Biodiesel Technical Training Course BIO 2.1: Understanding Diesel Fuel Presented by the National Biodiesel Board

The National Biodiesel Board (NBB) is the trade association for the U.S. Biodiesel Industry Receives funding from 3 sources: – Soybean Check-off program (i.e. farmers) – Government Grants and programs – Biodiesel Producer contributions Technical, Regulatory, Marketing and Lobbying Over $100MM over last 15 years 2

Objectives Understand the new face of diesel fuels What are today’s diesel fuel quality standards How are these standards set? How do these fuel standards affect the diesel engine operation? - performance - emissions - fuel economy

Learning Outcomes Understand the ASTM diesel fuel quality parameters Understand the ASTM biodiesel fuel quality parameters Understand the key differences and similarities between biodiesel and diesel Understand the importance of biodiesel fuel quality and the BQ-9000 program 4

Emissions Regulations in the driver’s seat The Clean Air Act of 1970 gave EPA broad authority to regulate motor vehicle pollution, and the Agency's emission control policies have become progressively more stringent since the early 1970's.

Diesel Emission Reductions

Fuel technology Combustion technology Aftertreatment technology Fuel system technology Better understanding of combustion Alternate Fuels (Biodiesel) Low sulfur De-NOx DOC PM trap Rate control High pressure Multi-injection EGR technology Others Control technology Technology Pathway

What is Diesel Fuel Various Petroleum Components: Paraffins Isoparaffins Napthenes Olefins Aromatic Hydrocarbons

How is diesel made? Petroleum coke is heated up to separate the complex mixture of hydrocarbons into usable products like diesel. Each petroleum derived product is distinguished by its boiling point. Diesel fuel undergoes a hydro-treating process to remove sulfur.

Typical Refinery Products SolidPetroleum Coke Asphalt Residual Oil Lube Oils #2 Diesel, Furnace Oil Kerosene, Jet Fuel, #1 Diesel Gasoline LPG ProductBoiling Range Deg. F Boiling Range Deg. C From: Schmidt, G.K. and Forster, E.J., “Modern Refining for Today’s Fuels and Lubricants,” SAE Paper , 1986.

Grades of Diesel Fuel 1-D ( S15) 1-D ( S500) 1-D (S5000) 2-D ( S15) 2-D ( S500) 2-D (S5000) 4-D S15, S500, & S5000 relate to sulfur content Off-road versus On-road use Varied in density and viscosity

ASTM American Society of Testing & Materials Diesel Fuel Specifications and Quality 13

ASTM Specifications for Diesel Fuel - ASTM D 975

Diesel Fuel Specification ASTM D 975 Flashpoint Water and Sediment Distillation Kinematic Viscosity Ramsbottom Carbon Residue Ash Sulfur Copper Strip Corrosion Cetane Number Cetane Index Aromaticity Cloud Point

Cetane Number Measures the readiness of a fuel to auto-ignite. High cetane means the fuel will ignite quickly at the conditions in the engine (does not mean the fuel is highly flammable or explosive). Most fuels have cetane numbers between 40 and 60. ASTM D 975 requires a minimum cetane number of 40 Premium Diesel fuel typically has a cetane of 47 ASTM methods are ASTM D-613 (ISO 5165) and D- 6890

Cetane Cetane engine shown above from petroleum testing facility Ignition Delay: the period that occurs between the start of fuel injection and the start of combustion; the higher the cetane number, the shorter the ignition delay and the better the quality of combustion.

3 PROPANE METHANOL ETHANOL 8 ISO OCTANE (GASOLINE) 20 CETANE (DIESEL FUEL) Benzene Toluene Xylene

Low Cetane Impact Poor Ignition Quality Long ignition delay Abnormal Combustion Possible High Combustion Pressure Increased Engine stress Excessive Engine Knock Smoke on Cold start

Cetane Index Cetane index is used as a substitute for the cetane number. cetane number The cetane index is calculated based on the fuel's density and boiling range. Two methods used ASTM D-976 or D Cetane improvers that may be added are not accounted for in the index

Boiling Point and Volatility Diesel fuel volatility needs vary for engine load, size, & speed Buses & trucks benefit from more volatile fuel ASTM D975 sets a min-max range Defines the upper and lower limits for 90% distilled point. – No. 1 diesel: no lower limit, upper = 288 C – No. 2 diesel: lower limit = 282 C, upper = 338 C. 282C - 338C

90% Distillation Temperature Volatility or Boiling Point is controlled by the Distillation specification or T90 Primarily used to separate diesel fuels into different grades. Limits the amount of wax allowed in No. 1 If distillation temperatures are too low, then the fuel may have difficulty meeting the flashpoint requirement. If distillation temperatures are too high, then there is an increased tendency of the fuel to deposit on the cylinder wall, where it can be swept down past the rings and into the lube oil.

Viscosity Low viscosity = power loss, component wear due to injector leaking or injection pump leak-down Low viscosity = poor lubrication ability High viscosity = Poor fuel dispersion, i.e. improper injector spray pattern High viscosity = high pump resistance and early pump failure Critical property for fuel injection system performance Measured with ASTM D 445. #1 diesel fuel = 1.3 – 2.4 mm 2 /s #2 diesel fuel = 1.9 – 4.1 mm 2 /s

Carbon Residue Measure of a diesel fuel’s tendency to form engine deposit Tests basically involve heating a sample of fuel to a temperature where the fuel will pyrolyze (decompose without oxygen), leaving a carbon-rich deposit (about 500°C) Test is frequently done on the 10% residue of fuel distillation. Limitation is 0.35 mass percent for No. 2 D Limitation is 0.15 mass percent for No. 1 D

Ramsbottom Carbon Residue There are many tests for carbon residue: – Ramsbottom (D 524) – Conradson (D 189) – Micro Method (D 4530) Diesel fuel specification requires Ramsbottom Carbon reside can vary with refinery processes

Sulfur Content Sulfur can impact engine wear and deposits due varying levels Sulfur in diesel will now harm new emission control devices of 2007 & newer vehicles Sulfur burns to sulfur dioxide and sulfur trioxide, which can combine with water to form sulfuric acid. Small droplets of sulfuric acid and other sulfates contribute to particulate emissions. Sulfur is limited by the EPA for both on & off road diesel fuels: In 1993: Reduced from 5000 ppm to 500 ppm In 2006: Reduced from 500 ppm to 15 ppm

Sulfur Testing ASTM D 129 was traditional method but did not have sensitivity for new low sulfur fuels. (Bomb method) ASTM D 2622, X-Ray Spectrometry, is more sensitive but may not be adequate for 15 ppm diesel fuels.

Flashpoint Measures the temperature at which the vapors above the liquid can be ignited. Primarily used to determine whether a liquid is flammable or combustible Flashpoint is important for safety and hazard rating Both DOT and OSHA say that any liquid with a flash point below 100F is flammable ASTM D 93 is most common test for diesel fuels. Can also be used to identify contamination from other fuels. No. 1 = 38°C, No. 2 = 52°C

Flashpoint

Low temperature Operation Cloud point is the measurement of low temperate operation It dictates the temperature at which fuel first starts to crystallize and wax up when cooled Cloud point can predicate fuel filter clogging in some fuel delivery systems, but not all Other Low temp tests include: CFPP: Cold Filter Plugging Point LTFT: Low Temperature Flow Test Pour Point and Cold Soak Filtration Test

Cloud Point No specific value is given in ASTM D975. Requirements vary depending on geography. 10 th percentile temperature map corresponds to the minimum temperature that would be reached no more than 3 days out of 30 for the month. ASTM D 975 contains similar maps for other low temperature months in the United States.

Ash Abrasive Solids Soluble metallic soaps Originates from inorganic fuel components D 975 requires ash to be < 0.01%, by mass Injector & Fuel pump wear Piston and Ring wear Solids = engine deposits Low ash lubricating oils - NEW

Copper Strip Corrosion Used to predict problems with copper, brass, or bronze components in a fuel system A measure of corrosiveness Polished copper strip is placed in fuel for 3 hours at 50°C, then cleaned with a solvent and inspected for tarnish or corrosion. The strip is given a score between 1 and 4 with subdivisions indicated by letters, i.e. 2c means moderate tarnish with lavender coloring. Diesel fuel is allowed to be No. 3, which allows all tarnish but no actual corrosion.

Water and Sediment Measures free, not emulsified, water and insoluble particles. Uses a centrifuge and cone-shaped or pear-shaped bottles. Total volume of water and sediment must be < 0.05%. (500 ppm) Contamination issue in supply line Engine impact: Filter plugging, fuel injection system wear, and corrosion, and opportunity for microbial growth

Lubricity Lubricity test methods are continually improving and being evaluated Most common tests available to test lubricity: – SLBOCLE (scuffing load ball on cylinder lubricity evaluator) ASTM D – HFRR (high frequency reciprocating rig) ASTM D D975 points to the HFRR test Limitation is 520 micron max of wear at 60C

SLBOCLE SLBOCLE “ Scuffing Load Ball-On Cylinder Lubricity Evaluator ” Steel ball bearing on a steel rotating-ring Immersed in the test fluid Weight is applied until a “ scuff ” mark is seen on the rotating ring Tangential force recorded High Friction coefficient = scuffing 3100 grams without scuffing passes the SLBOCLE. (SWRI)

HFRR High Frequency Reciprocating Rig (HFRR) A steel ball Reciprocated (1mm) 200g load at 50 Hz for 75 minutes 2 mL of Fuel Adjust to 25 °C or 60 °C (77 °F or 140 °F – 60°C preferred Ball contacts test disk (in fuel)

Enhanced Lubricity Equipment benefits – Superior lubricity – B2 has up to 66% more lubricity than #2 Diesel EPA required sulfur reduction in diesel No overdosing concerns

Density Specific gravity – ratio of the density of the fuel to the density of water. – #1 diesel = 0.81 – #2 diesel = – API gravity – common in petroleum industry. API = 141.5/SG – Can be one indicator of fuel economy, power, deposits, wear, and exhaust smoke For example, a low API (or high density) has bore BTUs/gallon which could improve fuel economy

Energy Content Heating value of the fuel Not specified by ASTM Typically expressed as BTUs/gallon Engine Manufacturers Impact fuel ecomony No. 2 D can vary up 15% between supplier & season  No. 2 D 130,000 BTUs/gallon  Gasoline 114,200 BTUs/gallon  Biodiesel (B100) 120,000 BTUs/gallon

Thermal & Oxidative Stability Chemical degradation occurs with contact with oxygen for long periods or at high temperatures. Oxidation of diesel fuel can form insolubles and peroxides Peroxides increase deposits and gumming on fuel pumps and injection systems Filter plugging will also occur ASTM D975 now specifies a stability parameter

Diesel Fuel Additives

Recent Changes in Diesel Fuel specification Acid Number Allowance of up to 5 % biodiesel content Lubricity Stability

Resources for Diesel Fuel Properties ASTM International EPA, Environmental Protection Agency Changes in Diesel Fuel USDA Biodiesel education Internal Combustion Engine Fundamentals, John B. Heywood, McGraw Hill, 1988 ISBN ISBN Automotive Fuels Reference Book, Keith Owen, Trevor Coley SAE, 1995, ISBN ISBN

Biodiesel Resources  Biodiesel Training Toolkit News Releases & Information Resources Technical Library, Spec Sheets & Videos OEM Warranty Positions on Biodiesel U.S. Diesel Vehicle List  Listing of BQ-9000 Certified Companies  Listing of BioTrucker retail sites  Dedicated to information exchange for biodiesel & diesel technicians 45

Thank You! Questions…? Rachel Burton OEM Diesel Technician Training Program Tel: Call NBB at Visit 46