2 Why Biodiesel? 1  Homogeneous catalysts require refined oils  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 difficult 1 Biodiesel Production via Continuous Supercritical Catalytic Packed Bed Reactor Project Objectives Operating Parameters Kinetic Model  Gas Chromatography (GC) with a Flame Ionization Detector (FID), used to detect electric current (Response) of eluting compounds, for determining sample composition  Two internal standards used for mass determination  Certified standards used for ethyl and methyl ester calibrations  Molar amount of esters present in product stream ignoring unreacted feedstock alcohol - this excess alcohol is recycled back into the alcohol feedstock storage tank  Reaction kinetics modeling of canola and soy bean oil conversion data  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  Establish optimal operating conditions for different feedstock oils to obtain the highest production at the lowest operating cost (low energy input and separation cost)  Determine feasibility of unrefined natural oil feedstocks obtained from national and local suppliers  Develop kinetic model of transesterification reaction under supercritical heterogeneous catalytic continuous flow conditions  Conduct economic comparison to classical batch processes  Reactor temperature (290°C & 305°C)  Alcohol to oil molar ratio (20:1 & 30:1)  Residence time within reactor based on standard flow conditions (4, 6 & 8 minutes)  Pressure of reactor (constant at 2500 psi) CanolaCastor Camelina Yellow Grease Soy Bean Jatropha Experimental Setup Cooling Loop & Pressure Regulation Reactor & Preheater Housing Electrical & Control Housing High Pressure Pumps Feedstock Oils  Food Grade Canola  Commercial Yellow Grease  Unrefined Jatropha  Expeller Pressed (MT) Camelina  Industrial Castor  Expeller Pressed (OR) Soybean  Expeller Pressed (OR) Camelina What is Biodiesel? How is Biodiesel Produced? Limitations of Current BD Technology Domestic Biodiesel Production Our Production Technology – Continuous, Supercritical, Catalytic Packed Bed Transesterification  Reaction of one large multi-ester molecule with three alcohols to make three esters and one glycerol 4  Catalyst Material  Homogeneous (i.e. liquid-liquid phase)  Heterogeneous (i.e. solid-liquid phase)  Analysis completed on classical batch method using soybean, methanol and base catalysts $2.15/gal  For a 60 million gallon production facility, when considering only raw material, utility and fuels costs from an economic analysis completed at Iowa State University 6  Need for a shift to more efficient, cost effective reaction methods to meet increasing demand  Reaction can take an hour or longer  Pretreatment required to prevent soap formation before combining with liquid catalyst and alcohol  In the supercritical state the miscibility (how well components mix) is greatly increased  Water content in the oil does not effect the conversion and has been shown to assist with the formation of esters. Additionally, glycerol is more soluble in water which makes product separation easier 9  Product quality is more consistent than batch methods  Free fatty acids (FFA) are converted to esters  Glycerol purity (> 96%) can be sold for cosmetic and pharmaceutical uses 9 Molar Ester Percent Gas Chromatography Data Analysis Time [min] Response [mV] 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 304 Stainless PowderTreated 304 Stainless Powder 4Catalyst Tin catalyst applied to μm 304 stainless steel plasma powder (OSU Patented Technologies) References available upon request. First Order Rate at 290˚C Second Order Rate at 305˚C Slope = k/X e 5  Reduces dependency on imported petroleum  Little or no modification to existing diesel engines  Reduced emissions such as (CO 2, CO, etc.), non-toxic and degrades 4 TIMES faster than petrodiesel  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)  Monoalkyl esters of long chain fatty acids derived from renewable lipid feedstocks 3  Produced from renewable vegetable oils, waste cooking oil, animal fat and non-edible oils 7 Dollar/barrel ($/bbl) 305°C – 20:1  4 minute  6 minute  8 minute  At the beginning of this project (March 2009) crude oil was $45/bbl  As of June 8 th, 2009 crude oil was $68.7/bbl 8 Economic Comparison  Analysis completed on raw material costs for ethanol and soybean oil including transportation costs  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  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 Camelina Oil Chromatogram Overlay $68.7/bbl Ester Percent of Reactor Products Variability of Crude Oil Price  Decrease dependence on petroleum based fuels  Build local economies  Reduce distribution costs Additional Motivation for Biofuels Slope = 2k(1/X e -1)C A0