溶剂萃取法净化磷酸中氟的研究

以三辛胺(TOA)为萃取剂净化磷酸中的氟离子,考察了稀释剂、萃取剂浓度、萃取时间、温度对萃取的影响,并研究了磷酸中杂质离子的存在对脱氟性能的影响。结果表明,在萃取剂TOA浓度0.5 mol/L(稀释剂为磺化煤油),萃取时间20 min,温度303 K,转速200 r/min,相体积比(O/A)=1∶1的条件下,脱氟率可达70%以上。磷酸中[Fe3+]=0.02～0.07 mol/L,[Mg2+]=0.06～0.08 mol/L范围内,对萃取脱氟是有利的,铝离子和钙离子的存在均不利于氟、磷的分离。     

Liquid-Liquid Extraction Studies of Trivalent Yttrium from Phosphoric Acid Solutions Using TOPS 99 as an Extractant

Liquid-liquid extraction studies of trivalent yttrium (Y) from phosphoric acid solutions have been carried out with commercial organophosphoric acid based extractant TOPS 99 (Talcher Organo phosphorus solvent, an equivalent of di-2-ethylhexyl phosphoric acid). The parameters studied include equilibration time, acid concentration, extractant concentration, diluent, metal concentration, temperature, stripping, and regeneration of the extractant. Increase of phosphoric acid concentration in the range from 0.01 to 0.5 M on the extraction of trivalent Y with 6 × 10^?3 M TOPS 99 (Talcher Organo phosphorus solvent) decreases the percentage extraction, indicating the transfer of metal follows ion exchange type reaction. The plot of log D vs. equilibrium pH gave a straight line with a slope of 3.1 indicating the exchange of three moles of hydrogen ions for every mole of trivalent Y extracted into the organic phase. Stripping of metal from the loaded organic with mineral acids indicate sulphuric acid as the best stripping agent. The extraction behavior of associated elements clearly follows their ionic radii with a maximum separation factor of 414 for Lu-Tb.     

Separation of butyric acid in fixed bed column with solvent impregnated resin containing ammonium ionic liquid

Batch equilibrium and fixed bed column extraction experiments for the extraction of butyric acid (BA) into solvent impregnated resin (SIR) have been done. Microporous Amberlite XAD-1180N was impregnated with an ammonium ionic liquid (IL) trialkylmethylammonium bis(2,4,4-trimethylpentyl)phosphinate. The BA extraction capacity isotherm has not a Langmuir type shape and no finite capacity was observed. The loading of the impregnated IL with the extracted BA at 37 °C is in agreement with the loading from L/L extraction equilibrium of BA at 25 °C. Capacity of freshly prepared SIR particles is superior to classical porous ion-exchangers. Both the temperature and the superficial velocity in column influence the shape of the breakthrough-curve in fixed bed extraction of BA using SIR. Sharpening of the breakthrough curve was observed with the increasing temperature and decreasing superficial velocity. Stripping with water is not efficient for the regeneration of the loaded column after extraction because of low concentration of the product acid in the obtained effluent. Higher BA concentration was achieved by stripping with 0.15 kmol m⁻³ and 0.075 kmol m⁻³ NaOH solutions. The combination of initial water stripping coupled with consecutive stripping by alkali can be beneficial for decreasing the consumption of chemicals and further processing of the product. After two extraction/stripping cycles, a stable capacity was achieved and sustained for 14 cycles, showing the possibility of long-term application of the prepared SIR in real technology.     

Valeric acid extraction with tri‐n‐butyl phosphate impregnated in a macroporous resin: II. Studies in fixed bed columns

Extraction and back‐extraction of valeric acid in a fixed bed packed with Amberlite XAD‐4 resin impregnated with tri‐n‐butyl phosphate were experimentally studied at 25 °C. The effects of the feed flow rate, acid concentration in the feed solution and extractant concentration in the impregnated resin on the breakthrough curves, were investigated. The bed saturation capacity was larger under the conditions of higher extractant concentration in the resin phase and higher acid concentration in the feed solution. A dynamic model that considers intraparticle diffusion and external liquid film diffusion as limiting steps in mass transfer rates was successfully applied. The intraparticle effective diffusivities (10^?9 dm² s^?1) were from one to three orders of magnitude lower than the diffusivities in the external liquid film (10^?8–10^?6 dm² s^?1). A fast and complete back‐extraction of valeric acid from the saturated bed was carried out with sodium hydroxide solutions. The operational life of the impregnated resin was also studied. Copyright © 2005 Society of Chemical Industry     

杂质对磷酸萃取过程的影响

研究萃取相比与磷酸萃取率和杂质分离系数之间的关系,考察硫酸和铁2种杂质对磷酸萃取率的影响。实验结果表明:随着相比提高,磷酸萃取率上升,且各杂质分离系数提高;硫酸的存在有利于磷酸萃取,且存在一个最佳含量,使磷酸对硫酸分离系数最大;而铁离子的存在则不利于磷酸萃取。     

乳化液膜技术分离湿法磷酸中铁的研究

采用乳化液膜法对湿法磷酸中铁的分离进行了研究。正交实验结果表明,在实验范围内,载体对除铁率影响最大,溶剂和反萃取剂的影响相对较小;较优的液膜物质组成为:N205为表面活性剂,CH3(C8H17)3NC l为流动载体,环己烷为膜溶剂,盐酸为反萃取剂。在实验条件下,随表面活性剂量和载体量的增大,除铁率都是先增加后降低;当盐酸浓度小于3 mol/L时,除铁率是随着盐酸浓度的增加而增加的;但是当盐酸浓度太大时,由于液膜的破碎率上升,导致除铁率反而降低。     

正丁醇萃取磷酸的实验研究

采用微分散法研究了磷酸的萃取特性;以正丁醇/磷酸/水为实验体系,以孔径为20 μm的不锈钢纤维烧结网为分散介质,在自制萃取器中研究了相比、流量、磷酸质量分数、装置横放与立放、先混合后分散与先分散后混合、有网与无网对萃取效率的影响.结果表明,萃取率随总流通量的增大而呈先增大后减小的趋势,最优总流量800 mL/min;随相比的增大而增大,最优相比为2∶1;随磷酸质量分数的升高而升高,最优磷酸质量分数为32％,且萃取率有高质量分数磷酸＞低质量分数磷酸;有网萃取率大于无网;在流量较小时,装置平放大于装置立放时的萃取率,在流量较大时,萃取率差别不大;先混合后分散的进料方式下萃取率大于先分散后混合.     

Studies on the solvent extraction of rare earths from nitrate media with a combination of di‐(2‐ethylhexyl)phosphoric acid and sec‐octylphenoxyacetic acid

BACKGROUND: Di‐(2‐ethylhexyl)phosphoric acid (D2EHPA, H₂A₂) has been used extensively in hydrometallurgy for the extraction of rare earths, but it has some limitations. Synergistic extraction has attracted much attention because of its enhanced extractabilities and selectivities. In the present study, sec‐octylphenoxyacetic acid (CA12, H₂B₂) was added into D2EHPA systems for the extraction and separation of rare earths. The extraction mechanism of lanthanum with the mixtures and the separation of lanthanoids and yttrium were investigated. RESULTS: The synergistic enhancement coefficient for La³⁺ extracted with D2EHPA + CA12 was calculated as 3.63. La³⁺ was extracted as La(NO₃)₂H₂A₂B with the mixture. The logarithm of the equilibrium constant was determined as 0.80. The thermodynamic functions, ΔH, ΔG, and ΔS were calculated to be 4.03 kJ mol^?1, ? 1.96 kJ mol^?1, and 20.46 J mol^?1 K^?1, respectively. The mixtures have synergistic effects on Ce³⁺, Nd³⁺, and Y³⁺, with an especially strong synergistic effect on Y³⁺. Neither synergistic nor antagonistic effects on Dy³⁺ and weak antagonistic effects on Lu³⁺ were found. CONCLUSION: Mixtures of D2EHPA and CA12 exhibit evident synergistic effects when used to extract La³⁺ from nitric solution. The stoichiometries of the extracted complexes have been determined by graphical and numerical methods to be La(NO₃)₂H₂A₂B with the mixture. The extraction is an endothermic process. The mixture exhibits different extraction effects on rare earths, which provides possibilities for the separation of Y³⁺ from Ln³⁺ at a proper ratio of D2EHPA and CA12. Copyright © 2008 Society of Chemical Industry     

Cadmium(II) recovery from hydrochloric acid solutions using Amberlite XAD-7 impregnated with a tetraalkyl phosphonium ionic liquid

Cyphos® IL-101 (tetraalkyl phosphonium ionic liquid, IL) was immobilized in a synthetic resin (Amberlite XAD-7) for preparing an solvent impregnated resin (SIR). This SIR was tested for Cd(II) sorption in HCl solutions. Optimum sorption occurs for HCl concentrations close to 3–4 M through an ion exchange mechanism involving phosphonium cation and . Sorption capacity increased with IL loading, though a fraction of the IL remained inactive, being bound to the polymer support. Sorption capacity is poorly influenced by metal ions that do not form chloroanionic species. Uptake kinetics are controlled by the resistance to intraparticle diffusion. The intraparticle diffusivity coefficient increased with temperature, initial metal concentration but decreased with increasing IL loading (probably due to a decrease of the interfacial area and a slow diffusion of metal ions in the organic phase that fills the porous network). Metal desorption and resin recycling can be performed using nitric acid (0.1 M) with sorption and desorption performances maintained for at least five cycles.     

乳化液膜法脱除磷酸中镉的研究

镉是磷酸中的有害杂质之一,其对环境的污染和对人体的毒害日趋严重,所以必须控制磷酸中镉等有害杂质的含量。用乳化液膜法除去磷酸中的镉,采用单因素实验法,重点考察了表面活性剂Span-80,T151,T154及用量、萃取剂TBP,P204及用量、萃取时间对脱除磷酸中镉的影响。结果显示：表面活性剂T154用量为2.0 mL及萃取剂P204用量为2.0 mL时,乳化液膜具有较好的稳定性,且萃取时间为15 min时,从磷酸中除镉的效果最优。     

微乳液膜萃取L-谷氨酸的研究

用NaOH皂化HA/煤油溶液能形成稳定的微乳液。通过该微乳液对L-谷氨酸水溶液进行萃取实验。结果表明,该微乳液萃取L-谷氨酸的最佳工艺条件为:萃取时间20 m in,油相中HA的浓度为1.0 mol/L,乳水比(体积比)为1∶4,外水相pH值为3,L-谷丙氨酸的一次性萃取率可达89.33%。微乳液膜具有稳定性好、无明显溶胀和泄漏、萃取效率高、可自动破乳且油相可重复使用等优点。     

Liquid–liquid extraction of Hg(II) from acidic chloride solutions using bis‐2‐ethylhexyl sulfoxide

The liquid–liquid extraction of Hg(II) from acidic chloride solutions has been studied using bis‐2‐ethylhexyl sulfoxide (B2EHSO) as an extractant. For comparison, extraction studies have also been carried out using di‐n‐octyl sulfoxide (DOSO) and diphenyl sulfoxide (DPhSO). The extraction data have been analysed by both graphical and theoretical methods taking into account aqueous phase speciation and all plausible complexes extracted into the organic phase. These results demonstrate that Hg(II) is extracted into xylene as HgCl₂.3R₂SO (where R₂SO represents the sulfoxide). The equilibrium constant of the extracted complex has been deduced by non‐linear regression analysis. The developed liquid–liquid extraction procedure has been applied for the recovery of mercury from the brine‐sludge of a Chlor‐Alkali plant. © 2001 Society of Chemical Industry     

Solid‐Liquid Extraction of Terbium from Phosphoric Acid Medium using Bifunctional Phosphinic Acid Resin,Tulsion CH‐96

Solid‐liquid extraction of terbium from phosphoric acid medium has been studied using the commercially available macroporous bifunctional phosphinic acid resin, Tulsion CH‐96. The parameters studied include equilibration time, acid concentration, amount of resin, metal concentration, temperature, loading, elution, regeneration, and recycling. In the wide range of phosphoric acid concentration 0.01–7.8 M the percent extraction of terbium decreases from 98.9% at 0.01 M to 16.0% at 1 M due to an ion‐exchange mechanism and increases to 36% at 7.8 M due to a coordination mechanism. The percent extraction increases with an increase in weight of the resin from 2.7% at 0.05 g to 80.7% at 1.2 g. Under the studied experimental conditions, the loading of Tulsion CH‐96 for terbium was determined to be 3.52 mg per gram of resin. The percent extraction of terbium increases with the increase in temperature, indicating the endothermic nature of the extraction process. Screening of various eluants suggested 1 M (NH₄)₂CO₃ as the best with an efficiency of 99.8%. The extraction behavior of commonly associated metals with terbium such as yttrium, holmium, erbium, dysprosium, ytterbium, and lutetium has been studied as a function of phosphoric acid concentration to determine the separation factors and possible separation.     

Recent advances in polybenzimidazole/phosphoric acid membranes for high‐temperature fuel cells

Proton exchange membrane fuel cells are one of the most promising technologies for sustainable power generation in the future. In particular, high‐temperature proton exchange membrane fuel cells (HT‐PEMFCs) offer several advantages such as increased kinetics, reduced catalyst poisoning and better heat management. One of the essential components of a HT‐PEMFC is the proton exchange membrane, which has to possess good proton conductivity as well as stability and durability at the required operating temperatures. Amongst the various membrane candidates, phosphoric acid‐impregnated polybenzimidazole‐type polymer membranes (PBI/PA) are considered the most mature and some of the most promising, providing the necessary characteristics for good performance in HT‐PEMFCs. This review aims to examine the recent advances made in the understanding and fabrication of PBI/PA membranes, and offers a perspective on the future and prospects of deployment of this technology in the fuel cell market. © 2014 Society of Chemical Industry     

湿法磷酸萃取制取高品质磷酸二氢钾工艺研究

磷酸二氢钾在当前的磷酸盐工业中具有重要的实用价值,其应用涉及到工业、农业、医药以及食品等多个行业。以尽可能低成本的原材料与更简易的工艺流程来生产具备更高品质特性的磷酸二氢钾为时下所需。以湿法磷酸与氯化钾为原料,进行了有机溶剂萃取法制备磷酸二氢钾的工艺研究。研究内容包括：在溶配过程中氯化钾与磷酸物质的量比对氟离子脱除率的影响;氯化钾与磷酸物质的量比、反应时间、反应温度以及萃取相比对萃取率及杂质脱除率的影响;不同洗涤相比对五氧化二磷洗涤率的影响;反萃取以及磷酸二氢钾浓缩结晶的相关工艺。通过实验确定湿法磷酸萃取制取高品质磷酸二氢钾适宜工艺条件：反应温度为60 ℃,反应时间为30 min,氯化钾与磷酸物质的量比为1.0,洗涤相比为12。在此工艺条件下所得磷酸二氢钾产品纯度高达97%,达到磷酸二氢钾农用级优等品标准的要求,同时五氧化二磷回收率可达到96%。     

正辛醇+煤油混合溶剂萃取净化湿法磷酸工艺研究

选用新型高效萃取体系正辛醇+煤油混合溶剂,研究了正辛醇+煤油混合溶剂在萃取净化湿法磷酸过程中萃取温度和相比（萃取剂与磷酸的体积比）与磷酸萃取率和杂质分离系数之间的关系, 考察了硫酸和铁两种杂质对磷酸萃取率和分配比的影响。实验表明: 随着相比提高, 磷酸萃取率上升, 各杂质分离系数提高。提高萃取温度和增加铁含量会使磷酸萃取率和分配比呈减小趋势,硫酸的存在有利于磷酸萃取。通过对正辛醇+煤油体系萃取湿法磷酸系统性的基础工艺研究,以期为设计工业化应用路线提供理论和技术支持。     

Copper and cadmium extraction from highly concentrated phosphoric acid solutions using calcium alginate gels enclosing bis(2,4,4‐trimethylpentyl)thiophosphinic acid

The availability of alginate gels enclosing Cyanex 302 [bis(2,4,4‐trimethylpentyl)thiophosphinic acid] for the uptake of cadmium and copper from highly concentrated solutions of industrial phosphoric acid wet process phosphoric acid (WPA)] was studied. For this purpose, beads of alginate gels enclosing microdrops of kerosene solutions of the industrial extractant Cyanex 302 at different concentrations were prepared. The experimental procedure gives rise to a composite bead in which alginate is the continuous phase and the organic extractant forms the discrete homogeneously distributed phase within the bead. The equilibrium in this three‐phase system (phosphoric acid–extractant solution–alginate gel) was modelled in terms of the corresponding distribution factors, the main chemical reactions and their equilibrium constants. Retention isotherms of both metal ions were obtained experimentally at four concentrations (1.0, 2.5, 5.0 and 7.5 mol L^?1) of pure phosphoric acid. High metal removal efficiency, due to liquid–liquid extraction processes, was observed even in the most acidic conditions. High values of the extraction constants were estimated, with the distribution coefficients between aqueous and alginate phase being near unity. Finally, the results obtained with industrial WPA are in close agreement with those predicted by the physicochemical model developed in synthetic media. Copyright © 2006 Society of Chemical Industry