Industrial countercurrent chromatography separations based on a cascade of centrifugal mixer-settler extractors.

In hydrometallurgy, traditional extraction technologies, in particular, for isolation and purification of rare-earth metals include a number of processing steps using up to hundreds of mixer-settler extractors. These technologies could be greatly simplified by using the methods of countercurrent chromatography (CCC) separation. However, the current CCC equipment cannot process large volumes of feed material formed during the industrial production of these metals. In this paper, the cascade of centrifugal mixer-settler extractors assembled as a multi-stage unit is suggested for industrial application of CCC and discussed.

Simultaneous concentration and separation of target compounds from multicomponent mixtures by closed-loop recycling countercurrent chromatography.

Closed-loop recycling countercurrent chromatography (CLR CCC) with multiple sample injection has been shown to provide simultaneous concentration and separation of target compounds from multicomponent mixtures. Previous analysis of CLR CCC with multiple sample injections has been limited to the ideal recycling model, which neglects the effects caused by the pump and connecting lines. In this study, an analysis of the process is carried out based on the non-ideal recycling model: recycling chromatograms at two points of the closed-loop - the inlet of the column (A) and the outlet of the column (B) - are considered. The sample is repeatedly introduced at the inlet of the column when the circulating peak of target compound passes point A. Analytical expressions are developed, allowing the design and simulation of different variants of simultaneous separation and concentration of target compounds from multicomponent mixtures. Examples of separation of target compounds from three and five-component mixtures are discussed. Experimental results are presented demonstrating a reasonable agreement between the theory and the experiment. Due to its ability to concentrate individual solutes, CRL CCC with multiple sample injections can become an efficient analytical method to determine minor components in complex mixtures.

Theoretical study of closed-loop recycling liquid-liquid chromatography and experimental verification of the theory.

The non-ideal recycling equilibrium-cell model including the effects of extra-column dispersion is used to simulate and analyze closed-loop recycling counter-current chromatography (CLR CCC). Previously, the operating scheme with the detector located before the column was considered. In this study, analysis of the process is carried out for a more realistic and practical scheme with the detector located immediately after the column. Peak equation for individual cycles and equations describing the transport of single peaks and complex chromatograms inside the recycling closed-loop, as well as equations for the resolution between single solute peaks of the neighboring cycles, for the resolution of peaks in the recycling chromatogram and for the resolution between the chromatograms of the neighboring cycles are presented. It is shown that, unlike conventional chromatography, increasing of the extra-column volume (the recycling line length) may allow a better separation of the components in CLR chromatography. For the experimental verification of the theory, aspirin, caffeine, coumarin and the solvent system hexane/ethyl acetate/ethanol/water (1:1:1:1) were used. Comparison of experimental and simulated processes of recycling and distribution of the solutes in the closed-loop demonstrated a good agreement between theory and experiment.

Steady state preparative multiple dual mode counter-current chromatography: Productivity and selectivity. Theory and experimental verification.

In the steady state (SS) multiple dual mode (MDM) counter-current chromatography (CCC), at the beginning of the first step of every cycle the sample dissolved in one of the phases is continuously fed into a CCC device over a constant time, not exceeding the run time of the first step. After a certain number of cycles, the steady state regime is achieved, where concentrations vary over time during each cycle, however, the concentration profiles of solutes eluted with both phases remain constant in all subsequent cycles. The objective of this work was to develop analytical expressions to describe the SS MDM CCC separation processes, which can be helpful to simulate and design these processes and select a suitable compromise between the productivity and the selectivity in the preparative and production CCC separations. Experiments carried out using model mixtures of compounds from the GUESSmix with solvent system hexane/ethyl acetate/methanol/water demonstrated a reasonable agreement between the predictions of the theory and the experimental results.

Multiple dual mode counter-current chromatography with variable duration of alternating phase elution steps.

The multiple dual mode (MDM) counter-current chromatography separation processes consist of a succession of two isocratic counter-current steps and are characterized by the shuttle (forward and back) transport of the sample in chromatographic columns. In this paper, the improved MDM method based on variable duration of alternating phase elution steps has been developed and validated. The MDM separation processes with variable duration of phase elution steps are analyzed. Basing on the cell model, analytical solutions are developed for impulse and non-impulse sample loading at the beginning of the column. Using the analytical solutions, a calculation program is presented to facilitate the simulation of MDM with variable duration of phase elution steps, which can be used to select optimal process conditions for the separation of a given feed mixture. Two options of the MDM separation are analyzed: 1 - with one-step solute elution: the separation is conducted so, that the sample is transferred forward and back with upper and lower phases inside the column until the desired separation of the components is reached, and then each individual component elutes entirely within one step; 2 - with multi-step solute elution, when the fractions of individual components are collected in over several steps. It is demonstrated that proper selection of the duration of individual cycles (phase flow times) can greatly increase the separation efficiency of CCC columns. Experiments were carried out using model mixtures of compounds from the GUESSmix with solvent systems hexane/ethyl acetate/methanol/water. The experimental results are compared to the predictions of the theory. A good agreement between theory and experiment has been demonstrated.

Steady-state and non-steady state operation of counter-current chromatography devices.

Different variants of separation processes based on steady-state (continuous sample loading) and non-steady state (batch) operating modes of CCC columns have been analyzed and compared. The analysis is carried out on the basis of the modified equilibrium cell model, which takes into account both mechanisms of band broadening - interphase mass transfer and axial mixing. A full theoretical treatment of the intermittent counter-current chromatography with short sample loading time is performed. Analytical expressions are presented allowing the simulation of the intermittent counter-current chromatography separations for various experimental conditions. Chromatographic and extraction separations have been compared and advantages and disadvantages of the two methods have been evaluated. Further technical development of the CCC machines to implement counter-current extraction separations is considered.