Biodiesel Fuel Quality - PDF Free Download

2012 Collective Biofuels Conference Temecula, California Biodiesel Fuel Quality August 17-19, 2012 Presented by Gorge Analytical, LLC

Significant effort and technical consideration has gone in to developing fuel quality specifications and standard methods to establish and maintain product quality. These fuel quality specifications establish the industry expectation ASTM D975 and D396 for blends up to B5 ASTM D7467 for blends B6-B20 ASTM D6751 for B100 intended for blending Dozens of standard methods establish a consistent basis for measuring fuel quality characteristics and properties ASTM for Free and Total Glycerin ASTM D664 for Total Acid Number EN 15751 for Oxidation Stability ASTM D7501 for Cold Soak Filterability to list a few.

Legislation currently shaping the industry contains critical elements that require fuels satisfy measurable and verifiable standard regulations Federal Register - RFS2 Calls for 1 billion gallons by 2012 This rulemaking proposes changes to the Renewable Fuel Standard (RFS) program at Title 40 of the Code of Federal Regulations, Subpart K which already contains voluntary consensus standard ASTM D6751 06a Standard Specification for Biodiesel Fuel Blend Stock (B100) for Middle Distillate Fuels. (Federal Register / Vol. 74, No. 99 / Tuesday, May 26, 2009 / Proposed Rules) Oregon Revised Statute (ORS) The Director of Agriculture may test motor vehicle fuel for the purpose of inspecting the motor vehicle fuel supply of any service station, business or other establishment that sells or offers for sale, or distributes, transports, hauls, delivers or stores motor vehicle fuel that is subsequently sold or offered for sale, for compliance with the motor vehicle fuel quality standards adopted pursuant to ORS 646.957. (http://www.leg.state.or.us/ors/646.html) Original Equipment Manufacturers (OEM) Biodiesel blend must meet all current petroleum industry specifications (ASTM D6751 and ASTM D975) and be purchased from a reputable commercial retail pump. (http://biodiesel.org/resources/oems/)

Quality = Money $ IRS Obligated Party RFS2 RINS Internal Revenue Code (Code) Sections 40A, 6426, and 6427(e) $ Tax Incentives For production, sale, and use of $ $ biodiesel and biodiesel mixtures $ Internal Revenue Code (Code) Sections 40A(d)(1) Biodiesel Monoalkyl esters of long chain fatty acids derived from plant or animal matter that meet: (i) the registration requirements for fuels and fuel additives established by the Environmental Protection Agency under section 211 of the Clean Air Act (42 U.S.C. 7545), and (ii) the requirements of ASTM D6751.

Fuel quality is vital to the increased use of biodiesel in a marketplace where demand is growing. New specifications promote (and expect) high quality biodiesel Petroleum Distribution Chain Production Facility Or Refinery Where in the lifecycle do you come in contact with the fuel.? Truck Rail Barge Pipeline How can you trust your fuel source? Validate fuel meets quality specifications. How can you maintain fuel quality? Track unique production lots. How can you diagnose and troubleshoot? Monitor and document that fuel quality is maintained Breakout Terminals Supply Terminals Distributors End Users Wholesale Marketers Resource: Biodiesel Troubleshooting Decision Tree

Good quality management practices are necessary to maintain fuel quality. Diagnostic testing is necessary to monitor fuel quality for contamination, degradation, or stability problems. Petroleum Distribution Chain Production Facility Or Refinery Seasonal low temperature conditions create challenges for distillate fuels. Winter filter plugging and operability challenges are not unique to biodiesel. Filter plugging can result from multiple un-related causes; and not all causes are related to cold temperatures. Effective filter plugging troubleshooting requires an understanding of limitations and causes. Breakout Terminals Supply Terminals Distributors End Users Truck Rail Barge Pipeline Wholesale Marketers Resource: Biodiesel Troubleshooting Decision Tree

Key Considerations to Promote Distribution of Quality Fuel Validate fuel meets quality specifications (D975, D396, D7467, D6751) Require a Certificate of Analysis (CoA). Review and Understand the content of the CoA. Locate the unique production lot identifier(s). Locate the required test results. Evaluate results to verify specification limits are met. Verify test results with periodic independent sampling and analysis. Track the production lot Use Bill of Lading for shipments (truck, rail, barge, etc..). Use site-specific procedures for terminals, tank farms, etc. Ensure traceability and the ability to isolate. Monitor and Document your inventory Consider BQ-9000 s Guidance. Collect and retain samples for each production lot. Perform periodic diagnostic testing. Water / Sediment (e.g. D2709, D6304, D4176) Stability (e.g. EN15751, D664)

A production lot is a homogeneous production volume of finished biodiesel from one or more sources that is held in a single container where representative samples are taken and analyzed to provide an authentic certificate of analysis (COA) for the specific volume. KEY WORDS: Homogeneous Single container Representative samples Certificate of Analysis Specific volume Photo Resource: http://www.ageratec.com Establish objective evidence validating the quality of a discrete quantity of fuel. Photo Resource: http://www.wisconsinbiofuels.com

Homogeneity Necessary to demonstrate that separate shipments from a production lot are represented by a single Certificate of Analysis (COA). Upper, middle, and lower tank samples analyzed for Relative Density IAW ASTM D1298 or D4052. Homogeneity is achieved if the relative density for the three layers are within a range of 0.006 (BQ-9000) If mechanically mix or agitate, then 5 consecutive production lots can be used to demonstrate steady state homogeneity. Thereafter, homogeneity can be assumed if there are no significant process changes. Also, check homogeneity when blending biodiesel made from different feedstock that were not pre-blended; particularly if cloud points are different by 5 o C or more. All Level Sample 10,000 gallons Upper layer Middle layer Lower layer Composite

Traceability The ability to correlate test results to a specific production lot with objective evidence. Production Details Lot Identifier Feedstock Lot Volume Production Date Sample Details Sample Identifier Sample Type Sample Location Collection Date Collection Time Testing Details Laboratory Identifier Test method Analysis Date Result All Level Sample 10,000 gallons Upper layer Middle layer Lower layer Composite Keep a Retain (1-2 liters)

Cetane Number D613 Distillation Temperature D1160 Copper Strip Corrosion D130 Kinematic Viscosity D445 Sulfated Ash D874 Micro-carbon Residue D4530 Phosphorus D4951 Calcium and Magnesium EN 14538 Sodium and Potassium EN 14538 Cloud Point D2500 Water and Sediment D2709 Sulfur D5453 Cold Soak Filtration Test D7501 Oxidation Stability EN 15751 Acid Number D664 Alcohol Content / Flash Point EN 14110 / D93 Free Glycerin Total Glycerin D4176 Tank Homogeneity D4052 Let s melt this list down

Cetane Number D613 Distillation Temperature D1160 Copper Strip Corrosion D130 Kinematic Viscosity D445 Sulfated Ash D874 Micro-carbon Residue D4530 Phosphorus D4951 Calcium and Magnesium EN 14538 Sodium and Potassium EN 14538 Cloud Point D2500 Water and Sediment D2709 Sulfur D5453 Cold Soak Filtration Test D7501 Oxidation Stability EN 14112 Acid Number D664 Alcohol Content / Flash Point EN 14110 / D93 Free Glycerin Total Glycerin D4176 Tank Homogeneity D4052 Are you controlling Free Fatty Acids and other organic acid formation?

Cetane Number D613 Distillation Temperature D1160 Copper Strip Corrosion D130 Kinematic Viscosity D445 Sulfated Ash D874 Micro-carbon Residue D4530 Phosphorus D4951 Calcium and Magnesium EN 14538 Sodium and Potassium EN 14538 Cloud Point D2500 Water and Sediment D2709 Sulfur D5453 Cold Soak Filtration Test D7501 Oxidation Stability EN 14112 Acid Number D664 Alcohol Content / Flash Point EN 14110 / D93 Free Glycerin Total Glycerin D4176 Tank Homogeneity D4052 Does your process preserve enough inherent stability or do you need an antioxidant?

Cetane Number D613 Distillation Temperature D1160 Copper Strip Corrosion D130 Kinematic Viscosity D445 Sulfated Ash D874 Micro-carbon Residue D4530 Phosphorus D4951 Calcium and Magnesium EN 14538 Sodium and Potassium EN 14538 Cloud Point D2500 Water and Sediment D2709 Sulfur D5453 Cold Soak Filtration Test D7501 Oxidation Stability EN 14112 Acid Number D664 Alcohol Content / Flash Point EN 14110 / D93 Free Glycerin Total Glycerin D4176 Tank Homogeneity D4052 Will your product support the ULSD requirements when blended with petroleum diesel?

Cetane Number D613 Distillation Temperature D1160 Copper Strip Corrosion D130 Kinematic Viscosity D445 Sulfated Ash D874 Micro-carbon Residue D4530 Phosphorus D4951 Calcium and Magnesium EN 14538 Sodium and Potassium EN 14538 Cloud Point D2500 Water and Sediment D2709 Sulfur D5453 Cold Soak Filtration Test D7501 Oxidation Stability EN 14112 Acid Number D664 Alcohol Content / Flash Point EN 14110 / D93 Free Glycerin Total Glycerin D4176 Tank Homogeneity D4052 Is your process adequately removing water and sediment?

Cetane Number D613 Distillation Temperature D1160 Copper Strip Corrosion D130 Kinematic Viscosity D445 Sulfated Ash D874 Micro-carbon Residue D4530 Phosphorus D4951 Calcium and Magnesium EN 14538 Sodium and Potassium EN 14538 Cloud Point D2500 Water and Sediment D2709 Sulfur D5453 Cold Soak Filtration Test D7501 Oxidation Stability EN 14112 Acid Number D664 Alcohol Content / Flash Point EN 14110 / D93 Free Glycerin Total Glycerin D4176 Tank Homogeneity D4052 How well will your product support low temperature performance?

Cetane Number D613 Distillation Temperature D1160 Copper Strip Corrosion D130 Kinematic Viscosity D445 Sulfated Ash D874 Micro-carbon Residue D4530 Phosphorus D4951 Calcium and Magnesium EN 14538 Sodium and Potassium EN 14538 Cloud Point D2500 Water and Sediment D2709 Sulfur D5453 Cold Soak Filtration Test D7501 Oxidation Stability EN 14112 Acid Number D664 Alcohol Content / Flash Point EN 14110 / D93 Free Glycerin Total Glycerin D4176 Tank Homogeneity D4052 These tests are to be performed on every production lot if you wish to meet the BQ-9000 quality program expectations.

Cetane Number D613 Distillation Temperature D1160 Copper Strip Corrosion D130 Kinematic Viscosity D445 Sulfated Ash D874 Micro-carbon Residue D4530 Phosphorus D4951 Calcium and Magnesium EN 14538 Sodium and Potassium EN 14538 Cloud Point D2500 Water and Sediment D2709 Sulfur D5453 Cold Soak Filtration Test D7501 Oxidation Stability EN 14112 Acid Number D664 Alcohol Content / Flash Point EN 14110 / D93 Free Glycerin Total Glycerin D4176 Tank Homogeneity D4052 Monthly Every production lot

Cetane Number D613 Distillation Temperature D1160 Copper Strip Corrosion D130 Kinematic Viscosity D445 Sulfated Ash D874 Micro-carbon Residue D4530 Phosphorus D4951 Calcium and Magnesium EN 14538 Sodium and Potassium EN 14538 Cloud Point D2500 Water and Sediment D2709 Sulfur D5453 Cold Soak Filtration Test D7501 Oxidation Stability EN 14112 Acid Number D664 Alcohol Content / Flash Point EN 14110 / D93 Free Glycerin Total Glycerin D4176 Tank Homogeneity D4052 Every Six Months Monthly Every production lot

Cetane Number D613 Distillation Temperature D1160 Copper Strip Corrosion D130 Kinematic Viscosity D445 Sulfated Ash D874 Micro-carbon Residue D4530 Phosphorus D4951 Calcium and Magnesium EN 14538 Sodium and Potassium EN 14538 Cloud Point D2500 Water and Sediment D2709 Sulfur D5453 Cold Soak Filtration Test D7501 Oxidation Stability EN 14112 Acid Number D664 Alcohol Content / Flash Point EN 14110 / D93 Free Glycerin Total Glycerin D4176 Tank Homogeneity D4052 Once per Year Every Six Months Monthly Every production lot

Cloud Point D2500 Water and Sediment D2709 Sulfur D5453 Cold Soak Filtration Test D7501 Oxidation Stability EN 14112 Acid Number D664 Alcohol Content / Flash Point EN 14110 / D93 Free Glycerin Total Glycerin D4176 Tank Homogeneity D4052

Cetane Number Distillation Temperature Copper Strip Corrosion Kinematic Viscosity Sulfated Ash Micro-carbon Residue Phosphorus D613 D1160 D130 D445 D874 D4530 D4951 Calcium and Magnesium EN 14538 Sodium and Potassium EN 14538 Cloud Point Water and Sediment Sulfur Cold Soak Filtration Test D2500 D2709 D5453 D7501 Oxidation Stability EN 14112 Acid Number Alcohol Content or Flash Point Free Glycerin Total Glycerin Tank Homogeneity D664 EN 14110 or D93 D4176 D4052 If you are confident fuel meets specification, what periodic tests help diagnose contamination, degradation, or stability problems?.and Water Determination by ASTM D6304 Coulometric Karl Fischer Titration

Good quality management practices are necessary to maintain fuel quality. Diagnostic testing is necessary to monitor fuel quality for contamination, degradation, or stability problems. Water and Sediment D2709 Oxidation Stability EN 14112 Acid Number D664.and Water Determination by ASTM D6304 Coulometric Karl Fischer Titration Tank Homogeneity D4176 D4052

Identify the seller the entity from whom you purchase Purchase order or other Seller s status EPA registration Verify quality ASTM D7467 (B6-B20) ASTM D6751 (B100) Resource: http://www.sustainableportland.org Establish consistent Control Points

Dissolved Water Not visible to the eye Low part per million (ppm) levels ASTM D6304 Karl Fischer Coulometric Titration Entrained / Emulsified Water Visible haze or cloudy complexion Haze rating is a standard reference ASTM D4176 Visual Inspection Free Water Build-up on the bottom of storage and transportation vessels Gross contamination / detectable with water finding paste ASTM D2709 Water and Sediment Water Concentration 47 ppm 705 ppm Haze Rating = 1 Haze Rating > 6

B20 Method ASTM D6304 Test Description Karl Fischer Moisture - Coulometric Analysis Date Result Rptg Units Rptg Criterion 7/1/2011 13.15 % Mass 0.05 max ASTM D664 Total Acid Number 7/1/2011 0.23 mg KOH/g 0.30 max

B100 Method Test Description Analysis Date Result Rptg Units Rptg Criterion ASTM D2500 Cloud Point 9/30/2011 13 Deg C n/a ASTM D2709 Water and 9/29/2011 0.040 % Volume 0.05 max Sediment of Middle Distillate Fuels by Centrifuge ASTM D6304 Karl Fischer 9/29/2011 0.0654 % Mass n/a Moisture - Coulometric ASTM D6371 Cold Filter 9/30/2011 10 Deg C n/a Plugging Point ASTM D93 Flash Point, 9/29/2011 94.5 Deg C 93 min Pensky Martens EN 14103:2003 Ester Content 9/29/2011 87.7 % Mass 96.5 min

B100 Method Test Description Analysis Date Result Rptg Units Rptg Criterion ASTM D5453 Sulfur by UVF 10/11/2011 4.7 ppm (wt/wt) 15 max ASTM D6304 Karl Fischer 10/11/2011 0.0592 % Mass n/a Moisture - Coulometric ASTM D6371 Cold Filter Plugging 10/12/2011 13 Deg C n/a Point ASTM D7321 Particulate 10/12/2011 18.0 mg/l n/a Contamination ASTM D93 Flash Point, Pensky 10/11/2011 166.0 Deg C 93 min Martens EN 14103:2003 Ester Content 10/11/2011 84.9 % Mass 96.5 min EN 15751:2009 Oxidation Stability (Accelerated Method) at 110 deg C 10/11/2011 8.8 Hours 3 min

B100 Method Test Description Analysis Date Result Rptg Units Rptg Criterion ASTM D6304 ASTM - 0 Total Glycerin Karl Fischer Moisture - Coulometric Total Glycerin (Free and Bound) 3/22/2011 0.0674 % Mass n/a 3/22/2011 1.057 % Mass 0.240 max ASTM - 00 Free Glycerin ASTM - 1 Monoglycerides, Total ASTM - 2 Diglycerides, Total ASTM - 3 Triglycerides, Total Free Glycerin 3/22/2011 0.023 % Mass 0.020 max Total Monoglycerides 3/22/2011 3.884 % Mass n/a Total Diglycerides 3/22/2011 0.106 % Mass n/a Total Triglycerides 3/22/2011 0.111 % Mass n/a

B20 Method Test Description Analysis Date Result Rptg Units Rptg Criterion ASTM D4176 - Part 1 Visual Inspection - Part 1 ASTM D4176 - Part 2 Visual Inspection - Part 2 ASTM D6304 Karl Fischer Moisture - Coulometric ASTM - 1 Monoglycerides, Total ASTM - 2 Diglycerides, Total ASTM - 3 Triglycerides, Total 6/3/2011 2 Haze Rating n/a 6/3/2011 Particulate Present n/a Free of Particulate 6/7/2011 0.0121 % Mass n/a Total Monoglycerides 6/3/2011 0.132 % Mass n/a Total Diglycerides 6/3/2011 0.036 % Mass n/a Total Triglycerides 6/3/2011 0.019 % Mass n/a ASTM D664 Total Acid Number 6/3/2011 0.06 mg KOH/g 0.30 max ASTM D7371 Biodiesel Content 6/8/2011 16.15 % (V/V) 6. - 20. (FTIR-ATR-PLS)

Method Test Description Analysis Date Result Rptg Units ASTM - 1 Monoglycerides, Total Total Monoglycerides 6/14/2011 11.564 % Mass ASTM - 2 Diglycerides, Total Total Diglycerides 6/14/2011 0.082 % Mass ASTM - 3 Triglycerides, Total Total Triglycerides 6/14/2011 0.019 % Mass

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