Ethylic biodiesel: the bottlenecks for process optimization Antonio J. A. Meirelles Laboratory of Extraction, Applied Thermodynamics and Equilibrium (EXTRAE) School of Food Engineering (FEA) University of Campinas (UNICAMP), São Paulo, Brazil Co-workers: E. Batista, F. Batista, C. Rodrigues, C. Gonçalves. L. Bessa, M. Ferreira, M. Cuevas, T. Deboni, T. Porcina, S. Shiozawa.
Topics • Sources of fatty compounds for biodiesel production. • Biodiesel nowadays: methanol vs. ethanol. • An ethylic route for biodiesel production: extraction, refining, trans/esterification, purification and ethanol recovery.
Biodiesel in the World Million m3 USAGermany BrazilArgentina Vegetable Oils in the World, Million metric tons, 14/15 (USDA, 2015) Brazil: 4th Soybean Oil, <<< 5thPalm Oil, 3rd in Biodiesel, 2nd in Bioethanol.
A controversial subject Agro-ecological zoning by EMBRAPA on the deforested area of Amazon (2007=13.94% of the Legal Amazon region): 29.7 million ha appropriate for agricultural cultivation of oil palm (5,87% of the Legal Amazon region). (Embrapa, 2010) The area investigated by EMBRAPA is composed of 80% of degraded and abandoned pastures. Cultivation expansion restricted to the already deforested region according to the images collected before 2008. 2007: 10.92 million ha used worldwide for oil palm cultivation (C. Carter et al. Eur. J. Lipid Sci. Technol. 109 (2007) 307–314). Malaysia + Indonesia= (4+5) million ha cultivation of Palm (Homma, 2011). Indonesia: deforestation related to the expansion of oil palm cultivation (Becker, CONFINS, 2010).
Agribusiness based on Palm Oil/Palm Biodiesel is similar to that based on Sugar/Bioethanol • Oil palm trees/Palm oil: high productivity per hectare. • Palm Oil/Palm Biodiesel Agribusiness uses cogeneration based on palm tree residues. The ratio bioenergy generated/fossil energy used Sugar Cane Bioethanol (World Watch Institute). • EMBRAPA: new varieties adapted to Brazilian savannah (irrigation) and richer in unsaturated fatty acids(Embrapa, 13/10/2010, 23/05/2011). • Researches on Hydrolysis of lignocellulosic residues from palm tree (empty fruit bunches and palm press fiber): coupling production of palm oil biodiesel and bioethanol (Gutiérrez et al., Bioresource Technology, 2009).
“fatty acid methyl esters .. .are still among the most prominent alternative biofuels, and there are still a lot of challenges …including the use of ethanol instead of methanol” (M. Mittelbach, Editorial, Eur. J. Lipid Sci. Technol. 2009, 111, 745–746). Distillery (CD2) X Sugar + Bioethanol (JP2) FAEE X FAME GHG gains GHG Emission How to develop a feasible route for ETHYLIC BIODIESEL? Our Approach: i) bioethanol can be used in the entire sequence of biodiesel production, from the seed (oil extraction) to the tank; ii) the main bottleneck is concentrated in the purification steps and recovery, in a anhydrous form, of bioethanol used in excess.
Oil Extraction with Ethanol Replacing hexane as solvent: extraction of oils for Biodiesel and for edible purposes. Recovering Nutraceuticals of high added value (oryzanol, tocopherols, phytosterols, etc.) as byproducts or concentrated in the edible oil. Future of the oil industry biofuels + food + feed + high added value products. Extraction Yield (%) Soybean Oil Temperature (°C) Nitrogen Solubility Index (%) FoodResearchInternational 62 (2014) 662-670
Oil Deacidification By LLE with Ethanol By Ion Exchange ▲Rice Bran Oil ■Free Fatty Acids Breakthrough Curves ○Soybean Oil ■Free Fatty Acids
Solubility of anhydrous ethanol in palm oil at 45 oC 25 mass% 86 mol% Ethanol/oil mol ratio = 6.14
Close to Ethanol boiling point, Vegetable Oils highly soluble in Bioethanol. Strong acid used in Ion Exchange regeneration can be also used as the Esterification Catalyst.
Process Simulation and Catalysis Process development based on experimental studies and computer simulation (Aspen Plus) Simulation requires suitable methods for the calculation and prediction of properties, especially phase equilibrium and reaction kinetics.
Biodiesel reaction is a Two-Phase reversible reaction How the presence of two phases affects the reaction velocity? POSSIBLE MASS TRANSFER INFLUENCE Conversion (%) Palm Oil Conversion to Biodiesel (▲) 308 K; (●) 323K; (■) 338 K. Reaction Kinetics at 338,15 K Concentration (mole/L) Time (min) ♦, TAG; ■, DAG; ▲, MAG ×, Biodiesel; ○, Glycerol Time (min)
LLE for Oil-FFA-Solvent: UNIFAC Parameters readjustment Databank with 102 commercial fatty systems 360 (2013) 379– 391
LLE for TAG_Corn+DAG+MAG+Ethyllinoleate+Ethanolat 303.15 K:●, experimental; ─ NRTL; ∙∙∙∙∙∙ UNIFAC_LLE; --- ,UNIFAC_Readjust. LLE for HOSO+DAG+MAG+ethyloleate+oleicacid+ethanol at T = 303.15 K: ●, experimental; - - - -, UNIFAC-LLE; ∙∙∙∙∙∙, UNIFAC-Readjust. JCT, 89 (2015), 148-158 FluidPhaseEquilibria, 404 (2015), 32-41
Biodiesel Purification + Ethanol Recovery Purification of Ethylic Biodiesel Phase splitting and decanting: (biodiesel rich + glycerol rich) phases. Ethanol evaporation, dehydration and recycling. Biodiesel washing and drying. Main Problem: Ethanol Recycling Anhydrous bioethanol contains 0.5 m% Water. Without dehydration bioethanol recycle accumulates water. Ethanol Dehydration 3 Industrial Techniques: Extractive Distillation with EG, Azeotropic Distillation with CH, Molecular Sieve. Not the best solution: expensive in comparison to Methanol dehydration (no Azeotropy)
Ethanol Dehydration with Ethylene GlycolAlmost 1/3 of the Brazilian Production Industrial Installations for 300 to 1.000 m3/day Water Anhydrous Bioethanol Hydrated Bioethanol
Ethanol Dehydration GLYCEROL´s EFFECT on Ethanol + Water VLE similar to the observed for Ethylene Glycol
Process for ethylic biodiesel Byproduct GLYCEROL used for dehydrating Bioethanol to be recycled; Ethanol as new reactant can be fed to the process as hydrous ethanol and be dehydrated also using glycerol. Glycerol recycles around 10 times in the installation, being withdrawn before harmful effects can occur. Two Brazilian patents (INPI) for deacidifyingvegetable oils and for producing biodiesel.
Aspen Simulation Concentration/ mole/L ■Biodiesel Ethanol Oleic/Linoleic Acids 60 oC E/A=15:1 Concentration/ mole/L Biodiesel Ethanol Glycerol TAG DAG MAG 60 oC E/O=6:1 ■Kg Steam/L Biodiesel Oil Conversion/ % Time/ h Time/ h Molar Ratio Ethanol/Oil Biodiesel Loss, % Molar Ratio Ethanol/Oil
CONCLUSION Possibilities to integrate the production of biofuels and edible oils have been researched and developed in the case of ethylic biodiesel. Thank you for your attention Acknowledgments: