SOLVENT-FREE REFINING WITH MEMBRANE Cirad Univ.. Marrakech

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1 SOLVENT-FREE REFINING WITH MEMBRANE Cirad Univ.. Marrakech Standard chemical refining Crude oil MF based refining Neutralisation Neutralisation Centrifugation Water washing Soapstock MF Separation Centrifugation Water washing Effluent-Pond 2 steps only Centrifugation Drying Bleaching Deodorise Refined oil

2 COMPARED RESULTS OF MF BASED REFINING EITHER OF HEXANE MISCELLA or SOLVENT-FREE P Acidity Washing Security (ppm) (%) MF / miscella (soy) Hexane Owensboro Grain 5 0,2 Efficient Explosion proof unit MF / huile ( tournesol) Cirad < 1 0,01 Solvent-free No aqueous effluent Efficient Both sets of results are ok : oil quality; phospholipid production (Lecithin) - partial bleaching occurs & deodorization goes faster in both cases Choice : Security? Greener process?

3 Opportunities for Applying Membrane Technology to Processing of Fats and Oils I CHEMICAL COMPOSITION OF OILS CURRENT INDUSTRIAL REFINING II ALTRERNATIVE TECHNOLOGIES / MEMBRANES III MOLECULAR AND PHYSICO-CHIMICAL FEATURES IV PROSPECTS Crosflow Clusters Triglycerides

4 Glycerides medium Caracterization of colloidal suspensions Influence of oil conditioning / quality of partially refined oil flow rate of permeate membrane fouling «cake» property (permeability) Filtration media (membrane) Surface properties Modification of surface Oil - Membrane molecular interactions Fouling phenomena involved Chemical species involved

5 LACK OF BIBLIO. DATA ABOUT AGREGATION OF LIPIDS Water base media are well known PL, soap : polymorphism, cubic, hexagonal ; bilayer (+ sterols) Extensive research work / liposomes, cosmetic, cell walls ; medical Reverse media much less investigated Case of organic solvent : CMC of PL ~1-60mM/ L PL always associated to water up to 40 water mol / PL mol Case of triglycerides : CMC of lecithins ~10 1 mmole/kg (~10 ppm of P ) P inositol, P choline : hydratable ( degumming possible with water) PE, PA associated to Ca Mg : H2SO4 needed to free divalent cations FWe needed further investigations to get a physico chemical understanding of phenomena governing the filtration

6 STRUCTURE OF COLLOIDS IN CRUDE OILS? FREEZE - FRACTURE TRANSMISSION ELECTRON MICROSCOPY (Cirad results) Oil + PL Oil + Soaps Oil + PL Oil + PL + soaps + Soaps + hexane Particle size (µm)( < 0.01 Filtration process U.F. U.F. M.F. NF Anionic surfactant required to get PL in big stacks Best case : Glycerides + Phospholipids + Soaps Hexane not useful for large agregates Water : a critical parameter

7 INFLUENCE OF OIL CONDITIONNING (Neutralization step) ( 0.3% H3PO4, NaOH / H2O 20% ) On agregate size PL + savons (measuring particle size) On interlamellar distance (between two layers of PL and soaps) NaOH (Soja) 10% 20% 40% d ( A ) On mechanical resistance to constraints (pumping, filtration) NaOH conc. 20% : no effect of pumping 40% : size reduced after pumping of the crude oil

8 WETTING Contact angle solvents / membranes pre-coated with lipids Membrane type 0.2 µm, Hydrophilic Conditioning phase Wetting by Hexane (Contact angle) Trioleine Na Oleate Oleic acid Ideal Wetting θ = 0 Surface wetting by hexane is highly dependent of the type of lipid used to pre-coat the membrane

9 OIL - MEMBRANRE INTERACTIONS FT-IR spectra, diffuse reflexion Alumina membrane + Oleic acid Soaps & PL adsorb preferentially Crosflow Crude oil Clusters Membrane Refined oil Triglycerides Oil conditionning (neutralization) acts on : Specific resistance of cake built found to vary m Kg -1 Oil flow Throug High cake compressibility membrane

10 70 CONCLUSION / OUR RESULTS Physicochemical phenomena determine MF results of these complexe reverse media Flux (l/h.m ²) colza soja tournesol Temps (min) Partial optimisation of filtration parameters : Filtration pilote 100kg / sunflower, soy, rape : flow rate stable over 40hr (30-60 L/h.m² of refined oil) Oil quality after at end of trial still meets standard No water used during he process, no effluent to be cleaned before rejecting, 5 process steps saved

11 VARIOUS POTENTIAL INDUSTRIAL APPLICATIONS OF MEMBRANES TO VEG. OIL PROCESSING Application Company Country Miscella Dewaxing Asahai Chem Co 1998 Japan hexane / oil Degum + Neutra. Pilote plant De Smet-Ballestra 2006 Italy Oil alone Fractionnement MGLA 2000 France (solvent free) By-products Deoliling of Lecithins ADM «Ultralec» 1998 USA Intrants Gaz production N2 Cleaning of process water : heaters, cooling towers

12 OTHER APPLICATION OPPORTUNITIES : INDUSTRIAL PROCESSING OF OIL SEEDS PRODUCTS, BY-PRODUCTS, EFFLUENTS EXTRACTION Crushing BY-PRODUCTS REFINING FRACTIONNATION EFFLUENTS HYDROGENATION FRYING RECYCLING Water, oils OLEOCHEMISTRY Functionalisation BIO-DIESEL

13 PROSPECT Positive factors Fast developpement of oleaginous crops (demography, biofuels, green chemistry) Energie saving, protection of environment (clean processing) Negative factors Low financial gain : does not play in favor of innovation Scientific points to be improved : chemical resistence of membranes -> ceramic understanding physico-chem / molecular interactions lipids-membrane wall improving membrane surface properties Cooperation : Process specialist + physico-chimists research + industry

14 AKNOWLEDGEMENTS Cirad Montpellier, J. Graille, C. Larguèze, D. Pioch, P. Guiffrey Univ. Marrakech, H. Ajana, A. Hafidi, Food Science Laboratory Univ. Montpellier 2, J. Rouvière, F. Guizard, Europ. Institute of Membranes E. Anglaret Group Phase Condensée CNRS Gif / Yvette, T. Gulick, Laboratoire de Génétique Moléculaire French Ministry of Research / Aliment 2000 and Aliment Demain Funds ADEME and Région Languedoc Rousillon Cereol Refinery in Sete provided the oil samples Cirad PhD grant for C. Larguèze & A. Hafidi

15 BIBLIO. REF OF THE TEAM Hafidi, D. Pioch, and H. Ajana, Membrane-based simultaneous degumming and deacidification of vegetable oils, Innovative food science & Emerging technology. In press. Hafidi, D. Pioch, and H. Ajana, Soft purification of lampante olive oil by microfiltration, Food Chem. In press. Hafidi, M-L. Teyssier, D. Pioch, and H. Ajana, (2004). Influence of oil conditioning on the permeate flux and cake properties during microfiltration of lampante olive oil, Eur. J. Lipid Sci. Technol., 106, Hafidi A., Anglaret E., Pioch D. and Ajana H., Characterisation of vegetable oils-alumina membranes intreractions by diffude reflectance Fourier transform infrared soectroscopy European Journal of Lipid Science and Technology, 106, (2004). Hafidi A., Pioch D. and Ajana H., Adsorptive fouling of inorganic membranes during vegetable oil microfiltration European Journal of Lipid Science and Technology, 105, (2003) PIOCH D., LARGUEZE C., GRAILLE J., AJANA H., ROUVIERE J., 1998 Towards an efficient membrane based vegetable oils refining process Industrial Crops and Products, 7, PIOCH D., LARGUEZE C., Les techniques membranaires en lipotechnie. Oléagineux, Corps Gras, Lipides, 5, H. AJANA, D. PIOCH, J. GRAILLE Raffinage d'huiles végétales ou animales par filtration. French patent appication ne , 16 mars 1993, CIRAD.