Intensified reactive extraction of 4-hydroxypyridine with di(2-ethylhexyl) phosphoric acid in 1-octanol by using tributyl phosphate

The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl phosphate(TBP), di(2-ethylhexyl) phosphoric acid(D2EHPA) and TBP + D2EHPA dissolved in 1-octanol were investigated, respectively. The influences of the initial concentrations of TBP, D2EHPA and TBP + D2EHPA on distribution ratio(D) were discussed, as well as the reactive extraction mechanism were proposed. The obvious intensification effect was observed when the mixture of TBP and D2EHPA was used as extractant. The best extraction conditions were found to be of the molar ratio of D2EHPA and TBP at 2:1 and the equilibrium aqueous pH at 3.50-4.50. D values increased with the increase of the total concentration of TBP and D2EHPA in 1-octanol. Especially, the analysis on the extraction mechanisms clearly indicate(i) TBP in 1-octanol shows negligible reactive extraction toward 4-HP,(ii) D2EHPA in 1-octanol exhibits moderate extraction effect by forming 4-HP:D2EHPA(1:1) and 4-HP:2D2EHPA(1:2) type complexes, while(iii) D2EHPA in TBP/1-octanol demonstrates the maximum distribution ratio with the 4-HP:D2EHPA(1:1) type complex domination. The discussion provides new insights on the mechanism and opens a new way for the intensified extraction of amphoteric organic compounds by using the mixture of multiple extractants in the diluent.

Synergistic extraction of rare earth by mixtures of 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester and di-(2-ethylhexyl) phosphoric acid from sulfuric acid medium

The extraction of Nd^3＋ and Sm^3＋, including the extraction and stripping capability as well as the separation effect of Nd^3＋ or Sm^3＋, from a sulfuric acid medium, by mixtures of di-（2-ethylhexyl） phosphoric acid （HDEHP, H2A2（0）） and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester （HEH/EHP, H2L2（0）） were studied. The distribution ratios and synergistic coefficients of Nd^3＋ and Sm^3＋ in different acidities were also determined. A synergistic extractive effect was found when HDEHP and HEH/EHP were used as mixed extractants for Sm^3＋ or Nd^3＋. The chemical compositions of the extracted complex were determined as Nd.（HA2）2-HL2 and Sm.（HA2）2-HL2. The extraction equilibrium constants, enthalpy change, and entropy change of the extraction reaction were also determined.

Combination of on-line preconcentration by di(2-ethylhexyl) phosphoric acid resin in the presence of complexing agent with microwave plasma-atomic emission spectrometry for the determination of rare earths

The adsorption of rare earths,lanthanum,cerium,neodymium,and yttri um by di(2-ethylhexyl) phosphoric acid(D2EHPA) resin in the presence of a compl exing agent,EDTA,was investigated. Flow injection was selected as the injectin g method. Various parameters,sample pH,sample loading time,sample flow rate,EDTA concentration,EDTA flow rate,eluent concentration,and eluent flow rate,were studied and optimized. Under the optimum conditions,the method allowed the determination of rare earths with detection limits of 1.09 μg/L(lanthanum),3 .31 μg/L(cerium),2.05 μg/L(neodymium),and 1.25 μg/L(yttrium) . High repea tabilities were obtained for all the four rare earths(RSD【5%) . The proposed met hod was applied to the determination of the rare earths in water samples with a recovery range of 95.8%-103.3%.

Adsorption by Liquid-Liquid Extraction of Hg(II) from Aqueous Solutions Using the 2-Butyl-imidazolium Di-(2-ethylhexyl) Phosphate as Ionic Liquid

In this work, a novel room temperature ionic liquid (2-butyl-imidazolium di-(2-ethylhexyl) phosphate) ([C4mim] [D2EHPA]) was synthesized and tested as extractant in the mercury(II) liquid-liquid extraction. The effects of parameters such as aqueous to organic phase’s volume ratio, metal concentration IL concentration, pH levels, ionic strength, and temperature were reported. For the extraction of metal, [C4mim]3[R.HR]3[HgCl2]org and [C4mim]3[R.HR]3 [HgClOH]org species were formed where (H2R2) was D2EHPA. In the case of ionic strength, the results showed that the addition of sodium acetate at 0.302 mmol·L?1 to the aqueous phase strongly increased the mercury extraction yield (R = 100%). The extracted species were investigated by a calculation program using CHEAQS V. L20.1 inorder to determine the relation between the percentages of the extracted species and the extraction yield. The results showed that the extracted species in the best conditions were HgCl2 and HgClOH with respective percentages 80.66% and 18.29%.

低浓度有机磷萃取剂P204促进普通小球藻(Chlore11a vulgaris)生长的研究

本文以普通小球藻为实验对象,研究了有机磷萃取剂P204在低浓度（<EC_（50））时对其生长的影响,结果显示,与对照组相比,普通小球藻的生长量、蛋白质含量、叶绿素含量、碱性磷酸酶活力等都有明显的增长,表明在低浓度时,P204对普通小球藻的生长有明显的刺激和促进作用。

二(2乙-基己基)磷酸(D2EHPA)萃取Fe^(3+)的萃合物结构

以分离制革污泥淋滤液中Fe3+和Cr3+为背景,研究了二(2-乙基己基)磷酸(D2EHPA)分别从氯化物和硫酸盐介质中萃取Fe3+的效率,并应用配位化学理论结合MINTEQ程序,推测了可能的萃合物结构,讨论了D2EHPA浓度、溶液pH、溶液中阴离子对萃合物结构的影响.结果表明,在低Cl-浓度介质中,萃合物结构为FeA3(HA)2(H2O).在高Cl-浓度介质中,萃合物结构为FeClA2(HA)3.在SO42-介质中,萃合物结构为FeSO4A(HA)2(H2O)2和Fe2SO4(OH)2A(HA)2.

二(2-乙基己基)磷酸稀土配合物的红外和拉曼光谱

用稀土氯化物与二(2-乙基己基)磷酸反应制备了14种标题配合物,测定了配合物的红外和拉曼光谱,对其主要红外和拉曼谱带进行了归属。结果表明,Ln(DEHP)3应具有与Sm(DMP)_3和Pr(DMP)_3相同的配位形式和结构类型,每个稀土离子通过双O—P—O桥与邻近的三个稀土离子相连接,形成“双桥二十四元环”的多聚网络结构。Ln—O键基本上是离子键。

Tb(III) Transport in Dispersion Supported Liquid Membrane System with D2EHPA as Carrier in Kerosene

The transport of Tb（III） in dispersion supported liquid membrane（DSLM） with polyvinylidene fluoride membrane（PVDF） as the support and dispersion solution including HCl solution as the stripping solution and di（2-ethylhexyl） phosphoric acid（D2EHPA） dissolved in kerosene as the membrane solution, has been studied. The effects of pH value, initial concentration of Tb（III） 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 transport of Tb（III） have also been investigated, respectively. As a result, the optimum transport conditions of Tb（III） were obtained, i.e., the concentration of HCl solution was 4.0 mol/L, the concentration of D2EHPA was 0.16 mol/L, the volume ratio of membrane solution to stripping solution was 30：30 in the dispersion phase and pH value was 4.5 in the feed phase. Ionic strength had no obvious effect on the transport of Tb（III）. Under the optimum conditions, the transport percentage of Tb（III） was up to 96.1% in a transport time of 35 min when the initial concentration of Tb（IIl） was 1.0× 10 -4 mol/L. The diffusion coefficient of Tb（III） in the membrane and the thickness of diffusion layer between feed phase and membrane phase were obtained and the values were 1.82×10 -8 m2/s and 5.61 um, respectively. The calculated results were in good agreement with the literature data.

Selective Separation of Light and Heavy Rare Earth Elements from the Pregnant Leach Solution of Apatite Ore with D2EHPA

Different separation techniques such as solvent extraction, ion exchange, and precipitation are often used for recovery of rare earth elements (REEs) from pregnant leach solutions obtained from acid leaching. Solvent extraction is generally accepted as the most appropriate commercial technology for separating REEs due to the need to be able to handle larger volumes of diluted pregnant solutions. This study focused on the development of selective separation of light and heavy REEs from the pregnant leach solution obtained from leaching of apatite ore in 1 M sulfuric acid (H2SO4) using solvent extraction. Three different commercial organophosphorus extractants (di-(2-ethylhexyl) phosphoric acid (D2EHPA), 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC88A) and tributyl phosphate (TBP)), and the influences of experimental parameters such as extractant concentration, organic/aqueous phase ratio, diluent type, pH, extraction time and stripping agent concentration were examined. Results showed that light REEs (LREEs) and heavy REEs (HREEs) in the pregnant leach solution were selectively separated with D2EHPA via a two-stage extraction process. In the first-stage of solvent extraction, >90% of (0.05 g/L) HREEs was extracted with 1.8 M D2EHPA in kerosene while the vast majority (>95%) of LREEs was remained in raffinate. In the second-stage, >93% (1.01 g/L) of LREEs was extracted from the raffinate with 1.8 M D2EHPA dissolved in kerosene at pH 1.6. HREEs (>95%) and LREEs (>90%) loaded with D2EHPA after the first and second-stage of extraction were stripped by 4 M H2SO4 and 1 M H2SO4 solutions, respectively. Distribution of middle rare earth elements (MREEs) was discussed through the extraction processes in this study.

萃取剂HDEHP在不同稀释剂中的聚合性质

The dimeric property of bis(2 - ethylhexyl) phosphoric acid(HDEHP) in different diluents has been studied. The experimental results show that the dimeric degree of HDEHP increases with the decrease of the polarity of diluents.This kind of effect has been discussed from the point of view of intermolecular interactions between the extractant molecules and the diluent ones. The dimeric constantswere related to the physical constants and experiencial parameters of the diluents.The following expression hasbeen obtained lg K2 =6 .4 5 9- 4 .4 6 4 (ε- 1) /(2 ε+ 1) - 1.96 5 (n D2 - 1) /(n D2 +1) - 3.199α- 5 .6 6β.

有机膦萃取分离制革污泥淋滤液中Cr和Fe

采用磷酸二(2-乙基己基)酯(D2EHPA)和磷酸三丁酯(TBP)为萃取剂,萃取分离制革污泥淋滤液中的Cr3+与Fe3+.结果表明,在pH2·2时,采用5%D2EHPA-正己烷萃取体系,Fe3+的萃取率达到99%,有效地分离了制革污泥淋滤液中的Fe3+和Cr3+.以5mol·l-1的盐酸作为反萃剂反萃负载有机相,20min时的反萃率可以达到90%左右.以TBP和D2EHPA为萃取剂萃取分离Cr3+与Fe3+时,降低了污泥淋滤液中Fe3+的萃取率,这是由于TBP的加入降低了D2EHPA的有效浓度.同时TBP的加入阻碍了萃取物分子和反萃剂的接触,降低了Fe3+的反萃率.

磷类萃取剂萃取钼(Ⅵ)的性能研究

系统研究了酸性磷类萃取剂二(2-乙基己基)磷酸(P204)和中性磷类萃取剂磷酸三丁酯(TBP)从硫酸体系中萃取钼的性能,稀释剂为乙酸丁酯、二甲苯和煤油。试验结果表明,溶解在3种稀释剂中的TBP对钼萃取效果均不显著,而P204与3种稀释剂组成的有机相均对钼有良好的萃取性能,萃取率与水相pH、萃取时间、酸体系有关。萃取机理属于离子交换缔合机理。

有机磷和十二胺对制革废液中Cr^(3+)和Fe^(3+)的萃取分离研究

针对制革污泥淋滤液Cr3+与Fe3+的分离,研究了二(2-乙基己基)磷酸(D2EHPA)和十二胺(RNH2)2个不同萃取体系萃取分离Cr3+与Fe3+的适宜条件。结果表明,在pH=2左右,采用D2EHPA和RNH3Cl为萃取剂分离Cr3+与Fe3+时的分离系数β均在500以上,且水相中Fe3+的残留浓度可以控制在10mg/L左右,并且分别以5mol/L和1mol/LHCl为反萃剂反萃负载有机相,单级反萃率均可以达到90%左右,为制革产生的多金属废弃物的溶剂萃取法提供了1种处理工艺。

化学镀镍废液中镍的萃取及综合利用

利用二－ （２－ 乙基己基）磷酸作为萃取剂萃取化学镀镍废液中的镍，萃余液用硫酸反萃取，生产工业级硫酸镍，达到治理环境，废物利用的目的。

含Cr^(3+)废水的萃取与分离研究

利用磷酸二(2-乙基己基)酯作萃取剂,煤油为稀释剂,利用萃取分离技术萃取分离含Cr3+废水中的Cr3+,从而得到了萃取分离Ct3+的最佳条件:以体积分数为5%的磷酸二(2-乙基己基)酯-煤油作萃取剂,调节Cr3+溶液的pH值为4~4.5进行萃取,萃取完成后,用浓度为5 mol/L的HCl从有机磷中反萃Cr3+,通过这些条件的确定,可以为溶剂萃取回收含Cr3+废水中的Cr3+工业化途径提供实验理论和实践依据。

Mass Transfer of Copper（Ⅱ） in Hollow Fiber Renewal Liquid Membrane with Different Carriers

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 concen-tration 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 organic/aqueous volume ratio,reach the maximum and then decrease.

Solvent extraction of zinc from zinc sulfate solution

The extraction of zinc from zinc sulfate solution was investigated, using 20% saponified D2EHPA as an extractam and 260^# sulfonate kerosene as a diluent. The solution was stirred for 8 min at phase ratio （Vσ/Va） of 1.0：1.0, initial pH of 2.0 and stirring speed of 200 r/min. The results show that 75% zinc can be extracted from the zinc sulfate solution when the concentration of zinc is 18.7 g/L after being settled for 10 min. 88.60% zinc can be stripped by 196 g/L sulfuric acid, and zinc ion can be separated from ferric ion.

钒(Ⅳ)有机磷催化剂合成及其结构表征

通过以二(2-乙基己基)磷酸酯(P204)为主萃取剂、2-乙基己酸为助萃取剂来萃取钒(Ⅳ)水溶液,合成钒(Ⅳ)催化剂;经元素分析、红外光谱和紫外光谱表征钒(Ⅳ)有机磷催化剂的主要结构为VO(P204)2;另外,通过实验数据考察了萃取平衡pH值、助萃取2-乙基己酸的用量对钒(Ⅳ)有机磷一元酸催化剂溶液合成的影响,确定了制备钒(Ⅳ)催化剂的最佳工艺条件:30℃下,2-乙基己酸的摩尔分数为35%~45%,有机相pH值为6.5~7.0。在此条件下,钒(Ⅳ)萃取率可达90%,且催化剂溶液高度稳定。

Separation of Trivalent Samarium through Facilitated Stripping Dispersion Hollow Fiber Liquid Membrane Using p204 as Mobile Carrier

The separation of Sm（III） through stripping dispersion hollow fiber liquid membrane system （SDHFLM） containing feed phase adding acetate buffer solution and dispersion solution with HC1 solution as the stripping solution and membrane solution of di（2-ethylhexyl） phosphoric acid （p204） dissolved in kerosene, has been studied. A set of factors were studied, including pH value, initial concentration of Sm（III） and different ionic strength of feed phase, volume ratio of membrane solution and stripping solution （O/W）, HC1 concentration, carrier concentration, different stripping agents of dispersion phase on Sm（III） separation. Experimental results indicate that the optimum separa- tion conditions of Sm（III） were obtained as that HC1 concentration was 4.00 tool/L, p204 concentration was 0.150 mol/L, and volume ratio of membrane solution and stripping solution （O/W） was 1.00 in the dispersion phase, and pH value was 4.60 in the feed phase. Ionic strength had no obvious effect on separation of Sm（III）. When initial Sm（III） concentration was 1.00 × 10^-4 mol/L, the separation rate of Sm（III） was up to 93.5% in 85 min. The kinetic equation was developed in terms of the law of mass diffusion and the theory of interface chemistry. The modeled results were in good agreement with the experiment data.

Study on the Separation of Rare Earths with the Method of H(DEHP)-Extraction Chromatography

Separation of rare earths was investigated by extraction chromatography where H(DEHP)was used as a stationary phase,while HCl and H_2SO_4 solutions as a mobile phase.The average separation fac- tors of rare earths,β_(HCl) and β_(H_2SO_4),are 3.79 and 4.57.respectively.The β_(La)^(Ce) in HCl and H_2SO_4 systems are as high as 28.5 and 26.3,respectively.The elution acidity in the study can be down to one tenth and one four- teenth of that in HEH(EHP)system.