B io-diesel Basics and Quality Standards Presented by: CATHIE JOHNSTON Intertek Caleb Brett Laboratory Business Develo

1. Bio-diesel Basics andQuality StandardsPresented by: CATHIE JOHNSTONIntertek Caleb BrettLaboratory Business Development3 April 2006

2. New York Harbor, Regional Laboratory

3. MAIN LABORATORY

4. Biodiesel: What is it? • A clean burning, oxygenated diesel fuel made from vegetable oils or animal fats that is capable of replacing part or all of your diesel needs. Biodiesel: How is it made? • By reacting alcohol with natural fats, oils or greases through a conventional chemical process known as transesterification.

5. Raw Materials + + Natural Fats & Oils Soybean Rapeseed Cottonseed Tallow / Poultry Yellow Grease Alcohol MethanolEthanol Catalyst Sodium hydroxide Potassium hydroxide Sodium Methoxide End Products = Methyl Ester (a.k.a. biodiesel) Glycerine

6. Biodiesel: Key Benefits • Significantly reduces tailpipe emissions • Reduced dependency on foreign oil • Significantly reduces carcinogenic pollutants • B20 significantly reduces visible emissions • At B2 increases lubricity by up to 60% • The economical option for EPAct

7. Commercial Refining and Delivery

8. Bio-Diesel “HomeBrew”FROM THE FRYER TO THE FUEL TANK

9. Biodiesel: How is it used? • As pure (100%) = B100 • As a blend with petroleum diesel (20%) = B20 • In low levels (1% - 5%) = B1 – B5 • Any blend concentration requested = B1 – B99

10. Biodiesel: Benefits According to the Department of Energy • Clean and Renewable • For every 1 unit of energy needed for production 3.2 units energy are gained. • Produced from a renewable agricultural product Source EPA www.epa.gov/otaq/models/biodsl.htm

11. Biodiesel: Financial Impact? Biodiesel is less costly than other alternative fuel options! *Michael Wetzstein of the University of Georgia concluded that biodiesel is the most cost effective alternative fuel when considered on a cost per mile basis, considering factors like fuel economy, maintenance, engine rebuild mileage, and fueling infrastructure.

12. Fuel Quality B100 is covered by American Society of Testing and Materials standard D6751. Blends do not yet have a standard – however experience indicates that if D2 is D975-compliant, B100 is D6751-compliant, blends should be acceptable (poor cold-blending is an exception). Conformity of B100 to D6751 can be assured through adherence to industry quality program for producers and distributors, BQ-9000 – however, participation in this program is low with only two producers to date. Quality control of biodiesel is not well documented at this point, however, all producers certify B100 product conforms to D6751 (otherwise, the product is not eligible for the blenders tax credit). ( Information as provided by Virginia Clean Cities)

13. Biodiesel Testing Standards and Quality Control

14. QUALITY CONTROL TESTING • Quality Control Testing Importance • Quality Control Standards-ASTM D6751 • Other Analytical Methods Applicable to • Biodiesel • Production Level Quality Control • 3rd Party C of A Support • Questions & Discussion

15. Quality Control Testing Importance • Feedstock quality • Production optimization • Controls by-product production levels • Controls Feedstock or Raw Material • Requirements • Final product control confirmation • Internal • External, 3rd party Certificate of Analysis

16. ASTM D6751Standard Specification for Biodiesel Fuel Blendstock (B100) for Middle Distillate Fuels • Property Test Method Specification • Flash Point, Closed Cup ASTM D93 130°C min • Water and Sediment ASTM D2709 0.050 Vol. % Max • Kinematic Viscosity, 40°C ASTM D445 1.9-6.0 mm2/s • Sulfated Ash ASTM D874 0.020 Mass % Max • Sulfur ASTM D5453 0.0015 Mass %, Max • Copper Strip Corrosion ASTM D130 No. 3 Max • Cetane Number ASTM D613 47 Min • Cloud Point, °C ASTM D2500 Report • Carbon Residue ASTM D4530 0.050 Mass %, Max • Acid Number ASTM D664 0.80 mg KOH/g Max • Free Glycerin ASTM D6584 0.020 Mass %, Max • Total Glycerin ASTM D6584 0.240 Mass %, Max • Phosphorous Content ASTM 4951 0.001 Mass %, Max • Distillation Temperature ASTM D1160 360 °C Max • Atmospheric Equivalent Temperature • 90% Recovered

17. ASTM D93 Standard Test Method for Flash Point by Pensky-Martens Closed Cup Tester • Performed to define and guarantee the DOT product rating of “non-hazardous”, or non-flammable • Flash point of Methanol, <100 deg C • Flash point of Biodiesel, >130 deg C min • Indicates residual alcohol, methanol, left in final product • Methanol residue can cause degradation of elastomers and seals within engine • Important to monitor at the production level

18. ASTM D2709 Standard Test Method for Water & Sediment in Middle Distillate Fuels by Centrifuge • Indicator of the cleanliness of the fuel • 0.050 Volume % Max • Water & Sediment are both contaminant in the fuel • Water reacts with the esters to produce Free Fatty Acids (back reaction) • Water Supports microbial Growth • Sediment plugs fuel filters • Both may be sourced from feedstock, treatment during process or storage conditions

19. ASTM D445 Standard Test Method for Kinematic Viscosity of Transparent or Opaque Liquids • Viscosity of the fuel is considered when OEM’s design engine specifications, flow and lubricating properties • Specification Established with a Min/Max Range 1.9-6.0 mm2/s • Viscosity of Biodiesel considered due to its use as a blend component for the diesel product • Blendstock should not change overall diesel properties • Biodiesel specifications designed to allow for optimal blending without compromising overall flow properties • Injector performance can be compromised if viscosity is compromised

20. ASTM D874 Standard Test Method for Sulfated Ash from Lubricating Oils and Additives • Indicator of mineral ash residue left over after fuel is burned • 0.020 Mass % Max • Indicates residual metals from catalyst, spent Na or K salts • Importance is dependent on type of product

21. ASTM D5453Standard Test Method for Determination of Sulfur Content by UV Fluorescence • Indicator of contamination by protein material of feedstock or carryover from the catalyst material • 0.0015 Mass % Max, or 15 ppm • Sulfur should be measured in feedstock-virgin oil versus the rendered product • Critical as Diesel Specifications will change in 2006 to Ultra Low Sulfur (500 ppm versus new 15 ppm as delivered) • Biodiesel should not be a contributor to the overall sulfur of the final blended product • Biodiesel adds lubricity properties lost by reduction in sulfur in diesel product

22. ASTM D130Standard Test Method for the Determination of Copper Corrosion by Copper Strip Tarnish Test • Indicator of the relative corrosivity of the product • No. 3 Max Specification (rating on a 1-4, a-c scale) • Also indicator of presence of acids or free fatty acids derived from unreacted materials in the production process • Total Sulfur (ASTM D5453) is not always indicator of the sulfur species effecting the corrosivity of other sulfur species

23. ASTM D613Standard Test Method for Cetane Number in Diesel Fuel • Indicator of the ignition characteristics of the fuel in compression ignition engines, influences smoke and combustion roughness • Specification, 47 min • Feedstock ultimately determines the cetane number obtained in the final product • Performed on full scale cetane engine, Cetane Index Calculated is not applicable to biodiesel product • Not a production level analysis, cost for engine extremely high

24. ASTM D2500Standard Test Method for Cloud Point in Petroleum Products • Indicator of temperature in which cloud or haze of crystals appears under prescribed conditions, crystal precipitation • No current specification in place for D2500 • Producers should measure this property internally although there is no specification for the product • Consideration to use in cold climates, ie. Northeast • Controlled by blending of feedstocks

25. ASTM D4530Standard Test Method for Determination of Carbon Residue (Micro Method) • Indicator of the carbon depositing tendencies of the fuel • 0.050 Mass % Max • Performed on the 100% fraction due to the distillation characteristics of the fuel • (ie. Difficult to get the 10% bottoms for analysis)

26. ASTM D664Standard Test Method for Acid Number by Potentiometric Titration • Direct measurement of the FFA’s, free fatty acids, processing acids or degradation by-products in the final product • 0.80 mg KOH/g Max • FFA’s are unreacted materials • High Acid characteristics may cause corrosion, fuel system deposit or filter plugging problems • May be a symptom of water in the fuel product

27. ASTM D6584“Free and Total Glycerin in B100 by Gas Chromatography” • Free and Total Glycerin Specification and Definition • 0.020 Mass % Max Free Glycerin • 0.240 Mass % Max Total Glycerin • Total Glycerin-the sum of Free and Bonded Glycerin • Free Glycerin-unbound, incomplete esterification products • Bonded Glycerin-includes mono, di and triglycerides • Why is this property important? • Due to the nature of the glycerides in the final product • Can cause operability problems at low temperatures • Saturates monoglycerides cause filter clogging • Should be part of production level quality control

28. ASTM D4951Standard Test Method for Determination of Additive Elements in Lubricating Oils by ICP-AES • Feedstock Driven Property, not typically a problem in the US biodiesel production industry • 0.240 Mass % Max • Phosphorous can damage catalytic converters used in emission control systems. Cat Converters becoming more common on diesel-powered equipment • Not a production level quality control parameter

29. ASTM D1160Standard Test Method for Distillation of Petroleum Products at Reduced Pressure • Indicator of adulterants in the final product • 360°C, 90% recovered Max • Distillation curve of biodiesel is unique, saturated hydrocarbons effect the curve type • Not a production level quality control parameter

30. Product Qualities Important to BiodieselOutside of the ASTM D6751 Specification • Lubricity- ASTM D6079, provides indicator of the lubricating properties of the fuel • Biodiesel Content in Blended Middle Distillation • EN 14078-European Standard Method • Applies to blends from 1.7-25 Volume % • IR Method • Methanol Content EN 14110 GC-FID • Linoleic and Linolenic Methyl Esters • Oxidation Stability • Storage Stability-D4245

31. QC at the Production Level • Balance must be attained between testing on site and economics that meets product quality and production process control needs • Costs for establishing full ASTM D6751 capabilities extremely high and cost prohibitive to small production facilities • Costs can be controlled by identifying critical properties • Measure properties onsite that provide information as to production status • Technical Personnel Resources must be available to maintain the quality control function of the production facility • Costs for technical personnel high, mitigate these costs by minimizing technical depth of laboratory on site

32. Reduced Slate TestingOptimizing Testing Costs at Production Site • Define critical properties to be measured onsite • Define Costs associated with laboratory set-up and maintenance • Establish reduced slate testing for production measurement • National Biodiesel Board’s BQ 9000 program incorporates the following analyses in their reduced slate program: • D2709 Water and Sediment • D6584 Free and Total Glycerin • D664 Acid Number

33. Atomic Absorption and ICP for Metals Determination

34. Gas Chromatographs with Auto Samplers

35. CETANE ENGINES

36. Sulfur Analyzers with Auto Sampler

37. There is a Difference . . . Quality is our business

38. Intertek Caleb Brettcan help with your quality issues. • Cathie Johnston • Intertek Caleb Brett • Ph: 864-884-300/732-969-5200 • cathie.johnston@intertek.com