Current oilseeds biorefinery State of art

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1 sextractive Reactive Crushing Process (E-RCP) : a break- innovation in biorefineries of oleiferous fruits & seeds Extraction réactive de composants de graines oléagineuses et de fruits : valorisation de coproduits en chimie de spécialités Julien Magne(1, 2), Antoine Piccirilli (2), joel Barrault (1) et Jean-Luc Dubois (3) el) 1) Valagro carbone renouvelable, 2) Biosynthis, Dissay, 3) Arkema Coprinov, octobre 2016

2 Current oilseeds biorefinery State of art Storage & Shipment Oilseeds world market Crude seed oil Food Refined Seed oil Biodiesel glycerin oleochemicals Refining vitamin E phytosterols squalene beta-carotene Oil cake ( feed/food (for Molasses Lecithins Isoflavones Seeds crushing Fibers ( feed (for 2

3 What is reactive crushing process (RCP)? Oilseeds Mechanical extraction & solvent extraction Crude seed oil Rapeseed, soya, corn sunflower, avocado RCP Technology VALAGRO sinnovation LIMAGRAIN-VALAGRO WO Patent Chemical or physical refining Refined Seed Oil Methanolysis Ester ( biodiesel ) 3

4 Applications of the RCP Technology RCP Technology VALAGRO s innovation LIMAGRAIN-VALAGRO WO Patent Rapeseed Castor seed Avocado fruit Biodiesel methyl ricinoleate chemistry Avocadofuran extraction 4

5 ( France Pilot demo-plant (La Rochelle, T/y ethyl esters plant 100% biobased continuous process 5

6 ( demo-plant ) Continuous RCP RCP is validated for many oilseeds: rapeseed, sunflower, soya bean

7 Reactive Crushing Plant w detoxified seed meal RCP is validated for producting methyl ricinoleate and detoxified castor meal February 4th 2010 / Jean-Luc Dubois - CONFIDENTIAL Castor Oil Methyl Ester

8 Detoxification. Ricine and Allergen (CB-1A) Immunologic Assay + Mass spectrometry test done by CEA (Saclay) Seed/Seed meal Drying T C/(h) Solvent removal T C/(h) Final Drying (T C, h) Ricin (%) Active Ricine reduction (%) Defatted flakes (60 C, 10h) Batch process, agitated bed 100 C / 16h 120 C / 4h % Continuous fixed bed process 100 C / 16h 120 C / 4h % Continuous fixed bed process 100 C / 16h 120 C / 4h 100 C/4h % Seed/Seed meal Final Drying (T C, h) Acute toxicity on rats (DL50, mg/kg) Cutaneous sensitivity test (Local Lymph Node Assay) Defatted flakes (60 C, 10h) - 300< DL50 < 2000* (*mortality 100%) Allergenic at 10% Continuous fixed bed process 150 C, 4h > 2000 non allergenic at 10% Continuous fixed bed process 120 C, 4h > 2000 non allergenic at 10%

9 List of patents developed with ARKEMA FR Procédé de trituration réactive des graines de ricin FR Procédé de trituration réactive des graines de jatropha FR Procédé de trituration réactive directement sur un tourteau gras pargrasd acide Procédédepurificationd unesteralkylique FR extraction liquide / liquide

10 Communication in INFORM

11 Extractive RCP : a new concept of oilseeds biorefinery Patent WO 2011/ Valagro Sun Vitamin E E-RCP Green ethanol + ε NaOH in-situ transesterification ( FAEE ) Fatty Ethyl ester + native unsaponifiable phytosterols Tocopherols Squalene Sun Squalene Selective Unsap fractionation Native Unsaponifiable selective fractionation (biomass soft splitting) Sun Sterols Identity Preserved! Premium proteins ( oligopeptides (source of Premium cake Premium carbohydrates ( oligomers (source of sugars Premium FAEE ( distilled ) Premium Glycerin 11

12 Sunflower biorefinery : from the seed to fine phyto-actives Sun Vitamin E Sun Glycerin Sun Ethyl Linoleate Sun Squalene Sun Sterols ( proteins ) Sun Flour Sun Fibers ( scrub (exfoliating Sun Carbohydrates Sun Oligopeptide

13 Extractive RCP : a new concept of oleiferous fruits biorefinery Patent WO 2011/ Valagro Oilseeds & Oleiferous fruits Organic or conventional E-RCP Green ethanol + ε NaOH in-situ transesterification ( FAEE ) Fatty Ethyl ester + native unsaponifiable phytosterols Tocopherols Squalene Triterpenic alcohols phyto-actives Selective Unsap fractionation Native Unsaponifiable selective fractionation (biomass soft splitting) Phytochemicals Identity Preserved! Premium proteins ( oligopeptides (source of Premium cake Premium carbohydrates ( oligomers (source of sugars Premium FAEE ( distilled ) Premium Glycerin 13

14 Avocado biorefinery : from the fruit to fine phyto-actives Avocadofuran Avocado Glycerin Ethyl Avocadate Wasted and declassified fruits ( proteins ) Avocado flour Fibers ( C7 ) Perseitol ( scrub (exfoliating D-glicero-D-galaktoheptitol Oligopeptide

15 Extractive-RCP vs Sustainability & market expectations Sustainable criteria Environmental footprint Energy / atom economy Impact on biodiversity Impact on water ressource Land use conflict / food vs non food Sustainable identity preservation Safety Products naturability Profitability ans sustainbility Extractive-RCP 100% biobased raw materials & processing aids Co-products valorization / valorization : + 90% of fruit/seed Biogenic solvent recycling Very low wastes formation No adverse effects / high yield of valorization = energy and atom economy Ultra low use of water / water treatment unit is not needed Atom economy = high product yield /acre = land preservation Traceability (from the seed to the finished product) and identity prevervation (non GMO) can be guaranted Hexan free process / products free of contaminants or anti- ( cake ) nutritional products Very high Full-valorization of the fruit/seed improves drastically profitability allowing a better return to the farmers 15

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