BIODIESEL Overview and Lab Analysis

1. BIODIESELOverview and Lab Analysis 6th Combined Manager’s and Law Enforcement Seminar Mesa, Arizona September 14, 2007 Frédéric Boily, M.Sc. Chemist

2. Overview • General description and chemical properties • Biodiesel advantages • Feedstocks and production • Production, potential markets and tax incentives • USA • Canada • Lab analysis on Biodiesel/Diesel blends • Dyed biodiesel (Red dye added to biodiesel) • FTIR method (Lab) • On-road detection • Questions

3. General Description and Chemical Properties

4. General Description • What is biodiesel (general definition) : • Biodiesel is a domestic, renewable fuel for diesel engines derived from natural oils. Biodiesel is not the same thing as raw natural oils. • Biodiesel is produced by chemical process which removes the glycerin from the oil. • Biodiesel must meets the specifications of ASTM D 6751. • Technical Definition (ASTM D 6751) : • Biodiesel is a fuel comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or animals fats, designated B100, and meeting the requirements of ASTM D6751. • Biodiesel blends : • B10 is a blend of biodiesel with petroleum diesel, where 10 represents the volume percentage of biodiesel in the blend.

5. Present only in biodiesel Between 10 to 17 carbons General description Biodiesel molecule

6. General description B100 (animal fat) B100 (Vegetable oil)

7. Chemical Properties • Below B20 blend, no modification are necessary for diesel engine, distribution system and storage tank. • Pumps • Seals • Heating system in cold conditions • Four properties can explain the modifications. • Cloud point • Pour point • Viscosity • Acid number (acidity)

8. Chemical Properties • Cloud point : • The cloud point is the lowest temperature at which the wax crystals appear. The wax crystal block the engine filters. • Pour point : • The pour point is an indication of the lowest temperature at which a liquid can be pumped. • Viscosity : • The kinematic viscosity is the resistance to flow of a fluid under gravity. Viscosity increases with the lowering of the temperature. • Acid number (acidity) : • The acid number is used to quantify the amount of acid present in a sample of biodiesel. «Corrosion power»

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

10. Biodiesel Advantages, Feedstocks and Production

11. Biodiesel Advantages • Social and economic advantages : • New markets for agricultural producers. • Agricultural resources (soybean, canola) • Produce form renewable resources. • Non comestible vegetal oil • Waste oil • Recycled frying oil • Animal fat • Biodiesel is expected to reduce the world’s dependency on petroleum fuel. • Environmental advantages : • B100 produce from 64 % to 92 % less GHG emissions. • B20 produce from 12 % to 18 % less GHG emissions. • B2 produce from 1 % to 2 % less GHG emissions. • Reduction in the production of methane (CH4) in dumps.

12. Feedstocks and Production • Feedstocks : • United States • Canola (rapeseed) and soybean • Canada • 10 % non comestible vegetal oil • 45 % recycled frying oil • 45 % animal fat • Production of biodiesel (transesterification) : • We mix the fat or oil with an alcohol (methanol or ethanol). • To accelerate the reaction, we add a basic catalyst (NaOH) and we heat the blend to 140 °F. • From this chemical reaction, we produce the biodiesel and the glycerine.

13. 140 °F Fat / Oil Alcohol Biodiesel Glycerine Feedstocks and Production

14. Mass-production Dryer Biodiesel Methanol Catalyst Methyl esters Blend thank Separator Water washing Neutralization and separation Fat / oil Glycerol (50 %) Acid Acidification And FFA separation Wash water Water Methanol / water (purification) Methanol Water Methanol removal Crude Glycerine (85 %)

15. Production, potential markets and tax incentives

16. Production (USA) • According to NBB (June 7, 2007) • 148 commercial biodiesel production plants. • Total annual production capacity is 1.39 billion gallons. http://www.biodiesel.org

17. Production (USA) • According to NBB (June 7, 2007) • 101 biodiesel production plants under construction or expansion. • Anticipated annual production capacity is 1.89 billion gallons. The production cost is approximately 3.10 $ / gallons http://www.biodiesel.org

18. From 2005 to 2006, more than 200 % increasing Potential Markets (USA) • According to NBB, the estimated biodiesel demand. Biodiesel is the fastest growing alternative fuel in North America U.S. Government run with biodiesel : national parks, postal services, USDA and USDE http://www.biodiesel.org

19. Tax Incentives (USA) • Tax incentives : • Some States have tax incentives (26 States on IFTA website). • Some States have production incentives. • Federal Credit for the biodiesel producer. • 1 cent / % when it’s made with vegetable oil or animal fat. • ½ cent / % when it’s made with recycled frying oil. • According to NJBPA, the Federal Credit end in 2008. • Other incentives : • The Clean Air Act (1990) was the first incentive to favour emergence of alternative fuels (biodiesel and ethanol). • In his State of the Union Address in 2006, President Bush said ‛‛America is addicted to oil…from unstable parts of the world.’’ His Advanced Energy Initiative calls for replacing 75 % of oil imports from the Middle East by 2025. • Biodiesel is part of the solution. • Some States have obligation to add biodiesel in diesel (from B2 to B5).

20. Production (Canada) • According to CQB (June 2007) • 7 commercial biodiesel production plants. • Total annual production capacity is 31.7 million gallons. Between 2005 and 2006, the biodiesel production increased from 2.6 MG to 31.7 MG The price of biodiesel is from 10 % to 15 % greater than of the diesel price

21. Potential Markets (Canada) • According to CQB, the potential biodiesel market in Canada will be approximately 396 MG/year if we introduce the B5 blend in all sectors (transport, heat oil). • 22 biodiesel distributors : • Atlantic (2) • Quebec (2) • Ontario (6) • Alberta, Saskatchewan and Manitoba (3) • British-Columbia (9) • 12 sell points : • Ontario (3) • British-Columbia (9) More than 1000 in Germany !!!

22. Tax Incentives (Canada) • Tax incentives : • Some provinces have tax incentives. • Since 2003, no exice tax on biodiesel (4 ¢ / L). • Other incentives : • In the Canada’s Clean Air Act (2006), the government fixed to 132 MG the biodiesel production before 2012. • Minimal biodiesel content of 2 % in all sectors before 2010. • Renewable Fuel Strategy (RFS) : • 345 million $ for rural communities → new avenues for bioproducts. • 2 billion $ to support renewable fuels production. • No incentives for distribution of biodiesel. • The American biodiesel is more competitive.

23. Lab Analysis onbiodiesel / diesel blends

24. Dyed Biodiesel • Advantages : • None. • Disadvantages : • Dyed B100 is unstable (with organic dye). After two weeks, we can see a white cloud appearing in the bottom. • 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. • Currently, it’s impossible to determine the percentage of biodiesel in a blend with our lab methods (extraction of dye). Because the molecular structure of biodiesel is different form diesel, it’s difficult to extract the dye from the biodiesel. • With the dark color of the biodiesel, it’s difficult to detect the red colour on the road.

25. Dyed Biodiesel Dyed B100 B100 Dyed fuel

26. FTIR Analysis • Theory : • It’s a widespread analysis technique that provides information about the chemical bounding or molecular structure of materials. It’s used to identify unknown materials present in a specimen. • The technique works on the fact that bounds and groups of bound vibrate at characteristic frequencies. A molecule that is exposed to infrared rays absorbs infrared energy at frequencies which are characteristic to that molecule. • The specimen’s transmittance and reflectance of the infrared rays at different frequencies is translated into an IR absorption plot. • FTIR is a good tool for identifying types of chemical bounds in a molecule by producing an infrared absorption spectrum that is like a molecular ‛‛fingerprint’’. http://www.siliconfareast.com/FTIR.htm

27. Carbon double bound oxygen Functional group of biodiesel FTIR Analysis • The difference between biodiesel and diesel, it’s the presence of oxygen atoms in biodiesel molecule. • To identify biodiesel and determine the % in a blend, we put our attention on the C=O signal.

28. FTIR Analysis • FTIR : • No sample preparation. • 2-3 mL of sample.

29. FTIR Analysis Diesel spectrum Biodiesel spectrum Peak coming from C=O bound signal

30. Zoom FTIR Analysis B0 to B100 B0 to B100 The peak area increases with the addition of biodiesel in the blend

31. Biodiesel % Peak area FTIR Analysis • Fromdifferent standards of biodiesel blend (B0 to B100), we can plot the graph of biodiesel % on Y axis and peak area on X axis. • From this plot, we can determine the percentage of biodiesel in a unknown biodiesel blend sample. • The linearity of the curve is good for the blend under 50 % of biodiesel. • This FTIR analysis allows to determine with a very good precision, the percentage of biodiesel.

32. On-road Detection • On-road reagent : • Advantages • Very simple to use. • Very fast result. • Tested with many biodiesel. • Disadvantages : • Very expensive for one sample. • Dark sample or red dyes may cloud the interpretation of the results. • Fuel analyser (portable IR) : • Advantages : • Very fast result • Quantification of the result (%). • Disadvantages : • Very expensive for large distribution. • Used oil may cloud the interpretation of the result.

33. Conclusion • Biodiesel and petroleum diesel form a homogeneous blend. • Currently, the on-road detection system are very expensive. • To dye the biodiesel is not a good thing. • FTIR analysis gives good results for the blend under 40 %.

34. Acknowledgements • IFTA’s members • For the great organization. • Georges Sansfaçon • For his great collaboration.

35. Disclaimer • The content of this presentation reflect the views of the author, who are responsible for the facts and accuracy of the data collected and presented. • This document has been prepared in the sole interest of information exchange during the present seminar. It does not constitute a standard, specification, or guideline.