Extraction of citric acid from aqueous solutions with Alamine 336: equilibrium and kinetics

Citric acid is one of the organic acids for which the world market is growing every year. This article describes equilibria and kinetic studies for the extraction of citric acid by Alamine 336 with methyl‐iso‐butylketone (MIBK) as diluent. The theory of extraction accompanied by a chemical reaction has been used to obtain the intrinsic kinetics of extraction of citric acid by Alamine 336 in MIBK. The reaction has been found to be first order in both Alamine 336 and citric acid with a rate constant of 0.013 m³ kmol^?1 s^?1. Copyright © 2004 Society of Chemical Industry     

Equilibria and kinetics for reactive extraction of lactic acid using Alamine 336 in decanol

Lactic acid is an important commercial product and extracting this from aqueous solution is a growing requirement in fermentation‐based industries. The design of an amine extraction process requires (i) equilibrium and (ii) kinetic data for the acid–amine (solvent) system used. The equilibrium complexation constants for ratios of (1:1) and (2:1) have been estimated. The kinetics of extraction of lactic acid by Alamine 336 in decanol has also been determined. The reaction between lactic acid and Alamine 336 in decanol in a stirred cell falls in Regime 3, ie extraction accompanied by a fast chemical reaction occurring in the diffusion film. The reaction has been found to be zero order in Alamine 336 and first order in lactic acid with a rate constant of 0.21 s^?1. These data will be useful in the design of extraction processes. © 2002 Society of Chemical Industry     

三烷基胺萃取氨基磺酸及其废水的特性研究

p-Amino benzene sulfonic acid (PABSA) is selected as the solute with amphoteric functional group, Lewis acid and Lewis base, to be separated from its dilute solutions. An aliphatic, straight chain amine, Alamine 336, is used as the extractant, and kerosene, 1-octanol, chloroform, butyl acetate and benzene as the diluent. The effects of pH value of solution, extractant concentration, salt and types of diluent on the distribution coefficient, D, are studied. There is a peak of D value with pH value of solution, the polar diluents are favorable for extracting PABSA, and the salt in aqueous phase reduces values of D apparently. The extraction equilibrium is described using the mass action law, and the calculated data according to the proposed model agree with the experimental data well. Further, the extraction behavior for other amino benzene sulfonic acids, 1-amino-8-naphtol-3,6-disulfonic acid (H acid) and 4,4′-diaminostilbene-2,2′-disulfonic acid (DSD acid), is investigated in a wide pH value region. Finally. H acid and DSD acid are successfully removed from wastewater by the extraction with Alamine 336.     

liquid–liquid extraction of lactic acid with Alamine 336

The extraction of lactic acid (HL) from aqueous solutions by Alamine 336 (B) dissolved in toluene was studied. Experiments were performed in the temperature range of 25–60°C and for two amine concentrations of 20 and 40% (v/v) in toluene. The extent to which the organic phase (amine + toluene) may be loaded with lactic acid is expressed as a loading ratio, Z = C_HL /C_B. Z values are independent of the amine concentration and, hence, the extracted complex contains only one molecule of amine. Z decreases with increasing temperature. Experimental results indicate that the system presents overloading, i.e. Z > 1. The extraction equilibrium may be interpreted as a result of consecutive formation of three acid–amine species with stoichiometries of 1:1, 2:1 and 3:1.     

季铵盐(Aliquat 336)萃取对氨基苯磺酸的特性研究

利用季铵盐(Aliquat 336)为反应剂,在较宽的pH值条件下,研究了对氨基苯磺酸稀溶液的萃取相平衡特性;测定了反应剂浓度、稀释剂种类、盐的存在以及溶液pH值对反应萃取平衡分配系数的影响;提出了反应剂与对氨基苯磺酸负离子的阴离子交换反应机理,建立了平衡分配系数D值的表达式。结果表明,极性稀释剂不利于对氨基苯磺酸的萃取,惰性稀释剂能提供较大的萃取平衡分配系数,其顺序为:苯>四氯化碳>氯仿>正辛醇;盐的存在会降低Aliquat 336的萃取效率;与三烷基胺(Alamine 336)相比,Aliquat 336具有更宽的pH值适用范围。     

Solvent Extraction of Molybdenum and Technetium with Alamine 336 from Acid Solutions

Abstract

The distribution of Mo(VI) and Tc(VII) as molybdate and pertechnetate between Alamine 336 in benzene and other diluents and aqueous solutions of sulfuric and nitric acids was studied as a function of the concentration of acids and anions. The effect of the nature of the diluents and the presence of Tc on the extraction of Mo was studied.     

Extraction Equilibria of Trimellitic and [ 1,1′-Biphenyl]-2,2′-dicarboxylic Acid with 1-Octanol, 50%TBP,and 10%TRPO in Kerosene

To explore the feasibility of extracting aromatic acid products from oxidizing coal, two aromatic acids, trimellitic and [1,1′-biphenyl]-2,2′-dicarboxylic acid, were selected as the solutes, and the extraction equilibrium of the acids were studied with 1-octanol, 50% tributyl phosphate （TBP） in kerosene, and 10% trialkylphosphine oxide （TRPO） in kerosene. The results showed that the degree of extraction of [1,1′-biphenyl]-2,2′-dicarboxylic acid was larger than that of trimellitic acid for all of the solvent, and the extraction capacity with TRPO is more effective than the one with TBP. The extraction behavior of aromatic polyacid is different from that of carboxylic acid, and the reactive extraction function of aromatic acids with TBP and TRPO is not as effective as that of carboxylic acid. 1-octanol could be used to remove [1,1′-biphenyl]-2,2′-dicarboxylic acid from the mixture of trimellitic acid and [1,1′-biphenyl]-2,2′-dicarboxylic acid. Because the weak hydrogen bond association exists between -OH in 1-octanol and -COOH in aromatic acid, the extractive selectivity of [ 1, 1′-biphenyl]-2,2′-dicarboxylic to trimellitic acid depends on the stoichiometric ratio.     

Sorption of Citric Acid from Aqueous Solutions by Macroporous Resins Containing a Tertiary Amine Equilibria

Abstract

Experiments were conducted on equilibrium distribution of citric acid between relatively concentrated aqueous solutions and macroporous resins containing tri-n-octylamine (TOA). The equilibrium data were well described by the Langmuir isotherm equation. Chemical model analysis of the results showed that the sorption could be also explained by the formation of an acid-amine complex with general composition (acid)(TOA)_q in the resin phase. The loss of amine from the impregnated resins and the effect of temperature on equilibrium distribution were also discussed.     

Zirconium and Hafnium Separation,Part 1. Liquid/Liquid Extraction in Hydrochloric Acid Aqueous Solution with Aliquat 336

Abstract

The extraction of zirconium and hafnium from aqueous HCl solutions by means of Aliquat 336 in organic diluents was systematically studied. The following three aspects were discussed: the extraction dependence on HCl, the Aliquat 336 concentrations, and the nature of diluents. Both of the metals were stripped with deionized water and the influence of phase ratio on the efficiency of the stripping has been investigated. The stoichiometry of the extracted Zr and Hf species from single metal ion were studied and a possible extraction mechanism for the Zr‐Hf mixture is discussed in the light of the results obtained.     

基于流变特性的动力学模型研究及在柠檬酸发酵过程的应用

研究了基于流变特性的动力学模型,并以实验统计数据为基础,通过对模型进行分析,推断了模型参数,同时将模型应用于柠檬酸发酵过程中。结果表明模型的拟合效果良好,从而表明所建立的模型基本符合柠檬酸发酵过程,这为显示流变特性对发酵代谢过程的影响提供了理论依据,也为实现柠檬酸发酵过程最优化提供必要条件。     

Facilitated Pertraction of p-Aminobenzoic Acid with Amberlite LA-2 in Presence of 1-Octanol

p-Aminobenzoic acid has been facilitated pertracted with Amberlite LA-2 dissolved in dichloromethane, using a U-shaped pertraction cell which allows obtaining the free liquid membrane. The pertraction has been a carrier out in the presence of 1-octanol added in the liquid membrane. The addition of the alcohol led to the increase for up to 3 times of the acid initial and final mass flows, this effect being directly related to the process variables (pH-gradient between the aqueous phases, carrier and alcohol concentrations inside the membrane phase, mixing intensity). But, the influence of 1-octanol on the transport capacity of the pertraction system was negative, its addition inducing the accumulation of PABA in the liquid membrane, and requiring the reevaluation and optimization of the acid reextraction from the membrane phase to the stripping one.     

Adsorption of Crystal Violet From Aqueous Solution by Citric Acid Modified Rice Straw: Equilibrium,Kinetics, and Thermodynamics

Rice straw, an abundant, lignocellulosic agricultural residue was thermochemically modified with citric acid to develop a biodegradable cationic adsorbent. The application potential of the prepared adsorbent to remove hazardous Crystal Violet dye from its aqueous solution was investigated. The morphological and chemical characteristics of the adsorbent were established by scanning electron microscopy (SEM), surface area, and porosity analysis by the BET (Brunauer, Emmett, and Teller) nitrogen adsorption method and Fourier transform infrared (FTIR) spectroscopy. Batch adsorption studies were carried out as a function of solution pH, adsorbent dose, initial dye concentration, and temperature, in order to get insights into the effect of these independent parameters on the adsorption process. The Langmuir, Freundlich, and Dubinin–Radushkevich models were used to describe the equilibrium adsorption data. The sorption mechanism was also evaluated in terms of kinetics and thermodynamics. The adsorption equilibrium data was well described by the Langmuir isotherm model. The adsorption process followed the pseudo-second-order rate kinetics. Thermodynamic study showed spontaneous and exothermic nature of the adsorption process.     

异戊醇从氧化物-磷酸体系中萃取磷酸的动力学研究

采用上升液滴法研究了异戊醇从氯化物－磷酸体系中萃取磷酸的动力学，结果表明磷酸的初始正向萃取速率随两相界面积、水相初始磷酸、盐酸浓度的增大而增大，异戊醇对磷酸的萃取可能属扩散控制模式。在实验基础上建立了如下的萃取动力学方程：Ｒｐ＝４．７１９×１０－８Ｃ１．８０２ｐＣ１．００４ｃｌ，其计算值与实验值的相对标准偏差为５．０２％。     

三烷基胺萃取丙酸的动力学特性

为研究胺类萃取剂萃取有机酸的动力学行为 ,以丙酸稀溶液为分离溶质 ,三烷基胺 ( 730 1)为萃取剂 ,正辛醇和煤油的混合物为稀释剂 ,采用恒界面池法考察了萃取剂和溶质浓度、搅拌速率、两相接触面积、温度等操作参数对丙酸萃取动力学的影响。结果表明 :730 1萃取丙酸为准一级反应萃取过程 ;且萃取发生在相界面 ,即界面反应萃取机制 ;表观活化能为 2 8.5kJ/mol,萃取速率受温度的影响不显著 ;经计算 ,在一般的萃取塔操作条件下 ,该体系的萃取过程为反应和传质过程的混合控制。     

磷酸三丁酯萃取磷酸的动力学研究

本文简要介绍了磷酸的生产概况。采用上升液滴法研究了磷酸三丁酯从氯化物—磷酸体系中萃取磷酸的动力学。结果表明,磷酸的初始止向萃取速率随两相界面积、水相初始磷酸、盐酸浓度的增大而增大。磷酸三丁酯对磷酸的萃取可能属扩散控制模式。在实验基础上,建立了萃取动力学方程:R=4.71×10-8Cp0.70CC01.61,其计算值与实验值的相对标准偏差为4.82%。     

多元杂多酸在仲辛醇制己酸中的催化作用

采用磷、钼、钒系列多元杂多酸作为硝酸氧化仲辛醇制己酸的催化剂,对其催化性能和选择性进行了实验研究。结果表明:H6PMo9V3O40、H10PMo5V7O40、H11PMo4V8O40等多元杂多酸均可提高仲辛醇的转化率、己酸产率和己酸选择性,并确定了这3种催化剂的最佳用量:当它们分别为仲辛醇质量的1 4%、1 0%、1 4%时,仲辛醇转化率可达98 3%、97 6%、100%;己酸的选择性可达85 7%、85 8%、78 8%;其性能明显优于钒催化剂。     

反胶团萃取磷酸溶液中镁的动力学

采用恒界面池研究了二壬基萘磺酸(DNNSA)-煤油-磷酸体系萃取镁离子的动力学.考察了搅拌转速和传质界面积对萃取速率的影响,实验结果表明:磷酸中镁离子的萃取速率在200 r·min~(-1)时出现与搅拌强度无关的化学反应动力学"坪区",此时萃取速率正比于两相接触面积,说明萃取过程为界面化学反应控制过程.在动力学"坪区",镁离子萃取速率正比于萃取剂浓度和水相镁离子浓度,随着温度升高萃取速率增加;萃取反应活化能为70.01 kJ·mol~(-1),并得到了DNNSA萃取磷酸中镁离子的萃取动力学方程.