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Biodiesel Production via Continuous Supercritical Catalytic Packed Bed Reactor Oregon State University ◦ School of Chemical, Biological and Environmental Engineering Team Members: Staci Van Norman, Mike Knapp, Malachi Bunn Project Sponsors: Dr. Nick Wannenmacher, Dr. Brian Reed, Kevin Harris M.S., M.B.A. Chevron, Beaver Biodiesel, Willamette Biodiesel, Encore Fuels, ONAMI, MBI Gas Chromatography Data Analysis Little or no modification to existing diesel engines In the supercritical state the miscibility (how well components mix) is greatly increased Reduced emissions such as (CO2, CO, etc.), non-toxic and degrades 4 TIMES faster than petrodiesel Water content in the oil does not effect the conversion Glycerol purity (> 96%) can be sold for cosmetic and and has been shown to assist with the formation of 9 pharmaceutical uses esters. Additionally, glycerol is more soluble in water which makes product separation easier9 Gas Chromatography (GC) with a Flame Ionization Detector (FID), used to detect electric current (Response) of eluting compounds, for determining sample composition 2 Oxygen content in biodiesel (BD) improves combustion efficiency and also has a flash point of 302°F (150°C) compared to petrodiesel of 147°F (64°C) Product quality is more consistent than batch methods Free fatty acids (FFA) are converted to esters Project Objectives Establish optimal operating conditions for different feedstock oils to obtain the highest production at the lowest operating cost (low energy input and separation cost) What is Biodiesel? Monoalkyl esters of long chain fatty acids derived from renewable lipid feedstocks3 Produced from renewable vegetable oils, waste cooking oil, animal fat and non-edible oils How is Biodiesel Produced? 4 Two internal standards used for mass determination Camelina Oil Chromatogram Overlay Response [mV] Reduces dependency on imported petroleum Our Production Technology – Continuous, Supercritical, Catalytic Packed Bed Transesterification Why Biodiesel?1 Certified standards used for ethyl and methyl ester calibrations Determine feasibility of unrefined natural oil feedstocks obtained from national and local suppliers Reaction of one large multi-ester molecule with three alcohols to make three esters and one glycerol4 Time [min] Develop kinetic model of transesterification reaction under supercritical heterogeneous catalytic continuous flow conditions Operating Parameters Molar Ester Percent Reactor temperature (290°C & 305°C) Conduct economic comparison to classical batch processes Alcohol to oil molar ratio (20:1 & 30:1) Molar amount of esters present in product stream ignoring unreacted feedstock alcohol - this excess alcohol is recycled back into the alcohol feedstock storage tank Residence time within reactor based on standard flow conditions (4, 6 & 8 minutes) Catalyst Material Homogeneous (i.e. liquid-liquid phase) Heterogeneous (i.e. solid-liquid phase) Catalyst Tin catalyst applied to 50-250 μm 304 stainless steel plasma powder (OSU Patented Technologies) Pressure of reactor (constant at 2500 psi) Ester Percent of Reactor Products Limitations of Current BD Technology Homogeneous catalysts require refined oils Reaction can take an hour or longer Free fatty acid content over 0.5 wt% and water bearing oils cause soap and froth formation which reduces productivity and makes separation of products difficult1 Pretreatment required to prevent soap formation before combining with liquid catalyst and alcohol Domestic Biodiesel Production 305°C – 20:1 4 minute 6 minute 8 minute 304 Stainless Powder Treated 304 Stainless Powder 5 Analysis completed on classical batch method using soybean, methanol and base catalysts $2.15/gal Kinetic Model For a 60 million gallon production facility, when considering only raw material, utility and fuels costs from an economic analysis completed at Iowa State University6 Canola Feedstock Oils Castor Food Grade Canola Yellow Grease Need for a shift to more efficient, cost effective reaction methods to meet increasing demand Commercial Yellow Grease Unrefined Jatropha Expeller Pressed (MT) Camelina Industrial Castor Expeller Pressed (OR) Soybean Jatropha Variability of Crude Oil Price 7 As of June 8th, 2009 crude oil was $68.7/bbl8 Additional Motivation for Biofuels Decrease dependence on petroleum based fuels Build local economies Dollar/barrel ($/bbl) At the beginning of this project (March 2009) crude oil was $45/bbl Camelina Expeller Pressed (OR) Camelina Soy Bean Second Order Rate at 305˚C Slope = 2k(1/Xe -1)CA0 Reaction rate kinetics change from first to second order with increasing reactor temperature for canola oil Soybean oil continues to be first order with increasing temperature Economic Comparison Experimental Setup Analysis completed on raw material costs for ethanol and soybean oil including transportation costs $68.7/bbl This estimation does not include capital costs which would decrease with increasing production output $0.98-$0.99/gal Conclusions Minimal variation in % molar ester content using different oils No significant benefit to increasing temperature or reactant ratio within the tested operating conditions Reduce distribution costs High Pressure Pumps References available upon request. Reaction kinetics modeling of canola and soy bean oil conversion data First Order Rate at 290˚C Slope = k/Xe Electrical & Control Housing Reactor & Preheater Housing Cooling Loop & Pressure Regulation Initial economic analysis comparison, to classical batch production, demonstrates about 50% reduction in material costs per gallon produced using this technology High FFA content changes the reaction kinetics, making overall ester production faster Technology is ready for pilot scale production, including implementation of separation techniques