PC-88A为载体的大块液膜体系Cu(II)传输动力学

采用以2-乙基己基膦酸-2-乙基己基单酯(PC-88A)为载体、CHCl3为膜溶剂的大块液膜分离体系,研究了搅拌速度、载体浓度、体系温度对铜离子迁移的影响. 获得了不同反应温度下的表观反应速率常数,萃取与反萃取表观反应活化能分别为41.97和8.59 kJ/mol. 铜离子的迁移过程可用2个串联的准一级不可逆过程描述,萃取过程化学反应为控速步骤,反萃取过程扩散为控速步骤.     

MASS TRANSFER OF SULFURIC ACID BY TRIOCTYLAMINE THROUGH A SUPPORTED LIQUID MEMBRANE

The extraction of sulfuric acid in a supported-liquid membrane (SLM) process, and the kinetics of extraction and stripping of sulfuric acid in a cell of constant interfacial area by trioctylamine (TOA)/kerosene solvent were investigated. The kinetics of extraction and stripping were determined by examining the effects of the operating variables. The extraction rate is a function of the activity of sulfuric acid and the concentration of TOA; the stripping rate is a function of the concentration of trioctylamine sulfate salts in the organic solution. A generalized transport model, which included the film diffusion of sulfuric acid in the aqueous phase, the membrane diffusion within the SLM, and the interfacial chemical reaction, was built. The permeability of sulfuric acid through the SLM using TOA as a mobile carrier was determined. The rate-determining step of the extraction of sulfuric acid through a SLM was analyzed using the data obtained from the experiments of extraction kinetics and the mass transfer in the aqueous phase. Diffusion within the membrane dominates the process of extraction process of sulfuric acid by TOA through a SLM.     

Extraction and separation of HCl and Rh(III) with trioctylamine

In this paper the use of trioctylamine (TOA) to extract HCl from Rh(III)-containing solutions generated by a supported liquid membrane (SLM) process is investigated. TOA was found to extract HCl readily (in a single contact of 3 min duration) at a molar ratio [HCl]/[TOA] equal to one. For each mole of HCl extracted an equivalent amount of H₂O was found to be extracted as well. As far as Rh(III) extraction of TOA is concerned this was found to depend on the age of the solution and the Cl⁻ concentration. Prolonged aging (accelerated by heating) or [Cl⁻]⩾3 M was found to completely suppress the extraction of Rh(III) by TOA. The chloride ion concentration effect was attrib-uted to Le Chatelier's principle while the aging effect was attributed to the aquation/conversion of the extractable RhCl₆³⁻ complexes to RhCl₅(H₂O)²⁻. The aquation reaction was studied with UV–Visible spectroscopy in an effort to substantiate the solvent extraction (SX) results. On the basis of the findings of this work a combined SLM/SX process flowsheet is proposed according to which the Rh(III) and HCl co-transported through the supported liquid membrane are co-extracted by TOA and subsequently separated by differential stripping; Rh(III) with 0·5 M HCl/3 M Cl⁻ medium and HCl with NAOH.     

粉煤灰酸浸溶液中铁铝离子的萃取分离

采用N503和TBP、正辛醇、煤油组成的复合萃取体系,对粉煤灰酸浸溶液中的铝与铁进行萃取分离,考察盐酸浓度、氯离子浓度、萃取剂比例对Fe3+萃取率的影响,以低浓度HCl溶液反萃负载铁有机相,并通过逆流实验确定最佳工艺条件. 结果表明,采用N503:TBP:正辛醇:煤油=3:1:1:5(j)的萃取体系,在初始铁浓度为0.96 mol/L、铝浓度为0.22 mol/L、萃取相比O/A=2:1条件下,经5级逆流萃取,Fe3+的萃取率大于99.8%,铝几乎没有损失. 用0.01 mol/L HCl溶液作反萃剂,反萃相比O/A=2.5:1,经6级逆流反萃,反萃液中铁浓度达1.8 mol/L. 分析了有机相负载铁前后官能团的红外光谱图.     

Kinetic study on selective extraction of HCl and H3PO4 in a microfluidic device☆

In the extraction method for preparing KH2PO4, one of the key processes is the selective extraction of HCl over H3PO4. In our work, extraction kinetic studies have been carried out in a microfluidic device with a coaxial microchannel, using the extractant of 33.3%(by volume) trioctylamine (TOA) dissolved in n-octanol, with differ-ent aqueous phases:the HCl solution, the H3PO4 solution, and H3PO4 and KCl solutions of different concentra-tions. The changes of the extraction efficiency of HCl and H3PO4 and the selectivity for HCl along with the residence time were investigated. We found that fast extraction kinetics could be realized in microfluidic devices, and that HCl could be extracted faster than H3PO4 due to smaller mass transfer resistance and much stronger re-action between HCl and TOA. For the extraction of H3PO4 and KCl solutions, the selectivity for HCl first increased and then decreased when TOA was in excess of H3PO4 in the initial feeds, and in contrast, always increased when H3PO4 was in excess of TOA in the initial feeds. The diverse changes of selectivity for HCl along with the residence time indicate that a dynamic control of selectivity in microfluidic devices may be important and accessible for im-proving the KH2PO4 conversion efficiency in extraction method.     

Kinetic studies on the esterification of free fatty acids in jatropha oil

Kinetic studies have been carried out on the esterification of free fatty acids (FFAs) in jatropha oil with methanol in the presence of sulphuric acid catalyst at 5 and 10 wt% concentrations relative to free fatty acids (0.4–0.8 wt% relative to oil) and methanol–FFA mole ratios ranging from 20:1 to 80:1. It has been found that a 60:1 methanol–FFA mole ratio and 5 wt% catalyst at 60°C and 500 rpm or above provided a final acid value lower than 1 mg KOH/g oil within 60 min. A kinetic model has been proposed with second‐order kinetics for both the forward and backward reactions. The effect of temperature on the reaction rate constants and equilibrium constant has been determined using Arrhenius and von't Hoff equations, respectively. The heat of reaction was found to be ?11.102 kJ/mol.     

Kinetic Studies of Extraction and Stripping of Copper with Dibenzoylmethane

Abstract

Kinetic studies of the extraction of copper with dibenzoylmethane and the stripping of copper were carried out in a stirred transfer cell, along with a study of the extraction equilibrium of copper with the extractant at 303 K. The extraction and stripping rates were analyzed by a model of the interfacial reaction between the extractant and the adsorbed 1:1 copper chelate complex accompanied by the mass transfer steps of the species. Furthermore, the extraction rate was simulated by using the equilibrium and reaction rate constants obtained from the analysis.     

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。     

Absorption of carbon monoxide with reversible reaction in cualcl4-toluene-complex solutions

The absorption of CO in CuAlCl₄-toluene-complex solutions was studied in a stirred reactor. The reaction was found to occur in a fast reaction regime. The effect of CO partial pressure, CuAlCl₄-toluene-complex concentration and temperature on the rate of absorption was studied. The results have been interpreted using a theoretical model for mass transfer with reversible chemical reaction and the rate parameters were determined. The equilibrium constants were also determined experimentally. An interesting observation showing a decrease in the rate with an increase in temperature was made for this system. This is explained on the basis of a higher activation energy for the reverse reaction. The activation energies evaluated for the forward and reverse reactions are 32.93 and 97.42 kJ/mol, respectively.     

Melt transesterification of bisphenol acetophenone–polycarbonate: A kinetic study

This article deals with the development of kinetic parameters for bisphenol acetophenone–polycarbonate made by melt transesterification with diphenyl carbonate. The understanding of the influence of borosilicate glass of the reactor construction materials on the accuracy of the kinetic data is reported. During the development of analytical methods, the use of high performance liquid chromatography‐mass spectrometry (HPLC‐MS) was proven to be a valid tool to determine the oligomers existing in the reaction mixture. Accurate kinetics parameters were obtained by elimination of the interference of the construction materials. We provide the rate expressions, kinetic parameters [forward reaction frequency factor = 2.456 × 10¹³ ± 0.01 (cm³/mol)²/min, forward reaction activation energy = 45.69 ± 0.2 kJ/mol, reverse reaction frequency factor = 2.068 × 10¹⁴ ± 0.01 (cm³/mol)²/min, and reverse reaction activation energy = 56.37 ± 0.1 kJ/mol], and equilibrium constants at various temperatures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4072–4079, 2007     

KINETICS OF PHENOL EXTRACTION FROM AQUEOUS PHASE BY SULFURIC ACID SALTS OF TRIOCTYLAMINE

The kinetics of the extraction of phenol from the aqueous phase by sulfuric acid salts of trioctylamine (TOA salts) in kerosene and the stripping of phenol from the organic phase by sodium hydroxide solution were studied using a constant interfacial area cell. Measurements of the extraction and stripping rates were made by measuring the time-dependent phenol concentrations in the aqueous phase. It is found that the extraction rate of phenol is strongly dependent on the initial concentration of phenol in the aqueous phase and on the initial concentration of TOA salts in the organic solvent. However, the effect of the total sulfate concentration and the acidic concentration on the extraction rate are not significant. The stripping rate is only a function of the initial concentration of phenol in the TOA salt-organic phase. By analyzing the experimental data, it was recognized that the extraction of phenol occurs at the interface, rather than in the bulk of the solution. The diffusion resistance, rather than the resistance of chemical reaction, is the rate-controlling step for the phenol extraction. Based on the experimental data, simple expressions of the extraction rate and stripping rate of phenol were obtained.     

REACTIVE EXTRACTION OF LEVULINIC ACID FROM AQUEOUS SOLUTIONS WITH TRI-n-OCTYLAMINE (TOA) IN 1-OCTANOL: EQUILIBRIA,KINETICS, AND MODEL DEVELOPMENT

Levulinic acid, a carboxylic acid containing a ketone structure, can be used as an acidulant in foods and beverages. Reactive extraction is a promising alternative for the recovery of carboxylic acids from aqueous streams. The design of an amine extraction process requires kinetic data for the acid-amine + solvent system used. In this study, equilibrium and kinetic data on the extraction of levulinic acid from aqueous solutions using tri-n-octylamine (TOA) in 1-octanol have been determined. The mass transfer coefficients of levulinic acid, TOA, and 2:1 levulinic acid-amine complex in 1-octanol were calculated from the acetic acid mass transfer coefficient, which was determined by measuring its fluxes of simple diffusion from kerosene to water. Based on the Hatta number and the criterion given by Doraiswamy and Sharma, the reaction regime has been found to be instantaneous reaction regime occurring at the interface on the organic phase side. An extraction model comprising equilibrium complexation constant w.r.t 2:1 levulinic acid-TOA complex formation, K_E2i (14.794 (m³ kmol^?1)²), and complex mass transfer coefficient, k_B2A (2.193 × 10^?6 m s^?1), has been developed.     

Equilibrium and kinetic studies of the extraction of chelated copper(II) anions with Aliquat 336

The equilibrium and kinetics of solvent extraction of Cu²⁺ from aqueous solutions containing equimolar EDTA with Aliquat 336 in n‐decanol and kerosene at 298 K were investigated. The concentrations of Cu²⁺ (8–50 mol m^?3), Cl^? (5–60 mol m^?3), and Aliquat 336 (20–100 mol m^?3) were varied. A semi‐empirical model with three parameters was proposed to describe the equilibrium behavior, in which the non‐idealities in both aqueous and organic phases were considered. Over the ranges studied, the model agreed reasonably well with the experimental data (standard deviation, 15%). The forward and backward reaction rate constants were determined as (5.31 ± 0.16)×10^?6 m^9/4 mol^?3/4 s^?1 and (2.62 ± 0.09)×10^?7 s^?1, respectively, at 298 K. An interfacial reaction mechanism was proposed, which revealed that the reaction between the chelated anions and trimeric amine molecules at the interface was rate limiting. The derived rate laws were consistent with the experimental results. © 2002 Society of Chemical Industry     

乙酸正戊酯酯化反应动力学探讨与催化精馏模拟

在间歇釜式反应器中,以NKC-9阳离子交换树脂为催化剂,对乙酸和正戊醇催化合成乙酸正戊酯的酯化过程进行了研究。实验考察了不同催化剂用量及反应温度对乙酸转化率的影响,同时测定了实验条件下乙酸正戊酯酯化反应的反应动力学数据。采用拟均相模型对实验数据进行关联,得到了平衡常数和反应速率常数的计算式。在本实验条件下,该酯化反应为吸热反应,反应热及正、逆反应活化能分别为8.339kJ/mol、50.191kJ/mol和41.852kJ/mol,平衡常数及正、逆反应速率常数与温度的关系式分别为：K=54.2173e^-8338.8/RT,k₁=95402.5e^50191/RT,k₂=1759.6e^41852.2/RT。结合测定的动力学方程,建立了基于严格数学模型的过程模拟计算方法,对乙酸正戊酯催化精馏酯化过程进行过程模拟优化。优化后的操作条件为精馏段板数3、反应段板数9、提馏段板数14、进料位置7、混合进料酸醇摩尔比1.1∶1,此时塔釜乙酸正戊酯摩尔分数与正戊醇转化率达到99%以上。     

丙酮酸化学萃取的盐效应

以三辛胺为萃取剂,在不同离子类型及离子强度下对丙酮酸的络合萃取过程进行了研究。结果表明,在一定pH范围内,随无机离子浓度的增加,丙酮酸分配系数随盐浓度的增加而迅速降低;萃后水相pH随盐浓度的增加均有不同程度的升高,在同一离子强度下,萃取剂浓度越高,萃后水相pH上升幅度越大。红外光谱的分析结果证实了无机阴离子可能通过同离子竞争,抑制了丙酮酸根离子与络合剂的离子对缔合作用,从而降低了萃取效果。     

A new method for analysis of sunset yellow in food samples based on cloud point extraction prior to spectrophotometric determination

A simple new micelle mediated preconcentration method was developed for analysis of sunset yellow (SY) prior to its spectrophotometric determination. The method was based upon cloud point extraction of the ion associate of SY and trioctylamine (TOA) in HCl–Triton X-100. In the surfactant phase the SY species react with TOA yielding hydrophobic ion associate of SY^?·TOA⁺. The distribution coefficient of SY between surfactant-rich phase and aqueous phase was approximately 104. Validation was tested by comparing the results with standard HPLC. Isotherm and thermodynamic parameters, chemical equilibrium, extraction constants and stiochiometry of the associate were assigned.     

Solvent extraction and separation of rare earths from chloride media using α-aminophosphonic acid extractant HEHAMP

Solvent extraction and separation of rare earths (REs: La ~ Lu, plus Y and Sc) by a novel synthesized extractant, (2-ethylhexylamino)methyl phosphonic acid mono-2-ethylhexyl ester (HEHAMP, abbreviated as H₂A₂), were investigated in chloride medium. The favorable separation factors (SFs) between adjacent heavy REs suggested that HEHAMP has a better separation performance than P507. The extracted complex of trivalent REs was determined to be REClH₂A₄ by the slope analysis method. Thermodynamic parameters (ΔH, ΔG, and ΔS) of Lu were calculated as 7.47 kJ mol^?1, ?6.05 kJ mol^?1, and 45.4 J mol^?1 K^?1 at 298.15 K, respectively, which indicate that the extraction reaction of Lu is an endothermic process. The loading capacity of 30% (v/v) HEHAMP toward Lu(III), Yb(III), and Y(III) was about 15.17 g Lu₂O₃/L, 14.46 g Yb₂O₃/L, and 12.64 g Y₂O₃/L, respectively. HCl is the most efficient stripping acid, and 92% of the loaded Yb(III) can be stripped by one-stage stripping with 2 mol/L HCl.     

磷酸三丁酯/煤油支撑液膜体系中苯酚的传质分离

研究了苯酚在以多孔聚丙烯平板膜(Celgard2500)为支撑体、磷酸三丁酯(TBP)为膜载体和煤油为膜溶剂的支撑液膜体系中的传质过程;用传统萃取法测定了TBP/煤油体系中苯酚络合物摩尔比为1∶1,同时得到25.0℃萃取平衡常数为96.72;考察了原料相pH值、初始质量浓度、膜二侧转速、载体浓度和反萃取相碱浓度对苯酚传质的影响,确定了该体系分离苯酚的最佳条件:原料相pH<9,苯酚初始质量浓度<1 000 mg/L,膜二侧转速>300 r/m in,载体浓度为0.55 mol/L,反萃取相碱浓度0.10 mol/L;根据双膜理论提出苯酚的传质动力学方程,采用直线斜率法计算了苯酚在TBP/煤油支撑液膜体系中的扩散层厚度和膜内扩散系数,计算结果表明动力学方程计算值能较好地与实验值吻合,平均相对误差在2%以内。     

Iridium(IV) Transport across Trioctylamine Supported Liquid Membrane

Abstract

Transport behavior of iridium through a supported liquid membrane (SLM) was investigated using trioctylamine (TOA) as a mobile carrier. Iridium(IV) was almost quantitatively extracted with TOA in kerosene from a low HCl solution, and extracted Ir(IV) was stripped with an HClO₄ or HNO₃ solution. Based on the extraction and stripping data, transport of Ir(IV) through a TOA-SLM was performed. Iridium(IV) in the feed solution with low HCl concentration was effectively transported into the HClO₄ or the HNO₃ product solution. Iridium(IV) was recovered and concentrated in the 1 M HClO₄ product solution by reducing the volume of strip solution relative to the volume of feed solution, yielding a sufficient enrichment factor.