二（2-乙基已基）磷酸萃取氨基苯甲酸的平衡特性

A series of extraction equilibrium experiments for aminobenzoic acid with di(2-ethylhexyl)phosphoric acid (D2EHPA) dissolved in n-octane or 1-octanol was carried out. The effects of aminobenzoic acid concentration,D2EHPA concentration and pH on the distribution ratio were discussed in detail. The infrared spectra of the organic phase loaded with solute illustrated that pH had little effect on the structure of the complex formed. There proceed ion association and cation-exchange.reaction in the extraction. An expression of the equilibrium distribution was proposed.     

二（2—乙基己基）磷酸萃取L—异亮氨酸的研究

以二（２－乙基己基）磷酸（Ｄ２ＥＨＰＡ）－正辛烷及Ｄ２ＥＨＰＡ－正辛醇萃取Ｌ－异亮氨酸为对象,研究了Ｄ２ＥＨＰＡ浓度、Ｌ－异亮氨酸初始浓度以及ｐＨ值对萃取平衡分配系数的影响。结果表明,在实验研究涉及的ｐＨ值范围内,分配系数先随ｐＨ的增加而增大,在３．５〈ｐＨ〈５区域,ｐＨ值对分配系数的影响较小。分配系数还随Ｄ２ＥＨＰＡ浓度的增加而增大。正辛醇加入有机相,萃取分配系数增大。Ｄ２ＥＨＰＡ与Ｌ－异亮氨酸     

二(2-乙基己基)磷酸萃取L-色氨酸

以二 (2 -乙基己基 )磷酸 (D2EHPA) -正辛烷 (体系A)及D2EHPA -正辛醇 +正辛烷 (体系B)萃取L -色氨酸为对象 ,研究了D2EHPA浓度、L -色氨酸初始浓度、稀释剂组成以及pH值对萃取平衡分配系数的影响 .结果表明 ,在实验研究涉及的pH值 (1.0     

二（2-乙基己基）磷酸/磷酸三丁酯复合萃取剂协萃对氨基苯甲酸

为强化两性官能团化合物的萃取分离性能,以对氨基苯甲酸（PABA）为被分离溶质,二（2-乙基己基）磷酸（D2EHPA）/磷酸三丁酯（TBP）/正庚烷的混合物为萃取剂进行了萃取平衡特性的研究,考察了溶液的pH值、D2EHPA浓度、TBP浓度对于萃取平衡的影响,建立了复合萃取剂协同萃取PABA的萃取平衡分配系数的表达式.结果表明,D2EHPA/TBP/正庚烷复合萃取剂萃取PABA具有明显的协萃效应,协萃机理为D2EHPA及TBP分别与PABA的Lewis碱性官能团（—NH2）和Lewis酸性官能团（—COOH）缔合形成亲油性更强的萃合物,且D2EHPA与TBP的浓度差异越小,协萃效应越明显.根据萃取平衡分配系数表达式拟合求取了表观萃取平衡常数,复合萃取剂的值远大于D2EHPA、TBP单独作为萃取剂的值,进一步证明了本文提出的协萃机理.     

二(2-乙基己基)磷酸钠离子交换萃取氨基葡萄糖盐酸盐的研究

氨基葡萄糖盐酸盐极性大,传统物理萃取方法分离效果不理想,今采用离子交换萃取方法用二(2-乙基己基)磷酸钠萃取氨基葡萄糖盐酸盐溶液。测定了氨基葡萄糖盐酸盐初始浓度、萃取温度、萃取剂初始浓度、以及pH值对分配系数的影响。结果表明,在其他实验条件相同的情况下,分配系数随温度变化不明显,随二(2-乙基己基)磷酸钠初始浓度增加而增大,随氨基葡萄糖盐酸盐初始浓度增加而减少,随pH值增加先增大后减小;氨基葡萄糖盐酸盐低浓度下的分配系数远大于其高浓度下的分配系数;为获得最佳萃取效果,萃取平衡体系要尽量接近中性。建立了分配系数模型,并讨论了四种特殊情况下的分配系数表达式。研究结果为工业用离子交换萃取法分离氨基葡萄糖盐酸盐提供了一定的技术依据。     

二(2-乙基己基)磷酸萃取L-苯丙氨酸

以二（2-乙基己基）磷酸（D2EHPA）-正辛烷萃取L-苯丙氨酸为对象,研究了D2EHPA浓度、L-苯丙氨酸初始浓度以及pH值对萃取平衡分配系数的影响。不同pH值下负载有机相的红外谱图分析表明,D2EHPA与L-苯丙氨酸形成的萃合物结构与pH值无关。提出了在萃取过程中同时存在着离子交换反应和质子转移反应的观点。1个氨基酸分子与2个二（2-乙基己基）磷酸二聚体相结合。本文建立的萃取平衡分配系数关联式,拟合精度令人满意。     

二（2-乙基己基）膦酸萃取Cr(Ⅲ)的陈化特性

近年来,关于溶剂萃取法回收Cr(Ⅲ)的文献报道较多,而对其反萃行为的研究则较少。酸性磷氧类萃取剂负载Cr(Ⅲ)后易发生缩合反应,形成难以被反萃的稳定缩合物,萃取剂难以再生,即发生“陈化”现象。本文使用10% D2EHPA/10%正辛醇/磺化煤油为萃取剂,0.6 mol·L^-1 H₂SO₄为反萃剂,以反萃为手段研究了陈化现象的机理。考察了Cr(Ⅲ)浓度和实验温度对陈化速率的影响,进而提出了缩合反应的机理和数学模型,并据此拟合了反应动力学参数,计算了反应活化能。结果显示,陈化反应速率随温度的升高而加快,反应级数为1.57,反应速率常数约（2.49×10^-3）～（4.06×10^-2）,反应活化能（43.0 kJ·mol^-1）较低,在常温下极易自发反应。采用拟合参数对陈化过程进行模拟,提出若以30 min内的陈化率控制在3%以下为目标,工业操作温度应控制在23 ℃以下。     

醇-酯复合萃取剂萃取湿法磷酸的相平衡研究

以醇-酯复合萃取剂为对象,对湿法磷酸溶剂萃取的液相平衡进行了研究,测定了复合萃取剂-磷酸体系在25、45、60、70 ℃相平衡时磷酸的分配曲线,考察了磷酸分配系数与温度、相比、磷酸初始浓度的关系。结果表明：复合萃取剂能萃取磷酸的最大质量分数不高于50%,温度和相比对分配系数的影响都不大,但水相磷酸初始浓度对分配系数影响很大。     

复合萃取剂-磷酸-水三元体系液液相平衡研究

研究了复合萃取剂-磷酸-水三元体系在25℃下的液液相平衡关系,绘制了三角相图,用Hand公式对相平衡数据进行了关联。考察了不同温度条件下磷酸分配系数随原料酸中磷酸含量的变化关系,结果表明磷酸的分配系数随温度变化不大;同时,研究了磷酸中钙镁离子在两相中的分配情况,结果表明复合萃取剂对离子具有很好的选择性。     

二-(2-乙基己基)磷酸萃取钴(Ⅱ)的微量量热法研究

用微量量热法研究了二 - ( 2 -乙基己基 )磷酸在正己烷中对钴 (Ⅱ )的萃取 ,得到了热功率—时间曲线 ,确定了 30 8K时此萃取过程的热效应 ,从而求出了不同温度下的有关热力学函数。     

Extraction Equilibria of 4-Hydroxypyridine using Di (2-ethylhexyl) Phosphoric Acid

Extractions of 4-Hydroxpyridine (4HP) from aqueous solutions using Di(2-ethylhexyl)phosphoric acid (D2EHPA) as extractant in 1-octanol and kerosene were studied. The factors that affected the distribution coefficient (D), such as equilibrium pH, the concentration of D2EHPA, and the type of diluents were discussed. The interaction mechanism between 4HP and D2EHPA was validated by infrared spectroscopic analysis. D increased with the increase of the concentration of D2EHPA and peak values appeared at equilibrium pH = 3.6–5.0. D in the polar diluent (1-octanol) was much higher than those in the non-polar diluent (kerosene). The extraction reaction was found to be a proton-transfer process and D2EHPA mainly reacted through its –OH with –N– of 4HP. The apparent reactive extraction equilibrium constants K ₁₁ and K ₁₂ were obtained by fitting the experimental data of extraction equilibrium. By comparing calculated D values from the proposed model with the experimental ones, the accuracy of the proposed model was examined.     

Equilibrium studies of the extraction of zirconium(IV) from sulfuric acid solutions with Di(2-ethylhexyl)phosphoric acid

Equilibrium studies were made at 25°C in the extraction of zirconium(IV) from sulfuric acid solutions with di(2-ethylhexyl)phosphoric acid (D2EHPA, HR) dissolved in kerosene. The reaction stoichiometry was numerically determined and the compositions of the extracted species were found to be ZrR₄ and ZrR₄(HR) at low loading ratios of D2EHPA (α < 0.09), but became ZrR₄ and ZrR₄(HR)₃ at relatively higher loading ratios (0.10 < α < 0.32). The equilibrium constants for the formation of these species were also obtained. Furthermore, numerical treatment of the experimental data excluded the existence of polynuclear complexes under the conditions studied (α < 0.32).     

Synergic Extraction of Folic Acid with Di(2-ethylhexyl) Phosphoric Acid and Amberlite LA-2

The influences of extractants concentrations and solvent polarity on the efficiency of folic acid separation by synergic extraction with Amberlite LA-2 and di(2-ethylhexyl) phosphoric acid (D2EHPA) mixture have been analyzed. The results indicated the formation of an interfacial compound which includes one molecule of folic acid and one of D2EHPA, the hydrophobicity of this compound being increased by solvation with Amberlite LA-2 molecules. The number of aminic molecules participating in the interfacial complex formation is controlled by solvent polarity and D2EHPA concentration, decreasing from 3 to 1 with the increase of these two parameters. The results indicated that the most important synergic effect corresponds to the extractants mixture dissolved n-heptane, at low D2EHPA concentration in the organic phase (5 g/l).     

有机胺类稀溶液的络合萃取

以P204(磷酸二(2-乙基己基)酯)为络合剂,加氢煤油为稀释剂,实验研究了不同的有机胺类稀溶液的络合萃取特性,讨论了有机胺类的pK_a值、络合剂的含量和溶液pH值等因素对络合萃取平衡的影响,提出了同时考虑络合萃取作用和物理萃取作用的萃取相平衡分配系数表达式。利用傅立叶红外谱图分析了P204络合萃取有机胺类的机理。     

Enantioselective Extraction of Racemic Mandelic Acid by Di(2‐ethylhexyl) Phosphoric Acid and Tartaric Acid Derivatives as Mixed Complex Chiral Selectors

The distribution behavior of mandelic acid (MA) enantiomers was examined in a two‐phase system containing di(2‐ethylhexyl) phosphoric acid (D2EHPA) with two tartaric acid derivatives as complex chiral selectors in n‐octanol. Factors affecting the extraction were investigated, including the structure and concentration of tartaric acid as well as the concentration of D2EHPA and D,L‐MA. The results showed that both the distribution ratio and enantioselectivity were greatly improved by using a complex chiral selector rather than using the tartaric acid derivative by itself. Finally, it was found that the formation of mixed complex chiral selectors by mixing two tartaric acid derivatives with D2EHPA can improve the capacity of enantioselective extraction.     

Extraction equilibria and separation of phenylalanine and aspartic acid from water with di(2‐ethylhexyl)phosphoric acid

The distribution equilibria of single and binary L ‐phenylalanine and L ‐aspartic acid between water and a kerosene solution of di(2‐ethylhexyl)phosphoric acid (D2EHPA) were studied. It was shown that the distribution ratios of phenylalanine generally increased with increasing aqueous pH (2–5) in the D2EHPA concentration range 0.1–0.5 mol dm^?3, but those of aspartic acid decreased with increasing solution pH. Different reaction stoichiometries were proposed for the extraction of phenylalanine and aspartic acid under the conditions studied. The extraction equilibrium constants were obtained. Competitive extraction in binary systems was more apparent in the pH range where the cationic form of amino acids was not predominant. The present results indicated that selective separation of phenylalanine to aspartic acid was possible with this cationic extractant when they were extracted at higher pH and stripped using higher acidity of HCl solution. Copyright © 2006 Society of Chemical Industry     

Extraction kinetics of Fe(III) by di-(2-ethylhexyl) phosphoric acid using a Y–Y shaped microfluidic device

The extraction kinetics of Fe^III by di-(2-ethylhexyl) phosphoric acid (D2EHPA) were investigated using a Y–Y shaped microfluidic device. Finite-volume simulations were used to examine the accuracy of a single-step dimeric reaction mechanism in fitting the experimental data. Results demonstrate the validity of the proposed mechanism and show that Fe^III extraction occurred at a slow rate (second-order forward rate constant of k₁ = (3.0 ± 0.1) × 10⁻⁶ m⁴/mol s) under a mixed reaction–diffusion resistance regime. The present study provides insight for the control of Fe^III extraction rates in hydrometallurgical processes.     

三烷基氧膦(TRPO)萃取有机羧酸的研究

络合萃取法对有机物稀溶液的分离具有高效性和高选择性。选择甲酸、乙酸、一氯乙酸、二氯乙酸、三氯乙本酸为分离对象,三烷基氧膦（TRPO）为络合剂,煤油为稀释剂,进行了系统的萃取相平衡实验。结果表明,溶质的pKa对络合萃取影响起主导作用。红外光谱定性分析表明,TRPO萃取有机羧酸为氢键溶剂比历程,负载有机酸的TRPO中的P＝0吸收峰的位移与有机羧酸的酸性有关。采用质量作用定量定律分析方法,建立了相平衡分配系数的表达式,模型拟合精度是令人满意的。     

Distribution Behavior of Amino Acid by Extraction with Di(2-ethylhexyl) Phosphoric Acid

Abstract

The distribution equilibrium of l-tryptophan (l-Trp) by extraction with di(2-ethylhexyl) phosphoric acid (D2EHPA) dissolved in n-hexane was studied. The effects of L-Trp and D2EHPA concentrations, pH, and ionic strength, particularly of L-Trp loading in the organic phase, on extraction equilibrium were examined in detail. When the amino acid loading ratio (the molar concentration ratio of the equilibrium amino acid in the organic phase to the initial dimeric D2EHPA) was less than 3 × 10^?3, one L-Trp molecule was extracted by forming a complex with four monomeric D2EHPA molecules, and the extraction equilibrium constant (K _e) was determined to be 0.045 dm³/mol. Above this loading ratio the equilibrium formula did not hold, and the apparent equilibrium constant (K _a) increased significantly with increasing loading ratio. The phenomenon was explained by taking into account two parallel reactions in which fewer D2EHPA molecules, two and one respectively, were needed to extract one l-Trp molecule.