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
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