Modeling of analytical, preparative and industrial scale counter-current chromatography separations.

Analytical, preparative and industrial scale counter-current chromatography (CCC) processes differ in the volumes of the loaded solution of components to be separated and in the design of the equipment. Preliminary mathematical modeling is necessary for selection of the optimal design and operation mode of these CCC separations. This study aims to compare simulations of CCC separations at different scales, using an exact description based on the model of equilibrium cells and a much simpler approximate solution based on the Gaussian distribution. Equations for modeling CCC separations of different scales and examples of simulation these separations are presented. It is shown that the discrepancy between the two simulations increases with an increase in the volume of the loaded solution of the components and a decrease in the number of equilibrium cells of a CCC device. In analytical and preparative separations, which are based on complex centrifugal devices, and relatively small sample volumes are injected, approximate equations can be used to simulate various options of CCC separation. In industrial-scale CCC separations, large volumes of the solution of components may be loaded, and as we have proposed previously, these separations can be based on a cascade of mixer-settler extractors. In this case, a more accurate mathematical description based on the cell model equations should be used for modeling.

Sm/Co Magnetic Materials: A Recycling Strategy Using Modifiable Hydrophobic Deep Eutectic Solvents Based on Trioctylphosphine Oxide.

Hydrophobic deep eutectic solvents (HDES) are widely used as extractants. Usually, when preparing HDES, only the extraction ability of one component is taken into account, with the second serving as an "inert" component, whose effect on the extraction process is not taken into account. The present study demonstrates the possibility of controlling the selectivity of a hydrophobic deep eutectic solvent based on trioctylphosphine oxide (TOPO) by varying the substance that acts as a hydrogen bond donor, but which does not have an extractive ability. In the course of the work, the influence of the "inert" component on the physicochemical and extraction properties of HDES was confirmed by experimental, spectroscopic, and also calculation methods. A number of phenols with different structural features were chosen as the HDES' hydrogen bond donors to modify: phenol (Ph), para-tert-butylphenol (PTBP) and thymol (Th). Using the example of separation of the Sm/Co pair, the influence of the structure of a hydrogen bond donor on the extraction ability of a hydrophobic deep eutectic solvent was established, where the degree of extraction of Sm (III) increased in the series Th:TOPO < PTBP:TOPO < Ph:TOPO. HDES based on TOPO and phenols can potentially be used to separate Sm and Co from the process leach solutions generated during the hydrometallurgical processing of waste SmCo magnets.

Modelling and Comparative Analysis of Different Methods of Liquid Membrane Separations.

This article is devoted to a brief review of the modelling of liquid membrane separation methods, such as emulsion, supported liquid membranes, film pertraction, and three-phase and multi-phase extraction. Mathematical models and comparative analyses of liquid membrane separations with different flow modes of contacting liquid phases are presented. A comparison of the processes of conventional and liquid membrane separations is carried out under the following assumptions: mass transfer is described by the traditional mass transfer equation; the equilibrium distribution coefficients of a component passing from one of the phases to another are constant. It is shown that, from the point of view of mass transfer driving forces, emulsion and film pertraction liquid membrane methods have advantages over the conventional conjugated extraction stripping method, when the mass-transfer efficiency of the extraction stage is significantly higher than the efficiency of the stripping stage. The comparison of the supported liquid membrane with conjugated extraction stripping showed that when mass-transfer rates on the extraction and stripping sides are different, the liquid membrane method is more efficient, while when they are equal to each other, both processes demonstrate the same results. The advantages and disadvantages of liquid membrane methods are discussed. The main disadvantages of liquid membrane methods-low throughput and complexity-can be overcome by using modified solvent extraction equipment to carry out liquid membrane separations.

Extraction of Copper from Sulfuric Acid Solutions Based on Pseudo-Liquid Membrane Technology.

Pseudo-liquid membranes are extraction devices in which a liquid membrane phase is retained in an apparatus consisting of two interconnected chambers while feed and stripping phases pass through the stationary liquid membrane phase as mobile phases. The organic phase of the liquid membrane sequentially contacts the aqueous phases of the feed and stripping solutions in the extraction and stripping chambers, recirculating between them. This extraction separation method, called multiphase pseudo-liquid membrane extraction, can be implemented using traditional extraction equipment: extraction columns and mixer-settlers. In the first case, the three-phase extraction apparatus consists of two extraction columns connected at the top and bottom by recirculation tubes. In the second case, the three-phase apparatus consists of a recycling close-loop, which includes two mixer-settler extractors. In this study, the extraction of copper from sulfuric acid solutions in two-column three-phase extractors was experimentally studied. A 20% solution of LIX-84 in dodecane was used as the membrane phase in the experiments. It was shown that the extraction of copper from sulfuric acid solutions in the apparatuses studied was controlled by the interfacial area in the extraction chamber. The possibility of the purification of sulfuric acid wastewaters from copper using three-phase extractors is shown. To increase the degree of extraction of metal ions, it is proposed to equip two-column three-phase extractors with perforated vibrating discs. To further increase the efficiency of extraction using the pseudo-liquid membrane method, it is proposed to use multistage processes. The mathematical description of multistage three-phase pseudo-liquid membrane extraction is discussed.

Three- and Multi-Phase Extraction as a Tool for the Implementation of Liquid Membrane Separation Methods in Practice.

To promote the implementation of liquid membrane separations in industry, we have previously proposed extraction methods called three- and multi-phase extraction. The three-phase multi-stage extraction is carried out in a cascade of bulk liquid membrane separation stages, each comprising two interconnected (extraction and stripping) chambers. The organic liquid membrane phase recycles between the chambers within the same stage. In multi-phase extraction, each separation stage includes a scrubbing chamber, located between the extraction and stripping chambers. The three- and multi-phase multi-stage extraction technique can be realized either in a series of mixer-settler extractors or in special two- or multi-chamber extraction apparatuses, in which the convective circulation of continuous membrane phase between the chambers takes place due to the difference in emulsion density in the chambers. The results of an experimental study of the extraction of phenol from sulfuric acid solutions in the three-phase extractors with convective circulation of continuous membrane phase are presented. Butyl acetate was used as an extractant. The stripping of phenol from the organic phase was carried out with 5-12% NaOH aqueous solutions. The prospects of using three-phase extractors for wastewater treatment from phenol are shown. An increase in the efficiency of three-phase extraction can be achieved by carrying out the process in a cascade of three-phase apparatuses.

Intermittent sample loading technique as a tool for obtaining high- concentration elution bands in recycling liquid-liquid chromatography: Theoretical study of periodic and semi-continuous separation processes.

To improve the efficiency of countercurrent chromatography (CCC) separations, we have previously proposed a new sample loading method called intermittent sample loading (ISL), in which continuous sample feed alternates with short periods of "clean" mobile phase feed to the CCC device. In semi-continuous separation processes, during sample feed periods, the sample is loaded in separate batches, each consisting of a series of intermittent sample loads. It was shown that the application of the intermittent sample loading method in the conventional isocratic CCC separations significantly increased process productivity and the concentration of compounds in the separated fractions. In this study, to further improve the CCC separations with intermittent sample loading, we discuss the application of the ISL method in the processes of close-loop recycling counter-current chromatography (CLR CCC). The advantage of the ISL CLR CCC over the ISL CCC is higher resolution and lower solvent consumption. Equations are presented that allow the simulation of periodic and semi-continuous ISL CLR CCC separations and the selection of optimal operational conditions for these separation processes. It is shown that the use of ISL technique in CLR CCC separations makes it possible to produce fractions of compounds with a much higher concentration than when using the conventional single sample loading method.

Closed-Loop Recycling Dual-Mode Counter-Current Chromatography with Specified Sample Loading Durations: Modeling of Preparative and Industrial-Scale Separations.

We previously reported on a new counter-current chromatography (CCC) operating mode called closed-loop recycling dual-mode counter-current chromatography (CLR DM CCC), which incorporates the advantages of closed-loop recycling (CLR) and dual-mode (DM) counter-current chromatography and includes sequential separation of compounds in the closed-loop recycling mode with the mobile x-phase and in the inverted-phase counter-current mode with the mobile y-phase. The theoretical analysis of several implementations of this separation method was carried out under impulse sample injection conditions. This study is dedicated to the further development of CLR DM CCC theory applied to preparative and industrial separations, where high-throughput operation is required. Large sample volumes can be loaded via continuous loading within a specified time. To simulate CLR DM CCC separations with specified sample loading durations, equations are developed and presented in "Mathcad" software.

Analytical, Preparative, and Industrial-Scale Separation of Substances by Methods of Countercurrent Liquid-Liquid Chromatography.

Countercurrent liquid-liquid chromatographic techniques (CCC), similar to solvent extraction, are based on the different distribution of compounds between two immiscible liquids and have been most widely used in natural product separations. Due to its high load capacity, low solvent consumption, the diversity of separation methods, and easy scale-up, CCC provides an attractive tool to obtain pure compounds in the analytical, preparative, and industrial-scale separations. This review focuses on the steady-state and non-steady-state CCC separations ranging from conventional CCC to more novel methods such as different modifications of dual mode, closed-loop recycling, and closed-loop recycling dual modes. The design and modeling of various embodiments of CCC separation processes have been described.

Data on the extraction of benzoic, salicylic and sulfosalicylic acids from dilute solutions using PEG-based aqueous two-phase systems.

The use of green chemistry principles in the extraction of aromatic acids from dilute aqueous solutions has been considered. The extraction of a number of aromatic acids important for the food and pharmaceutical industries in heterogeneous systems based on poly(ethylene) glycol 1500 (PEG-1500) has been studied for the first time. This research presents a data of the quantitative characteristics of the extraction of benzoic, salicylic and sulfosalicylic acids using a PEG-1500 (15 wt %)/Na2SO4 (9 wt %) aqueous two-phase system under various conditions (temperature and рН). The effect of various phase-forming salts (Na2CO3, (NH4)2SO4, and (NH4)2HPO4) in a PEG-1500-based aqueous two-phase system on the extraction of aromatic acids has been found. For salicylic and sulfosalicylic acids, distribution coefficients when using (NH4)2HPO4 have been obtained that considerably exceed values for conventional water-organic solvent systems.

Unusual effect of flow rate on retention in analytical supercritical fluid chromatography exemplified by polyethylene glycol separation.

We report a case of a peculiar effect of flow rate on retention in a separation of polyethylene glycol oligomers via supercritical fluid chromatography. During method development, we tested flow rate gradients and notices that for some PEG oligomers retention times at flow rate gradient were lower than at constant flow with the largest flow rate value used in a gradient. For instance, at BEH stationary phase and CO2-MeOH gradient from 10 to 35% at 20 min a PEG oligomer having mass of 1225 Da has a retention time 14 min at 1 mL/min flow rate, 10.3 at 2 mL/min and 9.5 min at 1-2 mL/min flow rate gradient. The effect is not unified for all PEG oligomers, it occurs only starting from a particular PEG molecular weight which depends on the stationary phase type and/or mobile phase conditions. We believe that such an unusual flow rate effects can happen in SFC on various occasions, not exclusively for flow rate gradients, and thus should be taken into account during method development or method transfer.

Complex Extraction of Metals in an Aqueous Two-Phase System Based on Poly(Ethylene Oxide) 1500 and Sodium Nitrate.

This article presents an ecologically safe aqueous two-phase system based on poly(ethylene oxide) with a molecular weight of 1500, designed for complex extraction of Ni(II), Co(II), Fe(III), Mn(II), Zn(II), Cu(II), and Al(III) from nitrate solutions. A kinetic dependence has been investigated for a distribution ratio for the metals examined. The influence of pH-values, temperature, initial metal concentration, and nitric acid content have on the extraction of a wide range of metals in the heterogeneous poly(ethylene oxide) 1500-NaNO3-H2O system has been discovered. As a result, the complex extraction of metals (EMe > 60%) was achieved in one step of extraction without introducing additional chemicals into the system.