Chromatographie à contre-courant simulé : développements et perspectives

From Batch Elution to Simulated Countercurrent Chromatography

Institut Français du Pétrole

Résumé

Les applications industrielles et le principe de fonctionnement du procédé de séparation en lit mobile ou en contre-courant simulé sont brièvement rappelés. La réalisation pratique de trois unités pilotes fonctionnant selon ce principe mais employant une technologie innovante est présentée. Cette mise en oeuvre particulière permet de tester par un simple changement de paramètres de contrôle toutes les configurations possibles de l'unité. Cet appareillage particulièrement souple est donc véritablement multitâche, ce qui permet en plus des applications en pétrochimie son emploi dans les domaines de la pharmacie, de la chimie fine et des bioséparations, où existe un grand nombre d'applications potentielles très différentes les unes des autres. Deux exemples de séparations réalisées à l'Institut Français du Pétrole sont succinctement présentés. La conclusion de ces essais est que la modélisation de ces procédés est indispensable pour pouvoir opérer correctement ce type d'unité. Une comparaison entre la chromatographie d'élution et cette technique de séparation ainsi que quelques propositions d'amélioration du procédé permettront au lecteur de se faire une idée sur l'extension potentielle de ce type de séparation.

Abstract

Distillation is and will for quite a long time remain the main separation technique in the refining, petrochemical and chemical industries. Some separations however cannot be performed by distillation when the products to be separated are subject to thermal degradation or when their boiling points are too close. Under these circumstances adsorption or chromatographic processes are interesting alternatives. In the 1960's and in the early 1970's the technology of the simulated moving bed, the UOP rotary valve and the application of these devices to separation processes were introduced by UOP. Nowadays simulated moving bedor countercurrentseparation processes may be found in the petrochemical industry where UOP still holds a quasi monopoly with the Molex process for n-isoparaffin separation and with the Parex process for paraxylene separation from C8 aromatic cuts. In the sugar industry competition is wide open. There are processes for glucose-fructose separation on the market (from Illinois Water Treatment, Mitsubishi Chemicals and UOP) while a xylose-arabinose-glucose separation and a sucrose extraction from molasses are available from Finnsugar. Within this context Institut Français du Pétrole and Separex have developed the LICOSEP technology and propose its adaptation to different separations in the fine chemicals, pharmacy, perfumes and related industries. The principle of the simulated moving bed separation may be understood through the real countercurrent of a solvent and a solid selective adsorbing phase. In the mixture to be separated some of the components are relatively adsorbed while the other ones are not. The operations consist in adjusting the different flowrates so that the adsorbed compounds will be entrained with the solid while the nonadsorbed compounds will travel along with the liquid solvent. Actually the circulation of a solid phase is technically difficult. This operation is simulated by permutations of injected and withdrawn streams through multiple ports located all along the separation column. The practical construction of three pilot plants working according to the simulated moving bed technique is shown. Twenty-four columns filled with a fixed phase are mounted in series. A metering pump is fitted between the 24th and the first column in order to create a recirculation stream. Between each two columns it is possible to inject the feed or the solvent stream or to withdraw either the extract or the raffinate stream. These four streams flow continuously and each of them is directed by a twenty-four position valve to the right intercolumn assembly depending on the period of the cycle. Solvent injection, feed injection and extract withdrawal are performed by metering pumps while the raffinate withdrawal is done by an upstream pressure-control valve. The four multiposition valves, the four metering pumps, the pressure control valve and various side devices such as online analyzers of the effluents are commanded by a computer. Two examples of separation performed in these pilot plants are shown: paraxylene separation from C8 aromatic feedstock and xylose separation from xylose-arabinose-glucose mixtures. The experiments performed made it possible to determine both static and dynamic parameters of the process. The main conclusion is that a modelization of the plant is necessary not only for process optimization but also to correctly operate these units. We have developed a model that accurately represents the separation of binary mixtures. Generally multicomponent separations are more difficult to represent and in this respect our model predictions are only qualitative ones. A guideline is then given for making choice between conventional elution chromatography and simulated moving bed separation. Some improvements in this process are also discussed. A five-zone simulated moving bed with reinjection of distilled extract provides great increases in extract purity. It is also possible to combine preparative supercritical chromatography with a simulated moving bed in a sixzone scheme in order to continuously separate three effluent streams. Thus great extensions of the field of application of simulated moving bed separations are expected in the coming years.