Cloud Point Extraction of Glycyrrhizic Acid from Licorice Root

Abstract

An attempt has been made to extract glycyrrhizic acid (GA) from licorice root by surfactant mediated cloud point extraction (CPE) using non‐ionic surfactant (Triton X‐100). Almost all of the GA molecules were concentrated in the surfactant‐rich phase (also called coacervate phase) after phase separation. The pH is the most critical factor regulating the distribution of GA in the micelle which related to the ionization form. The other effects of the concentration of GA and the surfactant, the temperature, and the salt concentration on the extraction efficiency of GA in the coacervate phase and aqueous phase have been studied. The mechanism of CPE of GA was explored with transmitting electron microscopy. It was deduced that aggregate GA molecules were adsorbed on micelles' outer poler mantle and inner cross‐linked micelles at high GA concentrations in coacervate phase.     

Cloud Point Extraction (CPE) of Parabens using Nonionic Surfactant Phase Separation

A cloud point extraction (CPE) method was developed using silicone-ethylene oxide surfactant, DC193C, to study the equilibrium phase separation of parabens in environmental water samples. The volume of the surfactant rich phase (V_s), aqueous phase (V_w), preconcentration factor (C_F), distribution coefficient (K_d), and percentage of recovery (%R) were evaluated to obtain the optimum condition for phase separation of parabens. Satisfactory results were obtained whereby the preconcentration factor for methylparaben, ethylparaben, propylparaben, and benzylparaben were close to 65, 60, 80, and 45, respectively, at 0.5% weight of surfactant. The presence of DC193C gave a low phase volume ratio but insignificant result was observed with the increased of surfactant concentration. The parabens were well separated on a reverse-phase Chromolith C₁₈ column (100 mm × 4.6 mm) with a gradient elution (acetonitrile: water; 30:70 v/v) and detected at 254 nm. The proposed method was successfully applied to environmental samples such as river water, treated wastewater, sea water, and tap water with satisfactory results. The method detection limit was 0.1–0.2 ppb and the recoveries were 71.2–97.7% with the relative standard deviations of 0.3–2.1%.     

Cloud Point Extraction of Four Triphenylmethane Dyes by Triton X-114 as Nonionic Surfactant

A method for removing four triphenylmethane dyes from wastewater by cloud point extraction with the nonionic surfactant Triton X-114 (TX-114) was developed. The triphenylmethane dyes were crystal violet, ethyl violet, malachite green and brilliant green. The cloud point of TX-114 generally increased in the presence of any of the four dyes. In the cloud point system, these dyes were solubilized into a coacervate phase that left a color-free dilute phase. The extraction efficiency of the dyes increased with the temperature, TX-114 concentration, and salt (NaCl and CaCl₂) concentration. More than 97% TX-114 in the dilute phase was recovered by adjusting the volume ratio of dichloromethane to the dilute phase. The Langmuir-type adsorption isotherm was used to describe the dye solubilization. The Langmuir constants m and n were calculated as functions of temperature. The results showed that the solubilization of the triphenylmethane dyes in the cloud point system was related to the partition coefficient and their molecular structures.     

相分离辅助方法对有机硅表面活性剂浊点萃取PAHs的影响

相分离性能和萃取率是评价浊点萃取(CPE)性能的两个重要因素.对于采用非离子表面活性剂的CPE,当溶液加热至浊点以上,仅依靠热运动来促使其发生相分离是十分缓慢的,因此通常需要一定的辅助方法来加速其相分离的进程.今利用两种聚醚型有机硅表面活性剂DC-193和DC-190,对蒽、菲、芘和苊四种多环芳烃(PAHs)进行浊点萃取研究,分别使用加热、加盐、离心和搅拌等辅助方法改变相分离过程的速度.通过测定表面活性剂富集相的体积百分率Vs/(Vs Vw)随时间的变化和最终的萃取率,研究上述四种不同辅助方法对相分离行为和萃取性能的影响.结果表明,相分离速度:加盐＜加热＜离心＜搅拌;Vs/(Vs Vw):搅拌＜离心＜加盐＜加热;萃取率:加热＜加盐≈离心＜搅拌.可见,离心与搅拌辅助CPE具有较大的优势,可同时提供更高的相分离性能和萃取率.与离心相比,搅拌的引入所需设备更简单,而且对于容器的体积没有限制,易于实现连续操作,更有望应用于实际的大规模水处理之中.     

多元渗透维里方程通式的表达：双水相系统的液液平衡计算

提出了基于三元系修正Ｐｉｔｚｅｒ模型的多元渗透维里方程通式，并应用于双水相系统液液平衡性质的关联和预测，用汽液平衡数据关联模型参数，预测了聚乙二醇／硫酸镁双水相系统的液液平衡；用汽液平衡数据和尽可能少的液液平衡数据关联模型参数。同时预测了焦点或不含电解质的ＰＥＧ／葡萄糖双水相系统的液液平衡和ＫＣｌ电解质在ＰＥＧ／ＤＥＸ系统中的分配系数。计算结果表明，模型有较好的预测功能。     

Tuning of Cloud Point by the Nature of Surfactant Headgroup: Influence of Counterion and Additives

Work was performed to distinguish the role of sulfonate (–SO₃ ^?) and sulfate (–OSO₃ ^?) with respect to the micellization and clouding phenomenon in ionic surfactant solutions. The clouding phenomenon is a recent addition to the conventional one observed with nonionic surfactants. Three ionic surfactants [sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and sodium dodecylsulfonate (SDSo)] are chosen and the effects of added tetra-n-pentylammonium bromide (TPeAB) and benzyl tributylammonium bromide (BTAC) have been studied on micellization and clouding behaviors in aqueous solution. Based on critical micelle concentration (CMC) and cloud point (CP) measurements, the following order has been observed: SDBS < SDS < SDSo. Though both SDBS and SDSo contain sulfonate groups, they are found at the two ends of the ordering. Therefore, the role of the phenyl ring is also having importance in clouding phenomena. For a typical surfactant, TPeAB was found to be more effective than BTAC. Based on the CP studies, two compositions of SDSo + TPeAB/BTAC were chosen and the effects of different additives (carbohydrate, amino acid, and l-ascorbic acid) on the CP were investigated. Additive may either decrease or increase CP, depending on the structure of the counterion or additive. The present work shows a few novelties: (1) headgroup/counterion dependence of CP and (2) hydrophobicity of counterion/surfactant has an important bearing on the phenomenon. The data can be utilised in improving cloud point extraction methodologies (CPEMs).     

Partitioning equilibria in multicomponent surfactant systems for design of surfactant-based extraction processes

Aqueous biphasic systems based on nonionic surfactants have perspective applications in extraction processes, in particular, cloud point extraction of hazardous compounds or high valued products, especially biomolecules. Additives (e.g., ionic surfactants, salts) and variations in pH can significantly affect the surfactant-based separation processes, representing an additional degree of freedom for their optimization. However, there are few systematic studies of phase and partition behavior for these multicomponent surfactant systems.In this study we examined the clouding, phase compositions and partitioning equilibria for aqueous mixed surfactant systems of a nonionic surfactant (Triton X-114), ionic surfactants (cetyltrimethylammonium bromide or sodium dodecyl sulfate) and NaCl, in order to improve the extraction efficiency. Vanillin was used as a model substance at three different pH values, specifically in (partly) dissociated or non-dissociated states. The partition coefficients obtained in the batch experiments were compared to the predictions by the thermodynamic model COSMO-RS. Based on this knowledge a continuous multistep extraction process was carried out.To the best of our knowledge this is the first demonstration of using a mixed surfactant system for continuous countercurrent cloud point extraction.     

Automatic Low‐Cost Method to Determine the Solubility of Liquid‐Liquid Mixtures by Continuous‐Flow Cloud Point Titration

A low‐cost, accurate, and fast technique to determine the solubility of liquid‐liquid mixtures by continuous cloud point titration is demonstrated. A light‐emitting diode (LED) is employed to illuminate the mixing liquids during the continuous‐flow titration process, and the transmitted light as well as Mie scattering from droplets is monitored using a simple webcam image sensor. The time‐resolved evolution of the signal allows the determination of the solubility. In order to prove the concept and to evaluate its accuracy and reproducibility, experimental results from the binary systems butan‐1‐ol/water and pentan‐1‐ol/water are presented and compared with literature data. The entire setup can be realized with a low investment and delivers results virtually identical to those in literature with established techniques. The approach is suitable for academic and industrial, but due to its simplicity also for educational purposes.     

Cloud Point Extraction and Preconcentration for the Determination of Cu and Ni in Natural Water by Flame Atomic Absorption Spectrometry

Abstract

In this work, a new cloud point extraction (CPE) method was developed for the separation and preconcentration of copper and nickel. The analyte was complexed with 3‐[(8‐{[(E)‐2‐hydroxyimino‐1‐methylpropylidene] amino}‐1‐naphthyl) imino]‐2‐butanone oxime (H₂mdo) in the initial aqueous solution and octylphenoxy polyethoxy ethanol (Triton X‐114) was added as a surfactant. After phase separation, based on the cloud point in the mixture, and dilution of the surfactant‐rich phase with methanol containing 0.1 mol l^?1 HNO₃, the enriched analytes were determined by flame atomic absorption spectrometry. After optimization of the complexation and extraction conditions (i.e. pH=8.5, H₂mdo=3×10^?4 mol l^?1, Triton X‐114=0.1% (w/v)) the enhancement factors of 65 and 59 and detection limits of 0.14 and 0.2 ng ml^?1 were obtained for copper and nickel respectively. The proposed method was applied to the determination of copper and nickel in several natural water samples with satisfactory results.     

Application of Micellar Extraction for Isolation of Famotidine from Aqueous Samples Prior to its Chromatographic Determination

Micellar extraction was applied to isolate famotidine from aqueous samples. This drug is an H₂ receptor antagonist used for the treatment of stomach diseases. The process was performed with a mixture of anionic sodium dodecylsulfate and nonionic Triton X‐114 surfactants. The effect of different parameters on the efficiency of the micellar extraction such as electrolyte and surfactant concentration, pH of sample, temperature, shaking and centrifugation time was investigated. The influence of foreign substances on a studied process was tested. The elaborated procedure was applied for HPLC–UV determination of famotidine in natural water samples. The calibration graph was recorded in the range 1.35–37.12 μg mL^?1 of the studied compound. The repeatability of the method was equal to 7.4%. The limit of detection and quantification values for the determination of famotidine by using the proposed method amounted to 0.40 and 1.25 μg mL^?1, respectively.     

Separation of Neutral Red and Methylene Blue from Wastewater using Two Aqueous Phase Extraction Methods

Abstract

The aim of this work was the two‐aqueous phase extraction of neutral red and methylene blue from wastewater. This has been achieved on the basis of phase separation properties of non‐ionic surfactants above the so‐called cloud point curve and the solubilization phenomena of coacervate micelles (surfactant rich phase). Three commercial surfactants were used in this work; the Oxo‐C₁₅E₇ which is an ethoxylate fatty alcohol (Dehydol LT 7), Triton X‐114 (iso‐C₈H₁₇‐C₆H₄‐(OCH₂CH₂)_7,5OH), and Triton X‐100 (iso‐C₈H₁₇‐C₆H₄‐(OCH₂CH₂)_9,5OH) which are alkyl phenol ethoxylate surfactants. The phase diagrams of binary water/surfactants systems were drawn and the effect of sodium sulphate on water‐surfactant systems was therefore studied. Oxo‐C₁₅E₇ and Triton X‐114 were used for the cloud point extraction of neutral red and methylene blue from their aqueous solutions at 100 mg/L and 7 mg/L, respectively. The experimental extraction results were expressed by the following three responses: percentage of the extracted dye (E), residual concentrations of dye in the dilute phase (X_s,w), and the volume fraction of coacervate (φ_C) at the equilibrium. The results obtained for each parameter were also represented on three‐dimensional diagrams using an empirical smoothing method. The empirical modelling data were in agreement with the experimental ones. The main advantage was sought between E, which has reached 99% in the case of neutral red, whereas in the case of mehtylene blue 92% was obtained with respect to (φ_C), which should have a minimum value. At the optimal conditions, neutral red and methylene blue concentrations in the effluent were reduced to about 500 times and 7 times, respectively.     

Molecular mechanism for liquid–liquid extraction: Two‐film theory revisited

We investigate here the molecular mechanism for liquid‐liquid extraction and revisit the classical two‐film theory. With equilibrium and non‐equilibrium molecular dynamics simulations, we illustrate the kinetics of solute crossing the interface and in particular the structure of the interface at which two stagnant liquid films adhere. Our simulation results show that beyond the two‐film theory, the interface is well structured and plays an essential role in solute transfer. We found that at the well‐developed interface region the overall density profile exhibits a dip, while the solute concentration shows a significant maximum. Free energy analysis demonstrates the interfacial enrichment of solute molecules serving as a potential well for solute adsorption. Thus, different from the assumption of the two‐film theory, our simulations show that there exists a resistance for solute molecules crossing the interface, which could be overcome only at high interface concentration of solute caused by interfacial enrichment. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2464–2470, 2017     

Thermal Effects During the Absorption of CO2 in Aqueous Solutions of 3‐Amino‐1‐Propanol

In this work, we study the process of CO₂ absorption, at high partial pressures, in aqueous solutions of 3‐amino‐1‐propanol (AP), with respect to the thermal effects of this operation. All of the experiments were performed in a stirred tank gas‐liquid reactor with a flat, known interface. The variables considered were the AP concentration in the range of 0.1 to 3.0 M and the temperature within the interval of 288–313 K. From the results, we deduce that the process takes place in the instantaneous nonisothermal regime, and we propose an equation which relates the experimental results of molar flux with the initial amine concentration. At the same time, we can evaluate the temperature increase at the gas‐liquid interface.     

环氧乙烷-环氧丙烷无规共聚物的水溶液浊点测定

通过对EOPO水溶液浊点数据的测定 ,研究了EOPO 水二元系统的相行为。考察了添加盐浓度和种类 ,聚合物浓度和分子质量等对EOPO水溶液浊点的影响。结合实际分离过程 ,就上述各因素对EOPO水溶液相行为的影响进行了分析和讨论     

Prediction of Two‐Phase Frictional Pressure Drop for the Concurrent Gas and Newtonian Liquids Upflow through Packed Beds

Correlations were developed to predict frictional pressure drop for concurrent gas‐liquid upflow through packed beds covering all the three identified flow regimes, i.e. bubble flow, pulse flow and spray flow. The observation that the gas and liquid flow rates have different influences on the two‐phase pressure drop in different flow regimes, was taken into consideration in the development of these correlations. More than 600 experimental pressure drop data from the present study and literature covering a wide range in gas‐liquid systems, flow rates and column packing were used.     

Heptakis(2,3‐di‐O‐methyl‐6‐O‐sulfopropyl)‐β‐cyclodextrin: A Genuine Supramolecular Carrier for Aqueous Organometallic Catalysis

The behavior of heptakis(2,3‐di‐O‐methyl‐6‐O‐sulfopropyl)‐β‐cyclodextrin as inverse phase transfer catalyst in biphasic Tsuji–Trost and hydroformylation reactions has been investigated. In terms of activity, this methylated sulfopropyl ether β‐cyclodextrin is much more efficient than the randomly methylated β‐cyclodextrin, which was the most active cyclodextrin known to date. From a selectivity point of view, the intrinsic properties of the catalytic system are fully preserved in the presence of this cyclodextrin as the chemo‐ or regioselectivity was found to be identical to that observed without a mass transfer promoter in the hydroformylation reaction. The efficiency of this cyclodextrin was attributed to its high surface activity and to the absence of interactions with the catalytically active species and the water‐soluble phosphane used to dissolve the organometallic catalyst in the aqueous phase.     

Organic media selection for the extraction of β‐hydroxyisobutyric acid produced by microbial biotransformation

The aim of this work is to evaluate both the toxic effect of different organic media on the stereospecific oxidation of 2‐methyl‐1,3‐propanediol to R‐(−)‐β‐hydroxyisobutyric (HIBA) in two‐phase systems and the extraction ability and selectivity of these non‐water miscible phases. Apart from traditional solvents, specific organic acid‐complexing carriers like TOPO, TOA and Aliquat 336 dissolved in different diluents have been studied. Special interest has been focused on the effect of the concentration of the organic phase extractants and the pH of the aqueous phase on the extraction system. TOPO dissolved in isooctane enabled higher K_p values at lower concentrations to be attained and resulted in lower toxicity, but its extractive capacity is strongly dependent on the pH. Our results suggest that using a compromise pH value between optimum for bioconversion and extraction, TOPO dissolved in isooctane can be successfully used as an extractive phase for HIBA production in a two‐phase system. © 2000 Society of Chemical Industry     

Properties and Catalytic Activities of New Easily‐Made Amphiphilic Phosphanes for Aqueous Organometallic Catalysis

Mono‐ and disulfonated amphiphilic versions of triphenylphosphane (PPh₃) and cyclohexyl(phenyl)phosphane were easily synthesized from commercial reagents and sulfuric acid. The behaviour of these phosphanes in solution was investigated by surface tension, isothermal titration calorimetry, nuclear magnetic resonance and cryo‐transmission electron microscopy. Two different supramolecular assemblies were evidenced according to the degree of sulfonation. The monosulfonated phosphanes formed well organized micelle‐like aggregates while the disulfonated phosphanes formed heterogeneous and disorganized vesicle‐like assemblies. The efficiency of these amphiphilic phosphanes was evaluated in the aqueous biphasic, palladium‐catalyzed cleavage of allyl alkyl carbonates.     

Comparison of Experimental Techniques for the Measurement of Mixing Time in Gas‐Liquid Systems

Measurements of the homogenisation characteristics during the agitation of a liquid and the mixing time by simple in situ conductivity probes are very well established. However, unless special precautions are taken, in the presence of the second phase such as gas, the conductivity trace becomes distorted to a greater or lesser extent, so that it is not possible to follow the transient change of concentration in the liquid phase or estimate the mixing time. In this paper it is confirmed that, without special precautions, simple in situprobes are unsatisfactory. However, by shielding the probe with a “cage”, the ingress of bubbles into the probe region is essentially prevented and satisfactory results can be obtained in situ with responses having as little noise as in the case without gas. A second technique involves elimination of the gas from a small sample stream and measurement of the stream's conductivity transient. By suitable and rather simple treatment of the response, results equivalent to that from the in situ shielded probes can be obtained. The latter technique is especially useful where the placement of in situ probes is difficult. It is also suggested that recent results, which disagree with much of the literature on liquid phase mixing times in gassed systems, arose due to the use of in situ unshielded conductivity probes.     

Two‐Phase Hydroformylation of Higher Olefins Using Randomly Methylated α‐Cyclodextrin as Mass Transfer Promoter: A Smart Solution for Preserving the Intrinsic Properties of the Rhodium/Trisulfonated Triphenylphosphine Catalytic System

The two‐phase hydroformylation of higher olefins with the rhodium/trisulfonated triphenylphosphine catalytic system in the presence of various chemically modified α‐cyclodextrins has been investigated. These cyclodextrins allowed us to increase greatly the reaction rate and the chemoselectivity of the reaction but, contrary to what has been observed previously with the chemically modified β‐cyclodextrins, the linear to branched aldehydes ratio was not affected by the presence of α‐cyclodextrin derivatives. Indeed, the latter was found to be similar to that obtained without any mass transfer promoter, suggesting that the catalytic species are stable in the presence of α‐cyclodextrin derivatives.