supercritical bio-diesel production through a …...biodiesel by law feed stocks can be grown on...

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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

Traditional2

Batch process involving a acid or base catalyst Requires extensive pre and post process purification involving catalyst

recovery

Supercritical3

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 ApplicationsTest other oil and alcohols (Jatrotha, tert-butyl alcohol, etc.) to expand upon

mathematical modelFind how oil and alcohol combinations correlate to Cetane number and Cloud-PointTest 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 distillationAlcohol is recovered and recycled

Supercritical Bio-Diesel Production Through a Packed-Bed ReactorSchool of Chemical Biological and Environmental EngineeringTeam 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 ValuesOil Camelina, Sunflower

Alcohol Ethanol, Methanol, Iso-Propanol, Tert-ButanolTemperatures [°C] 275, 290, 305

Pressure [psi] 2500Molar Ratio [alcohol:oil] 20:1, 30:1

Cetane Number Quantifies fuel combustionAverage diesel cetane number: 45 (47 is premium in Oregon)4

Cloud-PointTemperature at which fuel becomes cloudyTemperatures below cloud point clog injection systemsAdditives are used to drop cloud point but increase cost of fuelAverage 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, PEDr. Brian Reed

Kevin HarrisDr. Philip Harding, PEKit Boyle - South Oregon Seed Oils Inc

Acknowledgements

Separates samples and obtains compositions

Used to determine conversion of product

OilR-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

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Petro-diesel consumption

Biodiesel production

Average Biodiesel Cloud Point