-10 -8 -6 -4 -2 0 2 4 6 8 Temperature [°C] Camelina Sunflower 50% EtOH:CAM/50%EtOH:SUN Background Experimental System Analysis and Future Work Project Goals Find conversion data for 2 oils, 4 alcohols, 2 temperatures and 2 molar ratios Compare produced biodiesel to commercial petro-diesel Create a reaction kinetic model representing the oil and alcohol interaction Bio-Diesel Production Traditional 2 Batch process involving a acid or base catalyst Requires extensive pre and post process purification involving catalyst recovery Supercritical 3 Continuous production High temperature and pressure High conversions possible with no catalyst (60% to 70%) Supercritical with Tin Catalyst Continuous packed bed reactor at high temperatures and pressures (305 C, 2500 psi) Highest conversions (up to 98%) using a tin or tin-alloy catalyst No catalyst recovery required Two Methods of Comparison System Overview Future work and Applications Test other oil and alcohols (Jatrotha, tert-butyl alcohol, etc.) to expand upon mathematical model Find how oil and alcohol combinations correlate to Cetane number and Cloud-Point Test larger system with in-line separations to be built this summer [1] US Energy Information Administration. 2008 [2] Biodiesel Production and Quality. April 26, 2007 [3] Norman. Continuous Supercritical Biodiesel Production via a Catalytic Packed Bed Reactor. 2009 [4] Supplements to the 2011 Oregon Administrative Rules Compilation. Volume 50, No. 3. March 1, 2011 [5] National Biodiesel Board. Biodiesel Fuel Management Best Practices for Transit. November 27, 2007 [6] Phillips Petroleum Company, No. 2 Diesel Fuel MSDS. 2002 Safety High pressure system: 2500 psi ( 170 atm) –unique safety hazard Inhalation hazard: temperatures above the normal boiling point of alcohols Flammable reactants and products Why Biodiesel? Reduce dependence on petroleum-based fuels Commercial diesel must be blended with biodiesel by law Feed stocks can be grown on land incapable of food production. In 2010 over 3,000,000 barrels of petro-diesel was consumed per day, while only 20,000 barrels of biodiesel was produced per day. 1 Product Purification Product is a mixture of biodiesel, excess alcohol, glycerin, water, and trace impurities. Purified by distillation Alcohol is recovered and recycled Supercritical Bio-Diesel Production Through a Packed-Bed Reactor School of Chemical Biological and Environmental Engineering Team Members: Joseph DeWilde, Colin Reed, Keri Robinson Sponsors: Dr. Nick Wannenmacher, Dr. Dan Euhus PE How Bio-Diesel is Produced Glycerides from oil converted to esters (bio-diesel) Variable Values Oil Camelina, Sunflower Alcohol Ethanol, Methanol, Iso-Propanol, Tert-Butanol Temperatures [°C] 275, 290, 305 Pressure [psi] 2500 Molar Ratio [alcohol:oil] 20:1, 30:1 Cetane Number Quantifies fuel combustion Average diesel cetane number: 45 (47 is premium in Oregon) 4 Cloud-Point Temperature at which fuel becomes cloudy Temperatures below cloud point clog injection systems Additives are used to drop cloud point but increase cost of fuel Average diesel cloud point: 10 °F (with additives) 6 Traditional biodiesel cloud point: 34 °F (no additives) 5 Bio vs. Petro Gas Chromatography Dr. Nick Wannenmacher Dr. Dan Euhus, PE Dr. Brian Reed Kevin Harris Dr. Philip Harding, PE Kit Boyle - South Oregon Seed Oils Inc Acknowledgements Separates samples and obtains compositions Used to determine conversion of product Oil R-OH Bio- Diesel Glycerol Alcohol + Oil Bio-Diesel + Glycerol Camelina Oil Chromatograph Overlay High Pressure Oil Pump Reactor Cooling loop and Electrical Box Aluminum Heating Blocks Heating Block Temperature Pre-Heaters Reactor Pressure Sample Outlet High Pressure Alcohol Pump Hot Plate Sample Cooling Water Cooling Water v Vapor Liquid Samples (from left to right): Camelina &Ethanol Camelina &Methanol Camelina &Iso-propanol Sunflower & Iso-propanol Sunflower &Methanol Sunflower &Ethanol All samples taken at 305 °C and 20:1 molar ratio 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 2008 2011 2014 2017 2020 2023 2026 2029 2032 2035 Million Barrels per Day Year Petro-diesel consumption Biodiesel production Average Biodiesel Cloud Point