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Procédés et Fluides Supercritiques

Extraction supercritique

Fractionnement supercritique

Génération de particules, cristallisation, encapsulation

Imprégnation (matrices et implants polymériques, silices, …)

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Processes and Supercritical Fluids Team
Présentation

Supercritical (FSC) or subcritical fluids have specific properties which are exploited in a large number of applications at both laboratory and industrial scales. Their use represents an alternative to the use of organic solvents presenting pollution, toxicity and/or safety problems.

The “Supercritical Processes & Fluids” team has particular scientific and technological expertise enabling the design, operation and optimization of processes using supercritical CO2.
For better control of these processes, a multi-scale approach is favored. The team particularly studies the properties of supercritical fluids, phase equilibria, interface phenomena and transfers in pressurized media. Particular attention is also paid to the behavior of materials, both of synthetic and biological origin, in contact with supercritical CO2.
Modeling tools developed within the team make it possible to understand more specifically the transfer kinetics (flows, dispersion phenomena, mixing) and the thermodynamics of these pressurized environments. 

The team has strong activity focused on the following applications:
- Supercritical extraction, supercritical fractionation and shaping of plant origin products
- Development of sustained drug delivery systems (crystallization of active ingredients, encapsulation, impregnation, etc.)
- Supercritical sterilization of medical devices and health products
- Supercritical decellularization of grafts

Industrial partners (period 2020-2024):

BiotechOne ; Cousin Surgery ; Lattice Medical ; French Red ; Solvay ; Symrise ; THEA ; Total Energies

+ Supercritical extraction
+ Supercritical fractionation
+ Particle generation, crystallization, encapsulation
+ Impregnation (polymeric matrices and implants, silicas, ...)

Responsable

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Annuaire personnel permanent

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Doctorants, Post-Doctorants et CDD

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Equipement

- Autoclaves d'extraction, de cristallisation et d'imprégnation - de quelques mL à plusieurs litres.
- Montage expérimental de cristallisation ou d'encapsulation en milieu supercritique.
- Pilote de fractionnement supercritique
- Autoclave à fenêtre
- Cellules Haute Pression de mesures d'équilibres de phases résistant jusqu'à 700 bar. 

Dernières publications de l'équipe

  • 2025
    Zohra Laggoune, Yasmine Masmoudi, Seyed Ali Sajadian, Elisabeth Badens. Sirolimus solubility in supercritical carbon dioxide: Measurement and modeling.. Journal of CO2 Utilization, 2025, 93, pp.103034. ⟨10.1016/j.jcou.2025.103034⟩. ⟨hal-04954883⟩ Plus de détails...

    Sirolimus solubility in supercritical carbon dioxide: Measurement and modeling.

    The solubility of drugs in supercritical carbon dioxide is a key parameter in their processing. This study focuses on sirolimus, an immunosuppressive drug used in organ transplantation. Its solubility in supercritical carbon dioxide was measured using a static gravimetric method. Measurements were carried out at pressures ranging from 12.5 MPa to 25.0 MPa and temperatures from 313 K to 328 K. The findings revealed a molar fraction range of sirolimus between 1.20 × 10 6 and 2.73 × 10 6 and a direct solubility behavior in the investigated domain. The experimental data were correlated using several models. These included semi-empirical density-based models (Chrastil, Mendez-Santiago and Teja, Bartle et al., Kumar and Johnston, Sparks et al., and Sodeifian et al.), as well as equation of state-based models (Soave-Redlich-Kwong and Peng-Robinson). The results indicated that Sparks et al. and Soave-Redlich-Kwong showed the lowest average absolute relative deviation (AARD%) and the corrected correlation coefficient (Radj) of 4.12 %, 0.978 and 05.18 %, 0.980 respectively.
    Zohra Laggoune, Yasmine Masmoudi, Seyed Ali Sajadian, Elisabeth Badens. Sirolimus solubility in supercritical carbon dioxide: Measurement and modeling.. Journal of CO2 Utilization, 2025, 93, pp.103034. ⟨10.1016/j.jcou.2025.103034⟩. ⟨hal-04954883⟩
    Journal: Journal of CO2 Utilization
    Date de publication: 01-03-2025
    Auteurs:
    Digital object identifier (doi): http://dx.doi.org/10.1016/j.jcou.2025.103034
    Voir la publication sur Hal
  • 2024
    Adil Mouahid, Magalie Claeys-Bruno, Sébastien Clercq. A New Methodology Based on Experimental Design and Sovová’s Broken and Intact Cells Model for the Prediction of Supercritical CO2 Extraction Kinetics. Processes, 2024, 12 (9), pp.1865. ⟨10.3390/pr12091865⟩. ⟨hal-04791947⟩ Plus de détails...

    A New Methodology Based on Experimental Design and Sovová’s Broken and Intact Cells Model for the Prediction of Supercritical CO2 Extraction Kinetics

    Nowadays, supercritical CO2 extraction is highly regarded in industry, and several studies dealing with scale-up calculations aim to facilitate the transition from small scale to large scale. To complete this transition, it would be interesting to be able to predict supercritical CO2 extraction kinetics, which is the aim of this work. A new methodology based on the association of Sovová’s broken and intact cell model and response surface methodology was developed to predict SC-CO2 extraction kinetics from different biomass (Argan kernels, evening primrose, Punica granatum, Camellia sinensis, and dry paprika) at different operating conditions (200–700 bar, 40–60 °C, 0.14–10 kg/h) inside an operating domain. The absolute average relative deviations between the experimental and predicted data ranged from 1.86 to 29.03%, showing satisfactory reliability of this new methodology.
    Adil Mouahid, Magalie Claeys-Bruno, Sébastien Clercq. A New Methodology Based on Experimental Design and Sovová’s Broken and Intact Cells Model for the Prediction of Supercritical CO2 Extraction Kinetics. Processes, 2024, 12 (9), pp.1865. ⟨10.3390/pr12091865⟩. ⟨hal-04791947⟩
    Journal: Processes
    Date de publication: 31-08-2024
    Auteurs:
    Digital object identifier (doi): http://dx.doi.org/10.3390/pr12091865
    Voir la publication sur Hal
  • 2024
    Aymeric Fabien, Guillaume Lefebvre, Elisabeth Badens, Brice Calvignac, Damien Chaudanson, et al.. Contact angle of ethanol, water, and their mixtures on stainless steel surfaces in dense carbon dioxide. Journal of Colloid and Interface Science, 2024, 655, pp.535-545. ⟨10.1016/j.jcis.2023.10.163⟩. ⟨hal-04316090⟩ Plus de détails...

    Contact angle of ethanol, water, and their mixtures on stainless steel surfaces in dense carbon dioxide

    Hypothesis Contact angle can be a key parameter in chemical engineering. However, the development and the optimization of numerous processes using supercritical CO2, considered as environmentally friendly, requires new measurements under dense CO2 atmosphere. Besides, the influence of the roughness or the wetting regime on the contact angle is known at ambient conditions but remains to be discussed for systems under high pressure. Experimental Contact angle measurements of ethanol, water, and their mixtures, with ethanol mass fractions ranging from 0.25 to 0.75, on two stainless steels in saturated CO2 at pressures ranging from 0.1 MPa to 15.1 MPa, and at 313 K and 333 K were carried out in a set-up improving mass transfer between the studied liquid and the continuous fluid phase. Stainless steel surfaces have been characterized by atomic force and scanning electron microscopies allowing the application of the Wenzel equation. Findings Ethanol wetted totally both stainless steels while contact angles of all other liquids were increased by the rise of pressure, with contact angles up to 128 ° for water at 15.1 MPa. Trapped bubbles were observed at the solid/liquid interface and the bubble formation is discussed. Furthermore, the potential influence of bubble presence on the wetting regime is prospected through the question: could the pressure rise modify the wetting regime?
    Aymeric Fabien, Guillaume Lefebvre, Elisabeth Badens, Brice Calvignac, Damien Chaudanson, et al.. Contact angle of ethanol, water, and their mixtures on stainless steel surfaces in dense carbon dioxide. Journal of Colloid and Interface Science, 2024, 655, pp.535-545. ⟨10.1016/j.jcis.2023.10.163⟩. ⟨hal-04316090⟩
    Journal: Journal of Colloid and Interface Science
    Date de publication: 01-02-2024
    Auteurs:
    Liste des documents:
    Digital object identifier (doi): http://dx.doi.org/10.1016/j.jcis.2023.10.163
    Voir la publication sur Hal
  • 2024
    Adil Mouahid, Catherine Rébufa, Yveline Le Dréau. Supercritical CO2 extraction of Walnut (Juglans regia L.) oil: Extraction kinetics and solubility determination. Journal of Supercritical Fluids, 2024, 211, pp.106313. ⟨10.1016/j.supflu.2024.106313⟩. ⟨hal-04587482⟩ Plus de détails...

    Supercritical CO2 extraction of Walnut (Juglans regia L.) oil: Extraction kinetics and solubility determination

    Experimental and modelling investigations of supercritical CO2 extraction of oil from Juglans regia L. kernels were conducted at 200 and 400 bar, 313 and 333 K at a CO2 flow rate of 0.1 kg/h. Regardless of the pressure and the temperature, the highest achievable yield was estimated at about 0.7 kgoil / kgbiomass. The extraction kinetics were modeled with Sovov´a’s broken and intact cells model. Walnut oil apparent solubility in supercritical CO2 was determined and modelled with the Chrastil equation. A retrograde solubility behaviour was observed at 200 bar, the faster extraction kinetics were found at 400 bar and 333 K. The fatty acid composition of the supercritical CO2 extracted oil was compared to the quality of the oil extracted by press and n-hexane Soxhlet extraction.
    Adil Mouahid, Catherine Rébufa, Yveline Le Dréau. Supercritical CO2 extraction of Walnut (Juglans regia L.) oil: Extraction kinetics and solubility determination. Journal of Supercritical Fluids, 2024, 211, pp.106313. ⟨10.1016/j.supflu.2024.106313⟩. ⟨hal-04587482⟩
    Journal: Journal of Supercritical Fluids
    Date de publication: 01-01-2024
    Auteurs:
    Liste des documents:
    Digital object identifier (doi): http://dx.doi.org/10.1016/j.supflu.2024.106313
    Voir la publication sur Hal
  • 2023
    Vénicia Numa, Christelle Crampon, Arnaud Bellon, Adil Mouahid, Elisabeth Badens. Valorization of food side streams by supercritical fluid extraction of compounds of interest from apple pomace. Journal of Supercritical Fluids, 2023, 202, pp.106056. ⟨10.1016/j.supflu.2023.106056⟩. ⟨hal-04543465⟩ Plus de détails...

    Valorization of food side streams by supercritical fluid extraction of compounds of interest from apple pomace

    Supercritical CO2 (scCO2) extraction, a green technology still little applied to side streams, has been used to explore the potential recovery of beneficial compounds from apple pomace, a food industry byproduct. The study examines the potential of scCO2 extraction on freeze-dried and airflow dried apple pomace, using laboratory-scale equipment with varying pressures (200–400 bar), temperatures (35–55 °C) with a fixed CO2 flow rate. Extracts were analyzed through LC-MS and GC-MS, while antioxidant capacity was assessed using the ABTS assay. The results were compared to those from Soxhlet n-hexane extraction. Optimal conditions of 300 bar and 55 °C with freeze-dried apple pomace yielded the highest mass loss. The main compounds identified included glyceryl dilinoleate, linoleic acid, and diacyl glycerol, with significant ursolic acid content. A preliminary higher scale feasibility test under optimal conditions demonstrated promising, duplicable outcomes, supporting prior claim that apple pomace contains valuable ingredients that can be reused in various industrial sectors.
    Vénicia Numa, Christelle Crampon, Arnaud Bellon, Adil Mouahid, Elisabeth Badens. Valorization of food side streams by supercritical fluid extraction of compounds of interest from apple pomace. Journal of Supercritical Fluids, 2023, 202, pp.106056. ⟨10.1016/j.supflu.2023.106056⟩. ⟨hal-04543465⟩
    Journal: Journal of Supercritical Fluids
    Date de publication: 01-11-2023
    Auteurs:
    Liste des documents:
    Digital object identifier (doi): http://dx.doi.org/10.1016/j.supflu.2023.106056
    Voir la publication sur Hal
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Rencontres scientifiques

Archives récentes Archives

Soutenances de thèses et HDR

Actualités Archives récentes
18 juillet 2025 - La modélisation et la simulation, des outils essentiels pour une meilleure compréhension des procédés en CO2 supercritique et une mise à l’échelle industrielle plus efficace / Soutenance HDR Adil Mouahid
Date et lieu : le 18 juillet à 10h ; amphi du Cerege (Europôle de l'Arbois).

Résumé : Dans un contexte réglementaire écologique évolutif incitant à la mise en place de procédés propres et innovants, les procédés mettant en jeu le CO2 supercritique (CO2-SC) font l’objet d’un intérêt grandissant. En effet, les avantages sont nombreux : le CO2 est un sous-produit de l’industrie, non inflammable, il est recyclé au cours du procédé, dans sa phase supercritique, c’est un solvant apolaire à géométrie variable (sélectif selon les conditions de pression et température) et reconnu comme atoxique. Le CO2 étant gazeux à pression ambiante, une séparation naturelle s’opère sans avoir recours à des opérations de séparation additionnelles. Enfin, la technologie supercritique est compacte lui donnant un avantage en termes de coûts de production.

Dans le but d’envisager une transition efficace et rentable vers cette technologie, les procédés utilisant le CO2-SC doivent être maîtrisés. Aboutir à cette maitrise nécessite de passer par une étape l’approfondissement des connaissances théoriques via la modélisation qui elle-même nécessite de passer par des étapes d’expérimentations. En effet, les données expérimentales permettent d’alimenter les modèles qui eux-mêmes donnent accès à des paramètres physiques tels que les solubilités, les coefficients de transfert, etc. utiles à des calculs de scale-up précis.

Dans la littérature, les données expérimentales sont nombreuses. Cependant, les données de modélisation sont moindres et le choix des modèles n’est pas toujours le même d’une étude à une autre rendant leur exploitation difficile. Ce travail présente donc mes travaux de recherche mêlant expérimentation et modélisation réalisés dans l’objectif d’approfondir les connaissances théoriques des procédés utilisant le CO2-SC mais également de faciliter les études de scale-up afin d’envisager une transition technologique efficace. Mes travaux de recherche ont été réalisés dans l’équipe Procédés et Fluides Supercritiques (FSC) animée par Elisabeth BADENS du laboratoire M2P2 (UMR7340, Aix-Marseille Université) à travers des collaborations académiques et industrielles qui ont nécessité le développement de nouveaux bancs expérimentaux et d’approfondir les aspects de modélisation et simulation soit en utilisant des considérations théoriques (jeux d’équations basés sur des théories de transfert de matière ou autre) soit en utilisant les plans d’expériences.

Membres du Jury
Severine CAMY Pr, LGC, Université de Toulouse
Maryline VIAN Pr, GREEN, Université d’Avignon
Caroline WEST Pr, ICOA, Université d’Orléans
Christophe JOUSSOT-DUBIEN, Directeur (HDR) CEA ISEC Marcoule
Elisabeth BADENS Pr, M2P2
25 novembre 2024 - Design and optimization of supercritical treatment processes for interventional cardiology medical devices / Zohra Laggoune PhD Defense
Doctorante : Zohra Laggoune

Date : 25 novembre à 14h00, Cerege amphi Technopôle de l'Arbois-Méditerranée

Abstract: Atherosclerosis, a leading cardiovascular condition, involves arterial narrowing due to fatty deposits, impeding blood flow. Angioplasty, using stents or balloons, is a minimally invasive treatment for atherosclerosis. Recent advances have led to the development of active stents and balloons, which release antiproliferative agents (e.g., sirolimus) via a polymeric coating to prevent restenosis and promote arterial healing. Conventionally, these devices are manufactured using organic solvents, and may then contain harmful residues posing environmental and health concerns.
This thesis, conducted in collaboration with AlchiMedics, investigates supercritical CO2 technology as an eco-friendly alternative for manufacturing active coronary medical devices. The study first focuses on the behavior of the polymers that compose them in a supercritical CO2 environment. A Fourier Transformed InfraRed microscope coupled with a high-pressure cell was used to measure CO2 sorption in the polymers and their swelling. Additionally, a high-pressure visualization cell was used to assess the physical state of the polymers when exposed to supercritical CO2. Furthermore, the solubility in supercritical CO2 of sirolimus, the main active ingredient involved in this thesis, was determined using a static gravimetric method, followed by data modeling.
Based on this fundamental knowledge, supercritical CO2 was applied to extract residual solvent from pre-dried active stents (HT Supreme®). Semi-continuous mode extraction at 8 MPa, 308.15 K for 0.5 h resulted in an extraction efficiency of 91.80 % while minimizing polymer detachment and ensuring satisfactory in-vitro sirolimus release.
This study also explores supercritical impregnation of sirolimus to develop active balloons and stents, targeting a drug loading of 1.2 µg.mm-2 for both devices. Balloon impregnation was performed in batch mode based on a Design of Experiments. Operating conditions of 18 MPa, 323.15 K for a duration of 18 h were identified to maximize the drug loading to 0.68 µg.mm-2, while achieving positive ex-vivo results. In contrast, impregnations of two types of commercial stents (AMS® and HT Supreme®) resulted in low drug loadings and detachment of polymeric coatings. The development of the Fast Impregnation process (FIP), significantly improved drug loadings from 0.035 to 1.11 µg.mm-2 for AMS®, and from 0.015 to 7.3 µg.mm-2 for HT Supreme®. This process also preserved the integrity of polymer coatings under conditions set at 12.5 MPa and 308.15 K for AMS®, and at 25 MPa and 313.15 K for HT Supreme®.

Keywords: Atherosclerosis, active coronary stent, active coronary balloon, polymers, supercritical CO2, impregnation, extraction, sterilization

Jury :
Pr. Albertina CABAÑAS - Complutense University of Madrid - Reviewer
Pr. Iolanda DE MARCO - University of Salerno -  Reviewer
Dr. Thierry TASSAING - University of Bordeaux- Examiner and president of the jury
Pr. Loïc MACÉ - Aix Marseille University - Examiner
Pr. Elisabeth BADENS -  Aix Marseille University - Thesis director 
Dr. Yasmine MASMOUDI - Aix Marseille University - Thesis co-director
Dr. Christophe BUREAU - AlchiMedics - Thesis co-director and guest member