Phase Equilibrium and Purification Processes in the Production of Biofuels and Biocompounds Research Team: Antonio J. A. Meirelles Lab. EXTRAE - FEA/UNICAMP Pedro A. Pessoa Fo. EPUSP/USP Martín Aznar, M. Alvina Krahenbühl, Roberta Ceriani FEQ/UNICAMP Mariana Conceição da Costa FCA/UNICAMP Christianne E. C. Rodrigues, Cintia B. Gonçalves FZEA/USP Eduardo A. C. Batista - FEA/UNICAMP 37 Graduate Students + 2 Postdoctorates (Simone, Magno, Inês, etc.) National Collaboration: Luiza Silva UFPA, Érika Cren UFMG, Charles Abreu UFRJ, Lúcio Cardozo Fo. UEM, Elias Monteiro Fo. UFSJ, Adenilson UFMA, International Collaboration: Christian Stevens, Roland Verhé Ghent University, Belgium; Jérôme Pauly University of Pau, France; João Coutinho Aveiro University, Portugal; Rafiqul Gani, Technical University Denmark. Industrial Collaboration: Santa Adélia Mill, Müller Beverage Company, Desmet Ballestra (Belgium).
PROJECT GOALS 1.Simulation and Optimization of Bioethanol Industrial Distillation. 2.Development of Biodiesel Production by the Ethylic Route 3.Purification and Formulation of Biocompounds.
Industrial Distillation of Bioethanol Bioethanol Distillation 1. Topic frequently investigated in the literature 2. Most works focused on Bioethanol Dehydration (last step of the concentration process) 3. Oversimplified versions of the process: wine assumed to be a binary mixture Ethanol + Water; Distillation Equipment as a simple Binary Distillation Column. 4. Minor components are neglected and their role in the distillation of Special Alcoholic Products not considered Alcoholic products Fuel ( Hydrous/ Anhydrous ) Special/ Neutral Specifications alcoholic content, ph, acidity, conductivity, density, chloride, sulfate, iron, hydrocarbons alcoholic content, ph, acidity, conductivity, density, chloride, sulfate, iron, hydrocarbons, sulfur, copper, sodium, nitrogen, phosphorus, acetaldehyde, ethyl acetate, methanol, propanol, isopropanol, butanol, isobutanol, isoamilic alcohol, higher alcohols, crotonaldehyde, dioxane, ciclohexane, benzene, ethylene glycol, diethylene glycol, acetal Standards fixed by ANP Market
Investigating Bioethanol Distillation in Industrial Scale 1. Samples and Information collected in different sugar mills 2. Simulation of the real industrial equipment using ASPEN PLUS 3. Most important minor components taken into account Wine Composition 20 Components
Validation Results Evaluating Performance of Different Industrial Configurations Purification Factor F Total w w w w eth cont eth cont product wine
Heat Integrated Distillation Columns
ALCOHOL-CHEMISTRY requires PURE BIOETHANOL for avoiding damage to catalyst by minor components; secondary reactions; accumulation of minor components and final product contamination. Developing New Configurations for Distilling Neutral Alcohol Patent submission to INPI Conventional New Plant 1 New Plant 2 Steam Consumption (SC) (Kg/L) 5.22 3.31 5.22 Number of Trays (NT) 279 144 144 Decrease of SC 36 % 0 % Decrease of NT 48 % 48 % Purification Factor (F Total ) 8250 1092 8804
Developing an ethylic route for biodiesel production biodiesel are still among the most prominent alternative biofuels, and there are still a lot of challenges in the future for research including the use of ethanol instead of methanol (M. Mittelbach, Eur. J. Lipid Sci. Technol. 2009, 111, 745 746) Concept: bioethanol used in the entire sequence of biodiesel production, from the seed (extraction) to the tank. Problem: Bioethanol accumulates water during biodiesel production, it must be dehydrated before recycling. 2 Patents submitted to INPI.
Oil Extraction with Ethanol 1. Replacing Hexane as solvent used in the extraction of vegetable oils. 2. Combining the extraction of oils for producing Biodiesel and for edible use. 3. Recovering Nutraceuticals of high added value (oryzanol, tocopherols, tocotrienols, phytosterols, etc.) as byproducts or concentrated in the edible oil. 4. The future of the oil industry producing biofuels + food + feed + high added value products.
1. Close to Ethanol boiling point, Vegetable Oils highly soluble in Bioethanol. 2. Strong acid used in Ion Exchange regeneration can be also used as the Esterification Catalyst.
Oil Refining and biodiesel purification Conc TIME /Conc INITIAL 1.2 1.0 0.8 0.6 0.4 0.2 0.0 Soybean Oil FFA 0 200 400 600 time (min) Crude Oil must be deacidified for biodiesel production and for edible use. Deacidification by Ion Exchange of Crude Oil dissolved in Ethanolic Solutions. Initial Acidity (FFA)=2.12% Final Acidity=0.23% Purification of ethylic Biodiesel 1.Phase splitting and decanting: (biodiesel rich + glycerol rich) phases. 2.Ethanol evaporation, dehydration and recycling. 3.Glycerol recovery, use as dehydrator and purification as byproduct. 4.Biodiesel washing and drying. 5.Ethanol as reactant can be fed to the process as hydrous ethanol and be dehydrated also using glycerol.
Alcoholic and Fatty Biocompounds 1. Purifying and Obtaining Derivatives of High Alcohols (Fusel Oil) by Computational Simulation Using ASPEN PLUS. 2. Refining of Edible Oils Containing high Levels of Nutraceuticals ( carotene degraded during refining of Palm Oil can supply the worldwide requirements of Vitamin A - Mayomol et al., JAOCS, 84, 587-596, 2007). 3. Physicochemical Properties and Solid-Liquid Transitions of Fatty Systems: Important Information for Formulating Biodiesel Mixtures, Cosmetics, Pharmaceutical Products and Food Additives. Solid-Liquid Transition and Cloud Point Data Flash Point Data of Biodiesel Mixtures
Human Resource Training and Scientific Production Type 2009/2010 2010/2011 2011/2012 Postdoc 2/0 a 3/2 2/2 Dissertations, Theses, etc. PhD 19/2 18/3 21/1 MSc 17/4 21/6 16/6 Scientific Initiation 12/5 12/8 7/3 Technical Training 2/1 2/0 3/2 Publications International Journals Papers in Scientific Meetings 17 16 23 1.259 Impact Factors (2012) 4.268 25 21 19 a x/y: x=total of students in activity, y=total of students that finish their work in the period.
Thank you for your attention Acknowledgments: