1. Sustainable Castor Oil-based Production through Reactive Seed Crushing “in-planta” Catalysis for the production of methyl ricinoleate Introduction Castor oil has a worldwide demand that is rising 3 to 5% per annum. The major castor oil producer is India with 1.6 MT followed by China (170KT) and Mozambique (62KT) (FAOstat,2012). Over 100.000 T are imported annually from India to the EU to be used in various industrial applications, such as coatings, lubricants, surfactants, paper and oleochemicals. However, the total global production of castor oil is relatively very low compared to other oil seeds, which shows the growth potential of castor oil. The world’s largest single use of castor oil in one product is in the manufacture of polyamide 11,which is commercially produced by ARKEMA (CastorOIl.in, 2010). The present work proposes the reactive crushing of especially conditioned castor seeds, in the presence of a light alcohol and a basic catalyst, aiming at achieving in a single step both the seed crushing and the transesterification of triglycerides present in the castor oil for the production of an oil cake, glycerol and fatty acid esters, in particular ricinoleic acid. Futhermore, process alternatives are proposed, which include reactive extraction and detoxification of the oil cake for the production of a higher value castor meal suitable for animal feed. Countries Tons /2012 India 1 630 000 China,mainland 170 000 Mozambique 62 000 Brazil 25 989 Thailand 12 500 Paraguay 10 000 Ethiopia 7 000 South Africa 6 000 Vietnam 6 000 Pakistan 4 200 Angola 4 000 Ecuador 3 000 Kenya 3 000 United Republic of Tanzania 3 000 Madagaskar2 650 Castor oil seed production (FAOstat,2012 ) Castor oil trade: Exports from India & major applications Castor seeds Composition  Seeds are rich in Oil and Proteins: 40 to 60 % Oil, 15 to 20 % Proteins and contain a dangerous toxalbumine Ricine, and an allergen CB-1A  Oil contains mainly ricinoleic acid. Used in lubricants, raw materials for polymers (Rilsan) and source of undecylenic acid and sebacic acid Applications Polymers Polyurethane, PolyAmides, Polyesters 1st generation Biodiesel  acceptable only if diluted in other vegetable oil 2nd generation Biodiesel (full hydrogenation + isomerisation)  acceptable as such Other industrial applications Non-ricinoleic part to Fuel. 15 % of the Castor Oil ends up as Esterol A (methylester of non ricinoleic acid sold as a solvent) in Arkema’s process Castor oil composition Acid nameAverage percentage rate Ricinoleic85 to 95% Oleic6 to 2% Linoleic5 to 1% Linolenic1 to 0.5% Stearic1 to 0.5% Palmitic1 to 0.5% Dihydroxystearic0.5 to 0.3% Fatty acids0.5 to 0.2% Castor oil cake After the oil extraction, all toxic components concentrate into the cake making it inappropriate for use as animal feed. Castor oil historical prices Castor and Rapeseed meal Values in India (for export), US $/ton Arkema’s castor biorefinery Castor oil plants High value monomers C 10, C 11 Long chains Polyamides market Method for the reactive crushing of castor seeds Base case Castor seeds crushing Solvent Extraction Hexane cake Trans- Esterification Oil refining oil Castor Oil Castor Oil Methyl Esters New process Castor seeds Reactive crushing Separation Castor Oil Methyl Esters cake (detoxified) MeoH + NaOH Arkema patent : WO 2010/076527 Process steps Seeds processing (heating, flatenning, drying) with no necessary dehulling. Reaction of castor seeds with a light alcohol and a basic catalyst for the simultaneous extraction & transesterification of castor oil for the production of FAE, glycerol and an oil cake. (intermediate steps include: MeOH evaporation, Glycerine decantation, Methyl Ricinoleate purification) Detoxification of oil cake through heating or alternative treatment methods. Detoxified oil cake Less water intensive process Less number of stages: no refining, seed drying or pressing → less capital intensive process Glycerine Reactive crushing – Process Alternatives Castor seeds crushing Oil refining Oil Cake (fat) Reactive Extraction MeOH/NaOH Castor Oil Methyl Esters + cake (detoxified) + glycerol Castor seeds Reactive Extraction MeOH/Heptane/NaOH Methyl Ricinoleate >95% + “biodiesel” + cake (detoxified) + glycerol crushing Oil refining Oil Cake (fat) Castor seeds Reactive Extraction MeOH/Heptane/NaOH Separation Methyl Ricinoleate >95% + “biodiesel” + cake (detoxified)+ glycerol NaOH (g) Reaction time (min) Methyl ester yield (%) MeC18:1,OH (%) Test 11,16087,190,65 Test 20,76086,373,16 Test 30,356049,857,5 Test 41,16090,490,34 Test 51,13087,190,65 * Value above the saturation limit of the method ** + additional drying at 100°C, 4 h Arkema patent: WO 2012/160314 Process steps Reactive extraction of oil cake (3-30% oil) Improved stability & oxidation resistance of oil cake and FAE Possible mixed feedstock, i.e. oil seeds + oil cake for the reactive extraction Detoxified oil cake (<3% oil) Suggested use of a co-solvent, i.e. heptane, for optimal results Conclusions  Reduced CAPEX Smaller number of pieces of equipment  Reduced OPEX Lower maintenance, labor and processing costs  Reduced toxicity Lower traces of ricin and CB-1A in oil cake References: 1.CastorOil.in, Comprehensive Castor Oil Report- A comprehensive report on castor oil and castor oil derivatives, Nov. 2010 2.WO2010/076527, Jean-Luc DUBOIS, Julien MAGNE, Jacques BARBIER, Antoine PICCIRILLI 3.WO2012/160314, Jean-Luc DUBOIS, Antoine PICCIRILLI Jean-Luc COUTURIER, Jean-Luc DUBOIS, Mirela TSAGKARI/ ARKEMA France Aknowledgements: ADEME financial support RICHARB project Jacques BARBIER, Antoine PICCIRILLI, Julien MAGNE (Valagro) Effect of catalyst and reaction time Future perspectives  Integrated process design  Techno-economic evaluation to estimate project potential