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Processes and Supercritical Fluids

Supercritical extraction

Supercritical fractionation

Particle generation, crystallization, encapsulation

Impregnation (polymeric matrices and implants, silicas, ...)

suite...

Processes and Supercritical Fluids Team
About

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, ...)

Team leader

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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

  • 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
  • 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-04294235⟩ 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-04294235⟩
    Journal: Journal of Supercritical Fluids
    Date de publication: 01-11-2023
    Auteurs:
    Digital object identifier (doi): http://dx.doi.org/10.1016/j.supflu.2023.106056
    Voir la publication sur Hal
  • 2023
    Victorine Warambourg, Adil Mouahid, Christelle Crampon, Anne Galinier, Magalie Claeys-Bruno, et al.. Supercritical CO2 sterilization under low temperature and pressure conditions. Journal of Supercritical Fluids, 2023, 203, pp.106084. ⟨10.1016/j.supflu.2023.106084⟩. ⟨hal-04233306⟩ Plus de détails...

    Supercritical CO2 sterilization under low temperature and pressure conditions

    Sterilization using supercritical carbon dioxide has been proven to be efficient for decades now. The aim of this work was to implement a process of sterilization adapted to thermosensitive polymeric materials and highlight the lowest conditions of pressure and temperature which would enable a bacterial reduction higher than 6-log. Inactivation experiments were performed on spores of Bacillus subtilis over a pressure range lying from 60 to 200 bar, and a temperature varying from 35° to 60°C, with and without additive. Preliminary experiments allowed us to determine a restricted experimental domain used for the design of the experiments, investigating the influence of pressure, temperature, process duration, and additive content on bacterial reduction. It was shown that sterilization conducted at 110 bar, 40 °C, for 20 min with 200 ppm of H2O2, leading to a bacterial reduction of 8.73-log, may be considered as optimal for IMD sterilization.
    Victorine Warambourg, Adil Mouahid, Christelle Crampon, Anne Galinier, Magalie Claeys-Bruno, et al.. Supercritical CO2 sterilization under low temperature and pressure conditions. Journal of Supercritical Fluids, 2023, 203, pp.106084. ⟨10.1016/j.supflu.2023.106084⟩. ⟨hal-04233306⟩
    Journal: Journal of Supercritical Fluids
    Date de publication: 01-01-2023
    Auteurs:
    Liste des documents:
    Digital object identifier (doi): http://dx.doi.org/10.1016/j.supflu.2023.106084
    Voir la publication sur Hal
  • 2023
    Adil Mouahid, Magalie Claeys-Bruno, Isabelle Bombarda, Sandrine Amat, Andrea Ciavarella, et al.. Valorization of handmade argan press cake by supercritical CO2 extraction. Food and Bioproducts Processing, 2023, 137, pp.168-176. ⟨10.1016/j.fbp.2022.11.011⟩. ⟨hal-03992094⟩ Plus de détails...

    Valorization of handmade argan press cake by supercritical CO2 extraction

    The capability of supercritical CO2 to extract edible oil from handmade Argan press cake was investigated. The aim is to enable Moroccan cooperatives to improve their economic situation by valuing the handmade argan press cake, which is nowadays considered as a waste, applying a clean extraction process. Extraction experiments were conducted at 300 and 400 bar, 333 K and 0.14 kg/h on dried biomass. The fatty acids and tocopherols compositions of the extracted oil were found similar to previous studies and correspond to a commercial edible oil. The air flow dried biomass exhibits a higher extraction yield compared to the freeze-dried biomass. A pressure of 300 bar seems to be suffcient to allow the extraction of oil with a satisfactory extraction kinetic.
    Adil Mouahid, Magalie Claeys-Bruno, Isabelle Bombarda, Sandrine Amat, Andrea Ciavarella, et al.. Valorization of handmade argan press cake by supercritical CO2 extraction. Food and Bioproducts Processing, 2023, 137, pp.168-176. ⟨10.1016/j.fbp.2022.11.011⟩. ⟨hal-03992094⟩
    Journal: Food and Bioproducts Processing
    Date de publication: 01-01-2023
    Auteurs:
    Liste des documents:
    Digital object identifier (doi): http://dx.doi.org/10.1016/j.fbp.2022.11.011
    Voir la publication sur Hal
  • 2023
    Mathieu Martino, Adil Mouahid, Michelle Sergent, Camille Desgrouas, Catherine Badens, et al.. Supercritical millifluidic process for siRNA encapsulation in nanoliposomes for potential Progeria treatment (ex-vivo assays). Journal of Drug Delivery Science and Technology, 2023, 87, ⟨10.1016/j.jddst.2023.104804⟩. ⟨hal-04254108⟩ Plus de détails...

    Supercritical millifluidic process for siRNA encapsulation in nanoliposomes for potential Progeria treatment (ex-vivo assays)

    A millifluidic process working in continuous mode for the preparation of nanoliposomes using supercritical CO2 has been developed. Nanoliposomes with an average diameter ranging between 123.9 ± 3.0 and 165.7 ± 1.6 nm depending on the operating conditions were obtained. The effects of pressure (90–150 bar), temperature (35–45 °C) and phospholipid mass ratio (0.1–1.9 wt%) in feed solution on liposome sizes were investigated. The concentration of phospholipids was found to be the most significant parameter for controlling the mean diameter of nanoliposomes while pressure and temperature had a minor influence on liposomes’ properties. The encapsulation of siRNAs targeting the LMNA gene by nanoliposomes obtained with the millifluidic process was achieved at optimized operating conditions (150 bar, 35 °C and a phospholipid mass ratio in the feed solution of 0.1 wt%). The resulting formulations were compared with commercial transfection agents in ex vivo assays. These assays showed a decrease in the expression of the encoded protein lamin A for the formulations obtained with the process developed in this work. Therefore, the use of siRNAs targeting LMNA, encapsulated by nanoliposomes represents a potential new therapeutic approach for the treatment of progeria.
    Mathieu Martino, Adil Mouahid, Michelle Sergent, Camille Desgrouas, Catherine Badens, et al.. Supercritical millifluidic process for siRNA encapsulation in nanoliposomes for potential Progeria treatment (ex-vivo assays). Journal of Drug Delivery Science and Technology, 2023, 87, ⟨10.1016/j.jddst.2023.104804⟩. ⟨hal-04254108⟩
    Journal: Journal of Drug Delivery Science and Technology
    Date de publication: 01-01-2023
    Auteurs:
    Liste des documents:
    Digital object identifier (doi): http://dx.doi.org/10.1016/j.jddst.2023.104804
    Voir la publication sur Hal
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Rencontres scientifiques

Actualités Archives récentes

Soutenances de thèses et HDR

Actualités
24 septembre 2024 - Supercritical technology applied to the development of innovative intravitreal sustained-release drug delivery systems / Matthieu Schneider PhD defense
Doctorant : Matthieu SCHNEIDER

Date : le 24 septembre à 9h00, amphithéâtre du CEREGE, technopole de l'Arbois

Abstract : Age-related macular degeneration (AMD), manifested by the appearance of a dark spot in the center of the vision, has become a significant public health issue, with the number of patients set to rise over the coming decades. Since 2006, the pharmaceutical industry has introduced therapies with monthly intravitreal injections of anti-VEGF (vascular endothelial growth factor) antibodies to mitigate its development. Designing an intravitreal implant with antibody release controlled over twelve weeks has been proposed to simplify therapy management. Antibodies are thermally, chemically, and biologically sensitive therapeutic proteins. This study demonstrates the potential of the Sequential Dispersion Particles from Gas Saturated Solution (SD-PGSS) process for encapsulating sensitive active ingredients. The SD-PGSS process enables work to be carried out at moderate temperatures (38 °C) and without solvent. The study focused on the optimization of operating conditions through the investigation of polyesters (Polycaprolactone PCL, poly(Lactide-co-Glycolide) PLGA, and a polyether (Poly(Ethylene Glycol) PEG) biocompatible in the presence of supercritical CO2. Two operating conditions were selected: 38 °C/25 MPa for PCL and the PCL/PLGA blend (1:1 w/w) and 45 °C/25 MPa for PCL alone and the PCL/PEG blend (1:1 w/w). The implementation of the SD-PGSS process resulted in a repeatable process with high yields (80 - 95%). The study of two model molecules, lutein, a small hydrophobic molecule of therapeutic interest studied in an oral administration context, and bovine serum albumin, a hydrophilic protein studied in an intravitreal release scenario, demonstrated the repeatability of the process, the homogeneity of the final product, and the possibility of modulating the release in vitro. The antibody study demonstrated low activity maintenance and prolonged release for up to 8 weeks, leading to a prototype with compatible dimensions for ophthalmic use.

Jury
Géraldine PIEL                         Rapporteuse / Professeure, Université de Liège, Belgique
Ernesto DI MAIO                      Rapporteur / Professeur, Université de Naples-Federico II, Italie
Martial SAUCEAU                    Examinateur / Maître-assistant, Ecole des Mines d’Albi-Carmaux
John CONRATH                       Président du jury / Professeur - Chirurgien, Clinique Monticelli 
Elisabeth BADENS                   Directrice de thèse / Professeure, Aix-Marseille Université 
Yasmine MASMOUDI               Co-directrice de thèse / Maître de conférences , Aix-Marseille Université
Frédéric MATONTI                   Membre invité / Professeur - Chirurgien , Clinique Monticelli
Céline OLMIERE                      Membre invitée / Directrice scientifique, Théa Open Innovation 
10 avril 2024 - Vers une meilleure valorisation de la biomasse de'Arthrospira platensis (Spirulina): Contribution à sa culture et bioraffinerie / Soutenance de thèse Alejandra Gutierrez Marquez
Doctorante : Alejandra GUTIERREZ MARQUEZ

Date et lieu : mercredi 10 avril 2024 à 14h ; Salle P2A BIAM, Bat. 1900 ; Cité des énergies ; CEA-Cadarache

Résumé : Utilisée en agroalimentaire, nutraceutique et cosmétique sous forme brute ou de produit raffiné, A. platensis suscite un intérêt croissant mais sa culture et son bioraffinage représentent un réel défi. Ce doctorat s’est attaché à proposer et tester des procédés durables pour améliorer ces deux aspects.
Ce travail contribue à évaluer le potentiel de réutilisation du CO₂ par A. platensis lors de sa culture et l'impact des photopériodes sur sa productivité en biomasse et pigments. L'assimilation du CO₂ est caractérisée via un modèle adossé à des mesures expérimentales. Dans les conditions de laboratoire testées, une photopériode de 24 heures augmente à la fois la productivité en biomasse de 74 % et la teneur en phycocyanine de 35 %.
Les extractions sous pression sont réalisées par des mélanges éthanol/eau (PLE) et CO₂ supercritique (scCO2). Les conditions optimales trouvées en PLE sont 60°C/100 % d'éthanol et 65 °C/90 % d'éthanol (v/v) à 103 bar, respectivement pour une biomasse avec et sans extraction préalable des phycobiliprotéines par macération. L'extraction par scCO2, dont la cinétique a été modélisée par les équations de Sovová, induit une perte de masse de 7,7 % à 60 °C et 300 bar.
Ce travail permet de proposer un schéma de bioraffinerie en trois étapes, commençant par une première extraction de la biomasse par macération aqueuse afin d’extraire les phycobiliprotéines. Une deuxième étape d’extraction avec une solution d’éthanol sous pression permet ensuite la séparation d’un mélange de pigments lipophiles et composés phénoliques antioxydants. Puis, après séchage, l’extraction de la fraction apolaire par scCO2 permet d’isoler une fraction huileuse riche en caroténoïdes et d’obtenir une biomasse résiduelle riche en protéines.

Mots clés : A. platensis, CO2-mitigation, pigments, valorisation, solvants verts

Jury :
Céline LAROCHE Université Clermont Auvergne / Rapporteur
Miguel HERRERO Institute of Food Science Research, CIAL (CSIC-UAM) / Rapporteur
Abril LANSOY CRES-TOTAL ENERGIES / Examinateur
Luc MARCHAL Université de Nantes  / Président du jury
Elisabeth BADENS Aix-Marseille Université / Directrice de thèse
Christelle CRAMPON Aix-Marseille Université / Co-directrice de thèse
Gatien FLEURY MAP, CEA / Co-encadrant