2WhyWhy Biodiesel?Biodiesel?11

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 difficult1

Biodiesel Production via Continuous Supercritical Catalytic Packed Bed ReactorBiodiesel Production via Continuous Supercritical Catalytic Packed Bed Reactor

Project Objectives

Operating ParametersOperating Parameters

KineticKinetic ModelModel

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)

CanolaCanola CastorCastor

CamelinaCamelina

Yellow GreaseYellow Grease

Soy BeanSoy BeanJatrophaJatropha

Experimental SetupExperimental Setup

Cooling Loop & Pressure Regulation

Reactor & Preheater Housing

Electrical & Control Housing

High Pressure Pumps

FeedstockFeedstock OilsOilsFood Grade Canola

Commercial Yellow Grease

Unrefined Jatropha

Expeller Pressed (MT) Camelina

Industrial Castor

Expeller Pressed (OR) Soybean

Expeller Pressed (OR) Camelina

WhatWhat isis Biodiesel? Biodiesel?

HowHow is Biodiesel Produced?is Biodiesel Produced?

Limitations of Current BD TechnologyLimitations of Current BD Technology

Domestic Biodiesel ProductionDomestic Biodiesel Production

Our Production Technology – Our Production Technology – Continuous, Supercritical, Catalytic Packed Bed TransesterificationContinuous, Supercritical, Catalytic Packed Bed Transesterification

Reaction of one large multi-ester molecule with three alcohols to make three esters and one glycerol4

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/galFor a 60 million gallon production facility, when

considering only raw material, utility and fuels costs from an economic analysis completed at Iowa State University6

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 easier9

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 uses9

Molar Ester PercentMolar Ester Percent

Gas Chromatography Gas Chromatography Data Analysis Data Analysis

Time [min]

Res

pons

e [m

V]

Oregon State University ◦ School of Chemical, Biological and Environmental EngineeringTeam 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 Powder Treated 304 Stainless Powder

4

CatalystCatalyst Tin catalyst applied to 50-250 μm 304 stainless steel plasma powder (OSU Patented Technologies)

References available upon request.

First Order Rate at 290˚C Second Order Rate at 305˚CSlope = k/Xe

5

Reduces dependency on imported petroleum

Little or no modification to existing diesel engines

Reduced emissions such as (CO2, 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 feedstocks3

Produced from renewable vegetable oils, waste cooking oil, animal fat and non-edible oils

7

Dol

lar/

barr

el (

$/bb

l)

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 8th, 2009 crude oil was $68.7/bbl8

Economic ComparisonEconomic ComparisonAnalysis 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

ConclusionsConclusionsMinimal 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 Variability of Crude Oil Price

Decrease dependence on petroleum based fuels

Build local economies

Reduce distribution costs

Additional Motivation Additional Motivation for Biofuels for Biofuels

Slope = 2k(1/Xe -1)CA0