BIODIESELBIODIESELOverview and Lab AnalysisOverview and Lab Analysis

6th Combined Manager’s and6th Combined Manager’s and

Law Enforcement SeminarLaw Enforcement Seminar

Mesa, ArizonaMesa, ArizonaSeptember 14, 2007September 14, 2007

Frédéric Boily, M.Sc. ChemistFrédéric Boily, M.Sc. Chemist

OverviewOverview

General description and chemical propertiesGeneral description and chemical properties

Biodiesel advantagesBiodiesel advantages

Feedstocks and productionFeedstocks and production

Production, potential markets and tax incentivesProduction, potential markets and tax incentivesUSAUSACanadaCanada

Lab analysis on Biodiesel/Diesel blendsLab analysis on Biodiesel/Diesel blendsDyed biodiesel (Red dye added to biodiesel)Dyed biodiesel (Red dye added to biodiesel)FTIR method (Lab)FTIR method (Lab)On-road detectionOn-road detection

QuestionsQuestions

General Description and General Description and Chemical PropertiesChemical Properties

General DescriptionGeneral Description

What is biodiesel (general definition) :What is biodiesel (general definition) :Biodiesel is a domestic, renewable fuel for diesel engines derived Biodiesel is a domestic, renewable fuel for diesel engines derived from from natural oilsnatural oils. Biodiesel is not the same thing as raw natural oils.. Biodiesel is not the same thing as raw natural oils.

Biodiesel is produced by chemical process which removes the Biodiesel is produced by chemical process which removes the glycerin from the oil.glycerin from the oil.

Biodiesel must meets the specifications of ASTM D 6751.Biodiesel must meets the specifications of ASTM D 6751.

Technical Definition (ASTM D 6751) :Technical Definition (ASTM D 6751) :Biodiesel is a fuel comprised of mono-alkyl esters of long chain fatty Biodiesel is a fuel comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or animals fats, designated B100, acids derived from vegetable oils or animals fats, designated B100, and meeting the requirements of ASTM D6751.and meeting the requirements of ASTM D6751.

Biodiesel blends :Biodiesel blends :B10B10 is a blend of biodiesel with petroleum diesel, where is a blend of biodiesel with petroleum diesel, where 1010 represents the volume percentage of biodiesel in the blend.represents the volume percentage of biodiesel in the blend.

CH3

O

C

O

CH3

Present only in biodieselPresent only in biodiesel

General descriptionGeneral description

Between 10 to 17 carbonsBetween 10 to 17 carbons

Biodiesel moleculeBiodiesel molecule

General descriptionGeneral description

B100B100(animal fat)(animal fat)

B100B100(Vegetable oil)(Vegetable oil)

Chemical PropertiesChemical Properties

Below B20 blend, no modification are necessary for diesel Below B20 blend, no modification are necessary for diesel engine, distribution system and storage tank.engine, distribution system and storage tank.

PumpsPumps

SealsSeals

Heating system in cold conditionsHeating system in cold conditions

Four properties can explain the modifications.Four properties can explain the modifications.Cloud pointCloud point

Pour pointPour point

ViscosityViscosity

Acid number (acidity)Acid number (acidity)

Chemical PropertiesChemical Properties

Cloud point :Cloud point :The cloud point is the lowest temperature at which the wax crystals The cloud point is the lowest temperature at which the wax crystals appear. The wax crystal block the engine filters.appear. The wax crystal block the engine filters.

Pour point :Pour point :The pour point is an indication of the lowest temperature at which a The pour point is an indication of the lowest temperature at which a liquid can be pumped. liquid can be pumped.

Viscosity :Viscosity :The kinematic viscosity is the resistance to flow of a fluid under The kinematic viscosity is the resistance to flow of a fluid under gravity. Viscosity increases with the lowering of the temperature.gravity. Viscosity increases with the lowering of the temperature.

Acid number (acidity) :Acid number (acidity) :The acid number is used to quantify the amount of acid present in a The acid number is used to quantify the amount of acid present in a sample of biodiesel. sample of biodiesel. «Corrosion power»«Corrosion power»

Biodiesel blend with winter diesel (-40 Biodiesel blend with winter diesel (-40 °F).°F).B20 and higher blend are problematic in cold condition.B20 and higher blend are problematic in cold condition.

Chemical PropertiesChemical Properties

Biodiesel Advantages, Biodiesel Advantages, Feedstocks and ProductionFeedstocks and Production

Social and economic advantages :Social and economic advantages :New markets for agricultural producers.New markets for agricultural producers.

Agricultural resources (soybean, canola)Agricultural resources (soybean, canola)

Produce form renewable resources.Produce form renewable resources.Non comestible vegetal oilNon comestible vegetal oil

Waste oilWaste oil

Recycled frying oilRecycled frying oil

Animal fatAnimal fat

Biodiesel is expected to reduce the world’s dependency on Biodiesel is expected to reduce the world’s dependency on petroleum fuel.petroleum fuel.

Environmental advantages :Environmental advantages :B100 produce from 64 % to 92 % less GHG emissions.B100 produce from 64 % to 92 % less GHG emissions.

B20 produce from 12 % to 18 % less GHG emissions.B20 produce from 12 % to 18 % less GHG emissions.

B2 produce from 1 % to 2 % less GHG emissions.B2 produce from 1 % to 2 % less GHG emissions.

Reduction in the production of methane (CH4) in dumps.Reduction in the production of methane (CH4) in dumps.

Biodiesel AdvantagesBiodiesel Advantages

Feedstocks and ProductionFeedstocks and Production

Feedstocks :Feedstocks :United StatesUnited States

Canola (rapeseed) and soybeanCanola (rapeseed) and soybean

CanadaCanada10 % non comestible vegetal oil10 % non comestible vegetal oil

45 % recycled frying oil45 % recycled frying oil

45 % animal fat45 % animal fat

Production of biodiesel (transesterification) :Production of biodiesel (transesterification) :We mix the fat or oil with an alcohol (methanol or ethanol).We mix the fat or oil with an alcohol (methanol or ethanol).

To accelerate the reaction, we add a basic catalyst (NaOH) and we To accelerate the reaction, we add a basic catalyst (NaOH) and we heat the blend to 140 heat the blend to 140 °F.°F.

From this chemical reaction, we produce the biodiesel and the From this chemical reaction, we produce the biodiesel and the glycerine.glycerine.

Feedstocks and ProductionFeedstocks and Production

H2C

HC

H2C

O

O

O

C

C

C

O

O

O

R1

R2

R2

+ 3 CH3OHNaOH

H3C O C

O

R1

H3C O C

O

R2

H3C O C

O

R3

+

H2C

HC

H2C

OH

OH

OH

Fat / Oil Biodiesel GlycerineAlcohol

140 °F

Mass-productionMass-production

Methanol

Catalyst

Blend thank

Fat / oilSeparator Water

washing

Neutralization

andseparation

Methylesters

Dryer

Biodiesel

Washwater

Water

AcidGlycerol (50 %)

AcidificationAndFFA

separation

Methanolremoval

Crude Glycerine (85 %)

Methanol / water

(purification)

Water Methanol

Production, potential markets Production, potential markets and tax incentivesand tax incentives

According to NBB (June 7, 2007)According to NBB (June 7, 2007)148148 commercial biodiesel production plants. commercial biodiesel production plants.

Total annual production capacity is Total annual production capacity is 1.39 billion gallons1.39 billion gallons..

Production (USA)Production (USA)

http://www.biodiesel.orghttp://www.biodiesel.org

According to NBB (June 7, 2007)According to NBB (June 7, 2007)101101 biodiesel production plants under construction or expansion. biodiesel production plants under construction or expansion.

Anticipated annual production capacity is Anticipated annual production capacity is 1.89 billion gallons1.89 billion gallons..

Production (USA)Production (USA)

http://www.biodiesel.orghttp://www.biodiesel.org

The production cost is approximately 3.10 $ / gallonsThe production cost is approximately 3.10 $ / gallons

According to NBB, the estimated biodiesel demand. According to NBB, the estimated biodiesel demand.

Potential Markets (USA)Potential Markets (USA)

http://www.biodiesel.orghttp://www.biodiesel.org

0

50

100

150

200

250

Mill

ion

gal

lon

s

1999 2000 2001 2002 2003 2004 2005 2006

Year

From 2005 to 2006,From 2005 to 2006,more than 200 % increasingmore than 200 % increasingBiodiesel is the fastest growing Biodiesel is the fastest growing

alternative fuel in North Americaalternative fuel in North AmericaU.S. Government run with biodiesel :U.S. Government run with biodiesel :national parks, postal services, USDA and USDEnational parks, postal services, USDA and USDE

Tax Incentives (USA)Tax Incentives (USA)

Tax incentives :Tax incentives :Some States have tax incentives (26 States on IFTA website).Some States have tax incentives (26 States on IFTA website).Some States have production incentives.Some States have production incentives.Federal Credit for the biodiesel producer.Federal Credit for the biodiesel producer.

1 cent / % when it’s made with vegetable oil or animal fat.1 cent / % when it’s made with vegetable oil or animal fat.½ cent / % when it’s made with recycled frying oil.½ cent / % when it’s made with recycled frying oil.According to NJBPA, the Federal Credit end in 2008.According to NJBPA, the Federal Credit end in 2008.

Other incentives :Other incentives :The Clean Air Act (1990) was the first incentive to favour emergence The Clean Air Act (1990) was the first incentive to favour emergence of alternative fuels (biodiesel and ethanol).of alternative fuels (biodiesel and ethanol).In his State of the Union Address in 2006, President Bush said In his State of the Union Address in 2006, President Bush said ‛‛‛‛America is addicted to oil…from unstable parts of the world.’’ His America is addicted to oil…from unstable parts of the world.’’ His Advanced Energy Initiative calls for replacing 75 % of oil imports from Advanced Energy Initiative calls for replacing 75 % of oil imports from the Middle East by 2025.the Middle East by 2025.

Biodiesel is part of the solutionBiodiesel is part of the solution..

Some States have obligation to add biodiesel in diesel Some States have obligation to add biodiesel in diesel (from B2 to B5).(from B2 to B5).

Production (Canada)Production (Canada)

According to CQB (June 2007)According to CQB (June 2007)7 commercial biodiesel production plants.7 commercial biodiesel production plants.

Total annual production capacity is Total annual production capacity is 31.7 million gallons31.7 million gallons..

The price of biodiesel is from 10 % to 15 % The price of biodiesel is from 10 % to 15 % greater than of the diesel pricegreater than of the diesel price

Between 2005 and 2006, the biodiesel Between 2005 and 2006, the biodiesel production increased from 2.6 MG to 31.7 MGproduction increased from 2.6 MG to 31.7 MG

Potential Markets (Canada)Potential Markets (Canada)

According to CQB, the potential biodiesel market in Canada will According to CQB, the potential biodiesel market in Canada will be approximately 396 MG/year if we introduce the B5 blend in be approximately 396 MG/year if we introduce the B5 blend in all sectors (transport, heat oil).all sectors (transport, heat oil).

22 biodiesel distributors :22 biodiesel distributors :Atlantic (2)Atlantic (2)

Quebec (2)Quebec (2)

Ontario (6)Ontario (6)

Alberta, Saskatchewan and Manitoba (3)Alberta, Saskatchewan and Manitoba (3)

British-Columbia (9)British-Columbia (9)

12 sell points :12 sell points :Ontario (3)Ontario (3)

British-Columbia (9)British-Columbia (9)

More than 1000More than 1000in Germany !!!in Germany !!!

Tax Incentives (Canada)Tax Incentives (Canada)

Tax incentives :Tax incentives :Some provinces have tax incentives.Some provinces have tax incentives.

Since 2003, no exice tax on biodiesel (4 Since 2003, no exice tax on biodiesel (4 ¢ / L).¢ / L).

Other incentives : Other incentives : In the Canada’s Clean Air Act (2006), the government fixed to In the Canada’s Clean Air Act (2006), the government fixed to 132 MG the biodiesel production before 2012.132 MG the biodiesel production before 2012.

Minimal biodiesel content of 2 % in all sectors before 2010.Minimal biodiesel content of 2 % in all sectors before 2010.

Renewable Fuel Strategy (RFS) :Renewable Fuel Strategy (RFS) :345 million $ for rural communities 345 million $ for rural communities → new avenues for bioproducts.→ new avenues for bioproducts.

2 billion $ to support renewable fuels production.2 billion $ to support renewable fuels production.

No incentives for distribution of biodiesel.No incentives for distribution of biodiesel.

The American biodiesel is more competitive.The American biodiesel is more competitive.

Lab Analysis onLab Analysis onbiodiesel / diesel blendsbiodiesel / diesel blends

Dyed BiodieselDyed Biodiesel

Advantages :Advantages :None.None.

Disadvantages :Disadvantages :Dyed B100 is unstable (with organic dye). After two weeks, we can Dyed B100 is unstable (with organic dye). After two weeks, we can see a white cloud appearing in the bottom.see a white cloud appearing in the bottom.

If we blend a dyed fuel with dyed biodiesel, it will be impossible to If we blend a dyed fuel with dyed biodiesel, it will be impossible to determine if the dye comes from the fuel or the biodiesel. determine if the dye comes from the fuel or the biodiesel.

Currently, it’s impossible to determine the percentage of biodiesel in Currently, it’s impossible to determine the percentage of biodiesel in a blend with our lab methods (extraction of dye). Because the a blend with our lab methods (extraction of dye). Because the molecular structure of biodiesel is different form diesel, it’s difficult to molecular structure of biodiesel is different form diesel, it’s difficult to extract the dye from the biodiesel. extract the dye from the biodiesel.

With the dark color of the biodiesel, it’s difficult to detect the red With the dark color of the biodiesel, it’s difficult to detect the red colour on the road.colour on the road.

Dyed BiodieselDyed Biodiesel

Dyed B100Dyed B100 B100B100 Dyed fuelDyed fuel

FTIR AnalysisFTIR Analysis

Theory :Theory :It’s a widespread analysis technique that provides information about It’s a widespread analysis technique that provides information about the chemical bounding or molecular structure of materials. It’s used the chemical bounding or molecular structure of materials. It’s used to identify unknown materials present in a specimen.to identify unknown materials present in a specimen.

The technique works on the fact that bounds and groups of bound The technique works on the fact that bounds and groups of bound vibrate at characteristic frequencies. A molecule that is exposed to vibrate at characteristic frequencies. A molecule that is exposed to infrared rays absorbs infrared energy at frequencies which are infrared rays absorbs infrared energy at frequencies which are characteristic to that molecule.characteristic to that molecule.

The specimen’s transmittance and reflectance of the infrared rays at The specimen’s transmittance and reflectance of the infrared rays at different frequencies is translated into an IR absorption plot.different frequencies is translated into an IR absorption plot.

FTIR is a good tool for identifying types of chemical bounds in a FTIR is a good tool for identifying types of chemical bounds in a molecule by producing an infrared absorption spectrum that is like a molecule by producing an infrared absorption spectrum that is like a molecular molecular ‛‛‛‛fingerprint’’fingerprint’’..

http://www.siliconfareast.com/FTIR.htmhttp://www.siliconfareast.com/FTIR.htm

FTIR AnalysisFTIR Analysis

The difference between biodiesel and diesel, it’s the presence The difference between biodiesel and diesel, it’s the presence of oxygen atoms in biodiesel molecule.of oxygen atoms in biodiesel molecule.

To identify biodiesel and determine the % in a blend, we put our To identify biodiesel and determine the % in a blend, we put our attention on the C=O signal.attention on the C=O signal.

CH3

O

C

O

CH3

Functional group of biodieselFunctional group of biodieselCarbon double bound oxygenCarbon double bound oxygen

FTIR AnalysisFTIR Analysis

FTIR :FTIR :No sample preparation.No sample preparation.

2-3 mL of sample.2-3 mL of sample.

Biodiesel spectrumBiodiesel spectrum

FTIR AnalysisFTIR Analysis

Diesel spectrumDiesel spectrum

Peak coming fromPeak coming fromC=O bound signalC=O bound signal

FTIR AnalysisFTIR Analysis

B0 to B100 B0 to B100 B0 to B100 B0 to B100

The peak area increases with the addition of The peak area increases with the addition of biodiesel in the blendbiodiesel in the blend

ZoomZoom

FTIR AnalysisFTIR Analysis

FromFrom different standards of biodiesel different standards of biodiesel blend (B0 to B100), we can plot the graph blend (B0 to B100), we can plot the graph of biodiesel % on Y axis and peak area of biodiesel % on Y axis and peak area on X axis.on X axis.

From this plot, we can determine the From this plot, we can determine the percentage of biodiesel in a unknown percentage of biodiesel in a unknown biodiesel blend sample.biodiesel blend sample.

The linearity of the curve is good for the The linearity of the curve is good for the blend under 50 % of biodiesel.blend under 50 % of biodiesel.

This FTIR analysis allows to determine This FTIR analysis allows to determine with a very good precision, the with a very good precision, the percentage of biodiesel.percentage of biodiesel.

0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700

Aire sous le pic (1764,74 cm-1 - 1726,16 cm-1)

% d

e b

iod

iese

l

Peak area

Bio

die

sel

%

On-road DetectionOn-road Detection

On-road reagent :On-road reagent :AdvantagesAdvantages

Very simple to use.Very simple to use.

Very fast result.Very fast result.

Tested with many biodiesel.Tested with many biodiesel.

Disadvantages :Disadvantages :Very expensive for one sample.Very expensive for one sample.

Dark sample or red dyes may cloud the interpretation of the results.Dark sample or red dyes may cloud the interpretation of the results.

Fuel analyser (portable IR) :Fuel analyser (portable IR) :Advantages :Advantages :

Very fast resultVery fast result

Quantification of the result (%).Quantification of the result (%).

Disadvantages :Disadvantages :Very expensive for large distribution.Very expensive for large distribution.

Used oil may cloud the interpretation of the result.Used oil may cloud the interpretation of the result.

ConclusionConclusion

Biodiesel and petroleum diesel form a homogeneous blend.Biodiesel and petroleum diesel form a homogeneous blend.

Currently, the on-road detection system are very expensive.Currently, the on-road detection system are very expensive.

To dye the biodiesel is not a good thing.To dye the biodiesel is not a good thing.

FTIR analysis gives good results for the blend under 40 %.FTIR analysis gives good results for the blend under 40 %.

AcknowledgementsAcknowledgements

IFTA’s membersIFTA’s membersFor the great organization.For the great organization.

Georges SansfaçonGeorges SansfaçonFor his great collaboration.For his great collaboration.

DisclaimerDisclaimer

The content of this presentation reflect the views of the author, The content of this presentation reflect the views of the author, who are responsible for the facts and accuracy of the data who are responsible for the facts and accuracy of the data collected and presented.collected and presented.

This document has been prepared in the sole interest of This document has been prepared in the sole interest of information exchangeinformation exchange during the present seminar. It does not during the present seminar. It does not constitute a standard, specification, or guideline.constitute a standard, specification, or guideline.