Biodiesel 101 Biofuels…Moving Indiana Forward Merrillville, Indiana April 28, 2008 Presented by Hoon Ge
Summary of Topics • • • General info on biodiesel Emissions OEM stance on biodiesel 2007 Engines Biodiesel Supply & Demand BQ 9000 – Fuel Quality ULSD and Biodiesel; benefits & compatibility Filter plugging sources Good fuel “housekeeping” Useful informational resources
Machinery Exhibit – 1900 World’s Fair Rudolph Diesel demonstrated his compression ignition engine, which at the request of the French Government, ran on peanut oil. www. bc. edu/bc_org/avp/cas/fnart/arch/1900 fair. html - Jeffrey Howe
History of Biodiesel n Vegetable oils were used in diesel engines until the 1920's when engines began using diesel fuel
Biodiesel Defined n n Biodiesel, n. -- a fuel comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats, designated B 100, and meeting the requirements of ASTM D 6751. Biodiesel blend, n. -- a blend of biodiesel fuel meeting ASTM D 6751 with petroleum-based diesel fuel designated BXX, where XX is the volume percent of biodiesel.
Making Biodiesel (Catalyst) 100 pounds Triglyceride + 10 pounds = 10 pounds + Alcohol Glycerin 100 pounds Mono-Alkyl Esters _______________________________________________________ Soy oil Methanol - Raw Vegetable Oil is NOT Biodiesel! - Other ‘biomass’ products aren’t Biodiesel - Must meet ASTM D 6751 Biodiesel
Biodiesel Raw Materials Oil or Fat Soybean Corn Canola Cottonseed Sunflower Beef tallow Pork lard Used cooking oils Alcohol Methanol (common) Ethanol Catalyst Sodium hydroxide Potassium hydroxide
Biodiesel Attributes • • • High Cetane (avg. over 50) Ultra Low Sulfur (avg. ~ 2 ppm) High Lubricity, even in blends as low at 1 -2% High Energy Balance (3. 2 to 1) Low Agriculture Inputs: Soybeans 78% Life Cycle CO 2 Reduction Renewable, Sustainable Domestically Produced Reduces HC, PM, CO in existing diesel engines Reduces NOx in boilers and home heating
Biodiesel ASTM D 6751 Property • • • • • ASTM Method Calcium & Magnesium, combined EN 14538 Flash Point (closed cup) D 93 Alcohol Control (One of the following must be met) • Methanol Content EN 14110 • Flash Point D 93 Water & Sediment D 2709 Kinematic Viscosity, 40 C D 445 Sulfated Ash D 874 Sulfur • S 15 Grade D 5453 • S 500 Grade D 5453 Copper Strip Corrosion D 130 Cetane D 613 Cloud Point D 2500 Carbon Residue 100% sample D 4530* Acid Number D 664 Free Glycerin D 6584 Total Glycerin D 6584 Phosphorus Content D 4951 Distillation, T 90 AET D 1160 Sodium/Potassium, combined EN 14538 Oxidation Stability EN 14112 Limits Units 5 max ppm 93 min. (ug/g) Degrees C 0. 2 Max 130 Min 0. 05 max. 1. 9 - 6. 0 0. 02 max. % volume Degrees % vol. mm 2/sec. % mass 0. 0015 max. (15) 0. 05 max. (500) No. 3 max. 47 min. Report 0. 05 max. 0. 50 max. 0. 020 max. 0. 240 max. 0. 001 max. 360 max. 5 max 3 min % mass (ppm) Degrees C % mass mg KOH/g % mass Degrees C ppm hours
Materials Compatibility • B 100 may adversely affect some elastomers such as natural or nitrile rubbers over time. • Most elastomers used after 1993 are compatible with B 100 (Viton/Teflon). • Blends (B 20) effect is less or non-existent. • Normal monitoring of hoses and gaskets for leaks is sufficient with B 20. • Consult with your parts supplier or mechanical engineering partners.
Materials Compatibility • Biodiesel and biodiesel blends will form high sediment levels when in contact with the following metals: -Brass, Bronze, Copper, Lead, Tin and Zinc • Biodiesel is compatible with: - Stainless Steel, Aluminum
Emissions
EPA HD Emissions Averages Emission Type B 100 B 2 Total Unburned Hydrocarbons -67% -20% -2. 2% Carbon Monoxide -48% -12% -1. 3% Particulate Matter -47% -12% -1. 3% Oxides of Nitrogen (NOX) +10% + 2% +. 2%
Biodiesel and Global Warming • Closed Carbon Cycle: CO 2 Used to Grow Feedstock is Put Back Into Air • • • 78% Life Cycle Decrease In CO 2 Energy Balance 3. 24 to 1 Compression Ignition Platform 30% to 40% More Efficient Than Spark Ignition
Biodiesel Position with OEM’s Original Equipment Manufacturers: • B 100 Must Meet ASTM D 6751 • Most OEM HQ’s have B 20 experience: Won’t void warrantee Problems caused by the fuel are the responsibility of the fuel supplier Want to see additional experience in the field • Higher blends OK’d based on experience of OEM and their technology
2007 Engines
Engines Produced in 2007 • EPA regulations require reduced sulfur in diesel fuel for engines built in 2007 • 80% of highway diesel fuel must be ULSD (< 15 ppm sulfur) beginning june 1, 2006 • Catalyzed Diesel Particulate Filters can eliminate 99% of solid particles (soot & metals) and eliminate >90% of semi-volatile hydrocarbons. Source: EPA
Diesel Particle Filters (DPF) • Diesel particle filters (DPF) are found in all 2007 model year diesel vehicles. • What possible advantages or disadvantages may result from using biodiesel blends in these engines? • The National Renewable Energy Laboratory (NREL) has conducted a study in order to define these effects on DPFs.
Indicators of DPF Performance • Filter regeneration rate increased significantly when using blends as low as B 5. Lower particulate temperature and less particulate input contributed. “Biodiesel Effects on Diesel Particle Filter Performance. ” National Renewable Energy Laboratory, March 2006.
Biodiesel Supply and Demand
Demand for Crude 1 barrel (bbl) = 42 gallons (U. S. ) n Globally about 80, 000 bbl/day n Over 16, 000 bbl of crude oil processed every day in the US (650, 000 gal/day) n 800, 000 gal/day total product demand n n n 360, 000 gal/day gasoline 140, 000 gal/day distillate 68, 000 gal/day jet fuel Over 5 billion gallons of distillate fuel oil are imported each year 150 U. S. refineries with capacities ranging from 15 mbbl/day (600, 000 gallons/day) to over 500 mbbl/day (21, 000 gallons/day and operate at 90+% capacity
Biodiesel Demand
If Every Trucker Used B 2 The industry would utilize 761 million gallons of B 100 annually.
If Everyone Used B 2 n If every body using diesel fuels (on and off road) and home heating oil used 2% biodiesel then we would use 1. 2 billion gallons of biodiesel each year.
Fuel Availability n n Fuel available through direct shipment from over 1, 956 petroleum distributors nationwide Over 1, 234 retail filling stations nationwide 648 locations are semi-truck accessible Movement towards biodiesel at the terminal – over 158 terminals nationwide
n Blending is occurring at over 40 terminals nationwide.
Biodiesel Production Capacity
Production Locations (1/25/08)
Biodiesel Plants Under Construction and Expansion (9/7/07)
Production Capacity by State (9/7/07)
BQ-9000 Fuel Quality of Biodiesel
Fuel Quality • Fuel quality is of the utmost concern and importance to the biodiesel industry. • ASTM D 6751 is the specification for biodiesel fuels irrespective of the feedstock source and/or processing method. • National Quality Program (BQ-9000) Launched for Biodiesel Marketers and Producers • Look for BQ-9000 Certified Marketers: Biodiesel’s ‘Good Housekeeping’ Seal of Approval • Assures “cradle-to-grave” fuel quality “cradle” “grave”
BQ-9000 “Quality Assurance Program” “Specifies requirements for a quality assurance program where an organization needs to demonstrate its ability to provide product that meets ASTM D 6751… and applicable regulatory requirements, and to address quality assurance through the effective application of the program…” HELPS ENSURE THAT END-USER IS GETTING HIGH-QUALITY BIODIESEL!!
ALWAYS BUY PRODUCT FROM BQ-9000 CERTIFIED PRODUCERS OR MARKETERS!!!
BQ-9000 Information Through the NBB www. bq-9000. org www. biodiesel. org www. nbb. org Find information on the requirements for the program and a list of accredited producers/marke ters on the NBB website.
Biodiesel and ULSD Benefits and Compatibility
Benefits: Biodiesel and ULSD • • • Compatible with the compression ignition platform and with diesel fuel itself Greatly enhances lubricity of ULSD Compatible with 2007 diesel engine catalysts Aids with ULSD conductivity issues Reduces harmful emissions Power and performance virtually unchanged Seamless & transparent with existing petroleum infrastructure, (liquid not gaseous) Promotes national energy security Renewable, non-toxic, green blend stock option
Properties of ULSD & Biodiesel Blends ULSD B 2 B 5 B 20 33. 4 33. 2 32. 3 IBP 326°F 327°F 336°F 10% 402°F 403°F 404°F 418°F 50% 509°F 510°F 550°F 90% 605°F 604°F 608°F 638°F EBP 611°F 610°F 614°F 645°F Cetane Index 42. 7 42. 8 44. 4 Cloud Point 0°F 1°F 3°F -26°F -24°F -20°F API Gravity Distillation CFPP (3 -4 x Additive)
Lubricity
ULSD & Lubricity • • Sulfur compounds are natural lubricants in diesel. ULSD regulations are causing major concerns with diesel engine performance. ASTM lubricity requirement effective Jan 1, 2005 for diesel fuels. ASTM D 6079 High Frequency Reciprocating Rig (HFRR) Wear Scar Maximum = 520 micrometers
Biodiesel Adds Significant Lubricity to ULSD The average lubricity of Biodiesel blends compare to lubricity additives.
Lubricity Effects of Biodiesel on the Lubricity of Diesel fuel.
Cold Flow Properties
CFPP Testing of ULSD Bio Blends Sample Description Cloud Point °F Base Fuel CFPP °F w/ Additive -2 -22 B 11 ULSD (3 x) +1 -20 B 20 ULSD(4 x) +3 -17 B 5 ULSD -1 -18 B 2 ULSD -2 -20 B 2 ULSD -2 -22 ULSD
CFPP Testing of ULSD B 2 blends with No 1 ULSD Sample Description Cloud Point °F Base Fuel CFPP °F Base Fuel w/additive ULSD Sample 1 0 -20 ULSD 90/10 -4 -25 ULSD 80/20 -7 -30 ULSD 70/30 -11 -34 ULSD 60/40 -15 -38 ULSD 50/50 -18 < -40 (90% No 1 & 10% No 2)
Filter Plugging Sources
n n n Paraffin Wax The material on these filters was solid until touched or warmed to room temperature, then it melted. Laboratory analysis showed this material was in fact paraffin/hydrocarbon in nature. The high level of paraffin material could be from the way ULSD is processed. When the temperature of the fuel is at or below its cloud point, paraffin material will precipitate out and collect on the bottom of the tank. As a point of note, when the heavy paraffin's are disturbed from the filters, they liquefy. The minor ingredients associated with biodiesel will not liquefy and require heat to go back into solution. Paraffin build-up does not come from biodiesel fuel.
Aromatic compound H 2 C 6 H 6 Olefin Compound C 6 H 12 Cyclic, double bonds Straight, double bond n-Paraffin Compound C 6 H 14 Straight, single bonds H 2 Structures taken from www. chemfinder. com
Microbial Growth n n Several filters showed high content of live microbial organisms or a build-up of dead microbial material. The filters with microbial contamination often had an odor different from the normal fuel smell. MEG Corp believes that the lack of sulfur in biodiesel and ULSD aids in the build-up of such organisms since sulfur is a key component of many biocides and is a natural inhibitor of bacterial and fungal growth.
Bacteria § § Breakdown all grades of liquid fuel. Cause corrosion of metals, especially iron and steel. Different species can survive with oxygen (aerobic) or without oxygen (anaerobic). Plug fuel-system filters and lines, cause fuel gauge malfunctions, damage pumps and injectors, and feed on tank linings, hoses and coatings to obtain additional nourishment.
Bacteria § Grow better in warm climates because they are living organisms. “Climates” does not just mean the temperature of the storage structure, but also heated fuel returns, which means it is warm all year long. § § Usually present in high quantities. Favorable conditions mean they can double their population every 20 minutes.
Bacteria § Ø The level of contamination is hard to determine visually… 2 MILLION bacteria per milliliter have no effect on fuel clarity! Or in other words… Ø 8 Billion bacteria per gallon have no effect on fuel clarity!
Fungus § § § Hard to detect. Fewer in number and less evenly distributed in the fluid than bacteria. Tend to grow on solid surfaces. - Build up on filters and in piping. - Once established, the biomass will grow faster than a bacterial biomass. § Yeast are unicellular fungi.
Fungus § § Larger than bacteria and do not reproduce as rapidly. However, if only bacteria are killed suddenly (bactericide) there may be a rapid fungal bloom that is nearly impossible to control. Can grow over a wide range of temperatures. Grow quicker in summer with the higher ambient temperature, increased airborne contaminants and higher fluid temperature.
Where Do They Come From? § Air – Contains airborne microorganisms, yeast and mold spores, and dirt particles that can enter through tank vents. § Water – Water, unless sterilized, can contain a variety microorganisms.
Treatment and Prevention § Biocides -Three major groups: Fuel soluble, Water soluble, and Universally soluble. -Need to be EPA registered and compatible with the lubricant. § Preventing Fuel Contamination - Preventing contamination from air and water requires proper tank maintenance and cleaning
Icing of the filter n n When there is excess free water in fuel, it can form ice on the filter and cause filter plugging in cold temps. When MEG Corp received filters which had been plugged but were clean and new by the time MEG Corp received them, it was concluded that the cause was likely icing which had since dissipated. Since the temperatures of engines are warm, any moisture picked up within the engine can be brought back to the fuel lines. This moisture can freeze overnight in low ambient temperatures.
Oxidation n When MEG Corp received filters with a black and shiny surface but no microbial growth odor or gel or sediment, it was concluded they may be plugged by oxidation build -up. Because many newer engines run at higher temperatures, there may be a black “asphaltene” type material collecting on the filter. This phenomenon has been seen all around the country, often in newer engines.
Engines Hot Fuel Return New Technology delivers the unused fuel from the engine block back to the fuel tank much faster Hot Coking Fuel This hot fuel will cause degradation and oxidation of the fuel, which in turn will plug filters.
Monoglyceride Build-up n n One filter tested positive for a concentration of saturated monoglyceride material. Monoglyceride is one substance that can precipitate out of fuel if the glycerin levels are too high in the biodiesel used in the blend.
Quality Control n In 2006: 41% of B 100 samples tested passed the D 6751 specification n In 2007: 89. 6% of B 100 samples tested passed the D 6751 specification 100% of BQ-9000 certified fuel Past all ASTM D 6751 specifications
Troubleshooting Checklist n Paraffin Wax – Temperature at or below cloud point n n Microbial Growth – Exposure to air and water Icing of Filter – Excess water in tank Oxidation – Hot fuel return to fuel tank Monoglyceride Build Up – Off specification of Total & Free Glycerin
Tips for Biodiesel Handling
Tips for Biodiesel Handling n n n Buy biodiesel that meets ASTM D 6751. Buying from a BQ-9000 Accredited Producer/Marketer will help ensure quality. If buying blended biodiesel, buy it preblended from the supplier. Fuel tanks should be kept as full as possible to reduce the amount of air and water entering the tank.
Tips for Biodiesel Handling n n n Storage in on-site tanks should be limited to less than 6 months. The storage container should be clean, dry, and dark. Copper, brass, lead, tin and zinc should not be used to store biodiesel. Equipment with biodiesel blends in the fuel system should not be stored for more than 6 months.
Tips for Biodiesel Handling n n In the winter months, it’s important to use appropriate additives to ensure good winter-weather operability. If any biodiesel is spilled, it is important to clean it up quickly. Pure biodiesel may remove paint from equipment.
Tips for Biodiesel Handling § When switching from diesel fuel to biodiesel blend, it may be necessary to change the fuel filter an extra time or two. n One outcome of improper handling of biodiesel may be microbial contamination.
Useful Information Resources
Educational Resources • • • BEN: Biodiesel Education Network Web-based resource specifically for petroleum marketers Partnership between NBB/PMAA www. pmaa. org www. biodiesel. org
NBB Resources: www. biodiesel. org • Technical Library • Biodiesel Bulletin • Informational Resources • Technical Resources • Educational Videos Available • On-line Database & Spec Sheets
Other Biodiesel Resources • • www. bbibiofuels. co m Biodiesel Magazine A ‘MUST HAVE’ magazine • Biodiesel Industry Directory On-Line
Biodiesel Help-line Established to: n Provide triage for fuel problems not adequately addressed by distributors/producers n n n n Diagnose/analyze/assist with problems from: customers fleets fuel distributors Provide assistance through chemical analysis Through the use of third party Lab Help provide assistance to users to ensure the image/integrity of Biodiesel is maintained.
Contact Information n The National Biodiesel Helpline is: For when you cannot get help elsewhere. n Not meant for general guidance issues. n You should always begin by asking your fuel supplier, they will most likely be able to answer your question more accurately. 800 -929 -3437 952 -473 -0182
Questions
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