2O和Zn3(PO4)2·4H2O组成。     

4A沸石填充聚氨酯杂化膜的制备及气体分离性能

两步法制备了4A沸石填充的端羟基聚丁二烯基聚氨酯膜HTPB-PU/4A,并研究了CO2、H2、O2、N2的气体透过性能.结果表明:沸石与膜的相容性较好,添加4A沸石后,膜的热稳定性明显提高,O2渗透性及O2/N2选择性显著改善;随沸石添加时间的增加,膜对各种气体体系的选择性先增加后减小,而渗透性则先增加后趋于稳定;随硬...     

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.     

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.     

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.     

Selective Separation of Gallium from Acidic Leach Solutions by Emulsion Liquid Membranes

Abstract

The separation and concentration of gallium from acidic leach solutions, containing various other ions such as iron, cobalt, nickel, zinc, cadmium, lead, copper, and aluminium, by an emulsion liquid membrane (ELM) technique using tributyl phosphate (TBP) as carrier has been presented. Liquid membrane consists of a diluent, a surfactant (ECA 4360J), and an extractant (TBP), and 0.1 M HCl or 0.1 M H₂SO₄ were used as the stripping solution. The important variables governing the permeation of gallium and their effect on the separation process have been studied. These variables were membrane type and composition, mixing speed, diluent type, surfactant concentration, extractant concentration, HCl concentration in the feed, acid type of stripping phase, feed concentration, and treatment ratio. The optimum conditions were determined. It was possible to selectively extract 96.0% of gallium from the acidic leach solutions, containing Fe, Co, Ni, Zn, Cd, Pb, Cu, and Al, at the optimum conditions.     

Coupled transport of Tl3+ through triethanolamine–xylene–polypropylene supported liquid membranes

This study has been carried out for the uphill transport of Tl³⁺ across triethanolamine (TEA)–xylene based supported liquid membrane. The mechanism of transport of Tl³⁺ has been found to be based on the association of Tl³⁺ with six chloride ions to form anions, which associate with three protonated triethanolamine molecular cations (HOH₄C₂)₃N⁺H at the feed side of the membrane face and form a complex. The complex is extracted into the liquid membrane organic phase, from where it diffuses towards the stripping side of membrane due to the concentration gradient and is dissociated due to alkaline conditions present in the stripping phase. It is also confirmed that proton addition to triethanolamine takes place at the N site and not at the –OH sites. 5.26 mol/dm³ of TEA in xylene in membrane phase, 1.0 mol/dm³ of HCl in feed and 1.0 mol/dm³ of NaOH in stripping phase have been found to be the optimum concentrations for the extraction of Tl³⁺. The method developed for transport of Tl³⁺ has been successfully applied to remove Tl³⁺ from coal ash acid leach liquors along with nickel, chromium and zinc ions.     

中空纤维支撑液膜萃取法提铟工艺比较研究

采用中空纤维支撑液膜(SLM)技术,模拟酸性铟渣浸出液,以磷酸二异辛酯(P204)、磺化煤油体积比3:7为液膜萃取相,盐酸溶液为反萃相,研究了单组件膜萃取系统、双膜组件萃取-反萃系统、双膜组件萃取-超滤系统对酸性浸出液中In的提取与分离效率。结果表明,双膜组件萃取-超滤技术可同时实现浸出液中In的提取与反萃液中In的高纯度富集,浸出液中In的提取率可达90%以上,反萃液中In含量可达浸出液中In含量的70%,In的质量分数高于90%。     

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.     

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.