Equilibrium studies on reactive extraction of lactic acid with an amine extractant

Equilibrium studies on the extraction of lactic acid from aqueous solutions with tri-n-octylamine (TOA) in xylene were made in the temperature range 293–323 K. The formulation of the extracted species in the organic phase and the corresponding equilibrium constants were numerically determined at different temperatures. Also, the apparent thermodynamic functions were calculated. Finally, the effect of a water-insoluble organic acid, di(2-ethylhexyl)phosphoric acid (D2EHPA), on this extraction was investigated. Synergistic and antagonistic effects were observed in the presence of D2EHPA, mainly depending on the concentration ratio of D2EHPA to TOA.     

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.     

Efficacy of tri-n-octylamine,tri-n-butyl phosphate and di-(2-ethylhexyl) phosphoric acid for reactive separation of protocatechuic acid

ABSTRACT

Owing to its chemical and pharmacological significances, the efficacy of reactive separation of protocatechuic acid (0.001–0.01 kmol m^?3) from aqueous stream by means of tri-n-octylamine (TOA), di-2-ethylhexyl phosphoric acid (D2EHPA) as well as tri-n-butyl phosphate (TBP) in octanol has been investigated, in terms of extraction efficiency, loading ratio, equilibrium complexation constants, and distribution coefficients. Extraction ability was obtained in the order TOA (91.2%) > TBP (88.64%) > D2EHPA (86.43%). In all cases, 1:1 protocatechuic acid:extractant complex is obtained. Further, diffusion coefficients, number of stages for extraction systems, and relative basicity model were used for relating the efficacy.     

Extraction and recovery of rhodamine B,methyl violet and methylene blue from industrial wastewater using D2EHPA as an extractant

The extraction behavior of cationic dyes namely rhodamine B (RB), methyl violet (MV) and methylene blue (MB) from industrial wastewater has been investigated using di-(2-ethylhexyl) phosphoric acid (D2EHPA) in hexane as a carrier. The extraction of cationic dyes increases with decreasing feed phase pH and increasing D2EHPA concentration in organic phase. The stripping percentage of dyes using acetic acid as the stripping agent from loaded D2EHPA was found to increase with increasing acid concentration. 98% stripping efficiency of dyes was achieved with 8.5 mol/L acetic acid solution at an organic:aqueous phase ratio (O/A) of 2:1. Parameters examined include D2EHPA concentration, effect of diluents, effect of pH, effect of initial dye concentration, equilibration time, and various stripping agents, aqueous to organic phase ratio in extraction and organic to aqueous phase ratio in stripping.     

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.     

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.     

三辛胺萃取分离苹果酸的特性

为探讨有机羧酸的成键机理，以二元有机酸－苹果酸为分离溶质，实验测定了三辛胺（TOA）在正辛醇、甲基异丁基酮（MIBK）和氯仿三种稀释剂中萃取苹果酸的平衡及负载溶剂红外光谱特性，结果表明，TOA浓度，稀释剂种类对萃取平衡的影响与苹果酸的浓度有关；平衡水相酸的浓度较低时，萃取剂可提供较大的萃取能力，TOA的化学计量饱和后，存在“过载”现象，且过载量为MIBK＞正辛醇＞氯仿，TOA萃取苹果酸的萃合物主要为酸胺比为（2：1），（1：1）和（1：2）等三种形式，其中（1：2）萃合物中苹果酸与TOA之间的结合一个是离子对成盐，一个是氢键缔合，同时，以质量作用定律为基础，建立了描述萃取平衡的数学模型，求得了相应的反应萃取平衡常数K11，K12，K21。     

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.     

三辛胺络合萃取分离一氯乙酸和二氯乙酸

以三辛胺(TOA)工业品为萃取剂、正己烷为稀释剂,研究了一氯乙酸和二氯乙酸(质量比为322:1)水溶液的萃取分离特性,考察了温度和初始萃取剂浓度对萃取平衡的影响,建立了TOA萃取一氯乙酸和二氯乙酸的数学模型。结果表明,两酸分配系数随温度升高而增大,但影响有限;随萃取剂初始浓度的增大,一氯乙酸分配系数随之增大,二氯乙酸分配系数先升后降。基于TOA的表观碱度,建立了二氯乙酸单溶质模型,解释了其分配系数随萃取剂浓度增大先升后降的特殊规律;在此基础上,考虑协同萃取的影响,建立了双溶质萃取模型。上述研究为一氯乙酸工业品的进一步提纯分离提供了指导。     

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.     

三辛胺萃取丁二酸、苹果酸、马来酸、富马酸特性的研究

Extraction equilibrium features of succinic acid, malic acid, maleic acid and fumaric acid were investigated systematically with trioctylamine (TOA) in chloroform, 4-methyl-2-pentanone (MIBK) and 1-octanol. Fourier transform-infrared (FTIR) spectroscopic analysis of organic samples loaded with the acid shows that amine forms 1:1 complex of ion-pair association with succinic acid, malic acid and maleic acid, and 1:1, 2:1 complex of ion-pair association with fumaric acid. It is proposed that the complex forms depend on the second dissociation constant of the dibasic acid, pKa2 Results of equilibrium experiments show that diluents affect extraction behavior, and depend on the solute concentration. Protic diluents, chloroform and 1-octanol, are more effective than the others when the equilibrium solute concentration is lower than 1:1 stoichiometry of TOA to acid, otherwise the extraction ability shows that MIBK>l-octanol>chloroform for malic and maleic acids, and l-octanol>MIBK>chloroform for succinic acid.     

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.     

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     

Synergistic extraction and separation of Fe(III) and Zn(II) using TBP and D2EHPA

Waste chloride pickle liquors from hot-dip galvanizing plants, steel plants and flue dust contain reasonable amounts of heavy metals such as Zn, Cr, Ni, etc. Iron is invariably associated with most of these materials and comes into solution during leaching. Thus, the synergistic extraction of zinc(II) and iron(III) from leach solutions in tri-n-butyl phosphate (TBP)–di(2-ethylhexyl) phosphoric acid (D2EHPA) system diluted in kerosene was investigated. The Zn and Fe concentrations in the leach liquor used in the present study were 2 g/L. Experiments were carried out in the pH range of 0.5–4.0, temperature of 25°C, using sole D2EHPA, sole TBP and D2EHPA–TBP mixtures at different ratios. Results showed that the co-extraction of zinc(II) and iron(III) increased with increasing equilibrium pH using D2EHPA. It is demonstrated that the mixtures of TBP and D2EHPA are more efficient and selective than D2EHPA alone. At low pH values, the separation factor is low when pure D2EHPA is used as an extractant; however, using TBP as a synergist, the separation factor increases and results in a better separation of zinc from iron. Increasing TBP to D2EHPA ratios in the organic phase caused a slight shift to the right in the extraction isotherm of iron and a marked shift to the right in the extraction isotherm of zinc, and the maximum separation factor of 13.3 × 10³ was achieved at a TBP to D2EHPA volume ratio of 4:1 (0.58 M TBP: 0.12 M D2EHPA). Furthermore, the effect of equilibrium pH, organic to aqueous phase ratio and Cl^? concentration on the selective extraction was investigated. Using two extraction stages at the O/A ratio of 2:1 and pH_e (equilibrium pH) of 3 and 1 for zinc and iron, respectively, 99% of zinc(II) and 96.25% of iron(III) were extracted.     

Fractionation of Carboxylic Acids Mixture Obtained by Succinic Fermentation using Reactive Extraction

Formic, acetic, and succinic acids have been selectively separated from their mixture obtained by A. succinogenes fermentation using reactive extraction with tri-n-octylamine (TOA) dissolved in three solvents with different polarities (n-heptane, butyl acetate, and dichloromethane) without and with 1-octanol addition. This technique allows recovering formic and acetic acids from the mixture, the raffinate containing only succinic acid. The extractant concentration and organic phase polarity control the selectivity of acids extraction. Thus, at pH = 1, the selectivity factor increased from 92, in the absence of 1-octanol; to 148, in the presence of this alcohol in organic phase. The corresponding optimum concentrations of TOA in the solvent were 30 and 50 g/l, respectively. The total separation of monocarboxylic acids from the mixture with succinic acid is possible by a multi-stage extraction process, adjusting the extractant concentration in each stage to that stoechiometrically needed for reactions with formic and acetic acids only. The addition of 1-octanol reduces the number of required extraction stages.     

三辛胺萃取草酸的第3相特性

以三辛胺（TOA）萃取草酸时出现第3相的基本规律为研究对象,实验测定了无水溶剂及液液萃取平衡有机相中草酸的溶解度及其随TOA和正辛醇浓度的变化规律.结果显示,正辛醇对草酸及其与TOA形成的缔合物在溶剂中的溶解度影响显著;随正辛醇含量的增加,草酸及其缔合物在溶剂中的溶解度提高,因而溶剂对草酸的萃取能力随之增大;在TOA与草酸以1∶1的化学计量比饱和后,草酸溶解度出现阶跃现象,这与形成草酸二聚体的缔合物有关;相比之下,液液萃取平衡实验中有机相对草酸的溶解度大于无水溶剂的结果,溶剂中水的存在有助于缔合物溶解.同时建立了描述液液萃取平衡有机相中草酸及其缔合物溶解度的数学模型,并通过参数寻优求得了相应的模型参数.     

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     

络合萃取法从稀溶液中提取草酸

为深入认识二元酸的络合萃取平衡特性及萃取机理,以三辛胺（TOA）为络合剂,正辛醇为助溶剂,煤油为稀释剂,草酸为被萃溶质,进行了混合溶剂的萃取平衡实验研究,测定了络合剂的浓度、稀释剂的组成等因素对萃取平衡分配系数的影响,并对TOA萃取草酸的机理进行了探讨。实验结果表明,随TOA浓度的增大,萃取平衡分配系数呈增大趋势;随溶质初始浓度的增大,有机相的溶质浓度向饱和萃取量接近;饱和萃取量随络合剂浓度的增大而增大;稀释剂对萃取平衡的影响与TOA浓度有关,TOA浓度较小时,煤油的加入使萃取平衡分配系数减上,TOA浓度较大时,煤油的加入对萃取平衡影响较小。     

Study of lactic acid extraction with higher molecular weight aliphatic amines

Lactic acid extraction was studied with two extractants, trioctyl amine (TOA) and Aliquat 336, in three diluents (methylisobutyl ketone (MIBK), octanol and paraffin liquid). The effects of organic phase extractant concentration and aqueous phase pH on the extraction process were examined. Among the extractants, TOA was found to be a better extractant than Aliquat 336 in all the diluents. In experiments with 50% (v/v) TOA in methylisobutyl ketone, 79% lactic acid could be extracted (initial lactic acid concentration 86·96 g dm⁻³). MIBK had a profound effect on the extraction behaviour of TOA in comparison with octanol and paraffin liquid while none of the diluents affected the extraction with Aliquat 336. The extraction of lactic acid was favoured at low pH. The toxicities of TOA and the diluents to Lactobacillus rhamnosus NRRL B445 were also studied. While TOA was found to be highly toxic at the molecular and the phase level, the paraffin liquid was totally non-toxic. The extraction of glucose and yeast extract by TOA and the diluents used was found to be low, which thus enables the selective extraction of lactic acid. © 1998 SCI     

Comparative Study on Reactive Extraction of Picolinic Acid with Six Different Extractants (Phosphoric and Aminic) in Two Different Diluents (Benzene and Decan-1-ol)

The equilibrium study on reactive extraction of picolinic acid by six different extractants (phosphoric and aminic) dissolved in two different diluents (benzene and decane-1-ol) is carried out to evaluate the performance of extractants and diluents. The extraction ability in terms of the distribution coefficient (K _D) is found to be in the order of tri-n-octylamine (TOA) ≥ tri-n-dodecylamine (TDDA) > di-2-ehylhexyl phosphoric acid (D2EHPA) > tri-n-butyl phosphate (TBP) > tri-octyl methyl ammonium chloride (Aliquat 336) > tri-n-octyl phosphine oxide (TOPO) with both diluents. Decan-1-ol is found to be the better solvating medium for the acid-extractant complexes. A mathematical model based on mass action law is employed to estimate the values of partition coefficient (P) and dimerization constant (D) in physical extraction, and equilibrium extraction constants (K _E) in chemical extraction. The values of loading ratios (Z) less than 0.5 imply the formation of (1:1) acid:extractant solvates in the organic phase. Decan-1-ol with TOA is the most effective solvation medium with K _{D, max} = 9 at 0.01 kmol · m^?3 of picolinic acid and K _E = 19.448 m³ · kmol^?1.