Hoon Ge

Biodiesel Workshop: 

Biodiesel Workshop September 19th, 2007 Columbia, SC Hoon Ge

Biodiesel 101: 

Biodiesel 101

Making Biodiesel: 

Making Biodiesel (Catalyst) 100 pounds + 10 pounds = 10 pounds + 100 pounds Triglyceride Alcohol Glycerin Mono-Alkyl Esters _____________________________________________________________________________________________________________ Soy oil Methanol Biodiesel - Raw Vegetable Oil is NOT Biodiesel! - Other ‘biomass’ products aren’t Biodiesel - Must meet ASTM D 6751

Biodiesel Raw Materials : 

Biodiesel Raw Materials Oil or Fat Alcohol Soybean Methanol (common) Corn Ethanol Canola Cottonseed Catalyst Sunflower Sodium hydroxide Beef tallow Potassium hydroxide Pork lard Used cooking oils

Biodiesel Attributes: 

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 CO2 Reduction Renewable, Sustainable Domestically Produced Reduces HC, PM, CO in existing diesel engines Reduces NOx in boilers and home heating

Biodiesel ASTM D6751: 

Biodiesel ASTM D6751 Property ASTM Method Limits Units Calcium & Magnesium, combined EN 14538 5 max ppm (ug/g) Flash Point (closed cup) D 93 93 min. Degrees C Alcohol Control (One of the following must be met) Methanol Content EN14110 0.2 Max % volume Flash Point D93 130 Min Degrees Water & Sediment D 2709 0.05 max. % vol. Kinematic Viscosity, 40 C D 445 1.9 - 6.0 mm2/sec. Sulfated Ash D 874 0.02 max. % mass Sulfur S 15 Grade D 5453 0.0015 max. (15) % mass (ppm) S 500 Grade D 5453 0.05 max. (500) % mass (ppm) Copper Strip Corrosion D 130 No. 3 max. Cetane D 613 47 min. Cloud Point D 2500 Report Degrees C Carbon Residue 100% sample D 4530* 0.05 max. % mass Acid Number D 664 0.50 max. mg KOH/g Free Glycerin D 6584 0.020 max. % mass Total Glycerin D 6584 0.240 max. % mass Phosphorus Content D 4951 0.001 max. % mass Distillation, T90 AET D 1160 360 max. Degrees C Sodium/Potassium, combined EN 14538 5 max ppm Oxidation Stability EN 14112 3 min hours

ASTM - D6751: 

ASTM - D6751 Review your fuel analysis to ensure incoming fuel meets agreed upon specifications If either the biodiesel or generic diesel fuel fails to meet the agreed specification, notify your fuel supplier immediately Retain samples (quart) minimum should analytical work be required to evaluate future issues

Emissions: 

Emissions

EPA HD Emissions Averages: 

EPA HD Emissions Averages

Biodiesel and Global Warming: 

Biodiesel and Global Warming Closed Carbon Cycle: CO2 Used to Grow Feedstock is Put Back Into Air 78% Life Cycle Decrease In CO2 Energy Balance 3.24 to 1 Compression Ignition Platform 30% to 40% More Efficient Than Spark Ignition

Emission Benefits of B20: 

Emission Benefits of B20 Broad agreement on emission reductions: 10% to 25% reduction in PM, depending on engine, test cycle, and other factors 10% to 20% reductions in CO, HC, and toxic compounds Impact on NOx emissions is less certain

Biodiesel Emissions: 

Biodiesel Emissions B20 Blends: Reduce life-cycle petroleum consumption by 19% Reduce life-cycle CO2 emissions by 16% Further reduce hydrocarbon emissions by 20% Reduce Particulate Matter emissions Nitrogen Oxides emissions: area of further research. Analysis from NREL/TP-580-24772, May 1998

Historical Overview of NOx Issue: 

Historical Overview of NOx Issue Up until early in 2005 it was widely accepted that B20 caused a small, 2%, increase in NOx Conclusion of EPA review published in 2002 Based in large part on data acquired by McCormick and coworkers, Sharp and coworkers, etc. In February of 2005 we tested 3 vehicles that showed NOx reduction Subsequent review of EPA’s analysis showed that nearly half of the data reviewed were for one engine model Subsequent tests with a range of engine models are finding changes in NOx that range roughly from about +5 to -5% Varies with engine model Average change is zero Dataset is NOT representative of in-use vehicles

NOx Emissions, Chassis Data: 

NOx Emissions, Chassis Data Bus Chassis Dynamometer Testing: Using B20 in City Suburban Heavy Vehicle Cycle Cummins ISM 2000 Engine. Unexpected NOx REDUCTION of 5% with statistical confidence of >99%. Graph taken from NREL website: http://www.nrel.gov/vehiclesandfuels/npbf/pdfs/38296.pdf

Biodiesel Effect on NOx: 

Biodiesel Effect on NOx EPA study showed average reduction in NOx of 1.2% with B20. Inclusion of additional data shows no overall effect of biodiesel on NOx emissions. NOx emission changes are caused by differences in test cycles and engine technology. More research would be beneficial to determine the best technology and use of biodiesel to maximize NOx emissions reductions. Data from EPA420-P-02-001, October 2002 and additional information in public domain.

BQ-9000: 

BQ-9000

Slide17: 

NBB Fuel Quality Policy http://www.biodiesel.org/resources/fuelqualityguide/files/NBB%20Fuel%20Quality%20Policy%20.pdf

Fuel Quality: 

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

Fuel Quality: 

Fuel Quality Fuel Quality Outreach Program – State and Federal Agencies & NCWM Fuel Quality Outreach Program - $1.5 million petroleum industry outreach and education program BQ 9000 Quality Assurance Program 18 biodiesel plants = 40% of current production 8 certified marketers http://www.bq-9000.org Fuel Quality Enforcement Guideline – www.biodiesel.org/resources/fuelqualityguide In 2007, DOE supported effort to expand BQ 9000 program and fuel quality message

BQ-9000 Accreditation or Certification: 

BQ-9000 Accreditation or Certification Accreditation or Certification given by the National Biodiesel Accreditation Commission under NBB. BQ-9000 accredits companies, not fuel. There is no such thing as “BQ-9000 Biodiesel”. BQ-9000 does, however, help ensure the biodiesel being produced and sold will meet D6751

BQ-9000 “Quality Assurance Program”: 

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!!

BQ-9000 Initial Registration: 

BQ-9000 Initial Registration Complete the Application Submit Quality Manual Pay $750 application fee Provide proof of EPA Registration

BQ-9000 Accreditation: 

BQ-9000 Accreditation The Commission reviews the application and application materials: Applications considered administratively complete shall be accepted for processing and audit. $ 2,500 Certification Audit Fee

BQ-9000 Accreditation: 

BQ-9000 Accreditation Auditor is assigned, establishes the audit schedule with applicant. Desk audit to verify written compliance On-site audit to verify compliance. The Commission reviews results of audits, votes on the company’s status. If applicant passes audit, Commission grants accreditation for 2 years.

Slide25: 

ALWAYS BUY PRODUCT FROM BQ-9000 CERTIFIED PRODUCERS OR MARKETERS!!!

Supply and Demand: 

Supply and Demand

Biodiesel Demand: 

Biodiesel Demand

Slide28: 

Biodiesel Fuel Markets Federal State Selected Utilities Recreational Tour Boats Environmentally Sensitive Areas Lubricity Enhancement Conductivity Improver ULSD Sulfur Free Blend Stock

Future Growth and New Markets: 

Future Growth and New Markets Underground Mines Arbitrage Market Green Cargo Fleets & Greenhouse Gas Market Bioheat

Heating Oil Market: 

Heating Oil Market Almost as much heating oil is sold in the Northeast as on highway diesel fuel 5.1 billion gallons vs. 5.5 billion gallons Heating oil industry is attempting to remake itself as more environmentally friendly and renewable Could provide a good winter outlet for biodiesel Work is being done to integrate into Underwriters Laboratory certification

If Every Trucker Used B2: 

If Every Trucker Used B2 The industry would utilize 761 million gallons of B100 annually.

Availability: 

Availability Over 1,850 petroleum distributors now offer biodiesel. 1,051 retail locations 604 truck stops or truck accessible locations (BioTrucker.com) 37 terminals (biodiesel.org)

Distribution Locations: 

Distribution Locations

Slide34: 

Blending is occuring at over 37 terminals nationwide. DOE has supported this effort.

Pipelines?: 

Pipelines? 75,000 barrels of B5 moved on the Colonial Pipeline from Houston to New Jersey DOE supported the test Other test scheduled

Biodiesel Production Capacity: 

Biodiesel Production Capacity

Production Locations (6/7/07): 

Production Locations (6/7/07)

Industry Plant Size: 

Industry Plant Size Industry Capacity: 1.39 billion gallons per year Average Plant Size: 9.4 million gallons per year

Biodiesel Plants Under Construction and Expansion (6/7/07): 

Biodiesel Plants Under Construction and Expansion (6/7/07)

Size of Plants Under Construction & Expansion: 

Size of Plants Under Construction & Expansion Construction Capacity: 1.89 billion gallons per year Average Plant Size: 18.7 million gallons per year

Production Capacity Trends: 

Production Capacity Trends The industry is tending towards larger facilities Vegetable oil facilities are larger than recycled cooking oil plants Plants capable of handling multiple feedstocks are becoming more common Production capacity does not equal production for several reasons Some facilities are just starting up Some facilities choose to run less than 24/7 Some facilities have no effectively debottlenecked their systems to maximize their output Some facilities overestimate their capacity

Production Capacity by State (6/7/07): 

Production Capacity by State (6/7/07)

Blending ULSD and Biodiesel: 

Blending ULSD and Biodiesel

Why Blend Biodiesel into ULSD?: 

Why Blend Biodiesel into 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

ULSD and Biodiesel: 

ULSD and Biodiesel Biodiesel is slightly heavier than petroleum diesel with a gravity value of 0.88 versus 0.85. Biodiesel should be introduced after diesel fuel and should be agitated in the tank during splash blending procedures. Storage and blending of B100 should be maintained at +10 degrees F above the B100’s cloud and pour point to blend successfully. Blends will not separate in the presence of water.

ULSD & 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

Lubricity Study: 

Lubricity Study

Lubricity Study: 

Lubricity Study This study compared the lubricities of ULSD/biodiesel blends with additized ULSD

CFPP Testing of ULSD B2 Blends: 

CFPP Testing of ULSD B2 Blends

2007 Engines: 

2007 Engines

Engines Produced in 2007: 

Engines Produced in 2007 EPA regulations require reduced sulfur in diesel fuel for engines produced in 2007. 80% of highway diesel fuel must be ULSD (< 15ppm sulfur) beginning june1, 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) 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 conducting a study in order to define these effects on DPFs.

Indicators of DPF Performance: 

Indicators of DPF Performance Filter regeneration rate increased significantly when using blends as low as B5. Lower particulate temperature and less particulate input contributed. “Biodiesel Effects on Diesel Particle Filter Performance.” National Renewable Energy Laboratory, March 2006.

Materials Compatibility: 

Materials Compatibility B100 may adversely affect some elastomers such as natural or nitrile rubbers over time. Most elastomers used after 1993 are compatible with B100 (Viton/Teflon). Blends (B20) effect is less, or non-existent. Normal monitoring of hoses and gaskets for leaks is sufficient with B20. Consult with your parts supplier or mechanical engineering partners.

Materials Compatibility: 

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: -Mild and Stainless Steel, Aluminum

Biodiesel Position with OEM’s: 

Biodiesel Position with OEM’s Original Equipment Manufacturers: B100 Must Meet ASTM D 6751 Most OEM HQ’s have B20 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

Biodiesel Position with OEM’s: 

Biodiesel Position with OEM’s Engine Warrantees: Parts and Workmanship OEM’s Don’t Make Fuel OEM’s Don’t Warrantee Fuel As with diesel--problems caused by the fuel are the responsibility of the fuel supplier

Housekeeping: 

Housekeeping

Slide59: 

No matter where you are in the supply chain both you and your staff are responsible for ensuring optimum storage environments for your fuels The three basic ways which fuel may become contaminated are air, water and the fuel itself

Exposure to Air: 

Exposure to Air Enters through vent pipes and contains large amounts of moisture. Generally displaces the fuel as tank is emptied. It is not practical to keep air from entering the tank. Will increase the oxidation of fuel. Do not store fuels for long periods of time in partially empty tanks without stabilizers. Consider desiccant dryers.

Water: 

Water Free water in the fuel system accelerates corrosion and fuel degradation, it can also create a fertile growing place for “bugs.” Poor tank design has made complete removal of water impossible. Enters mostly as condensation from air. Vents and seals that are poorly constructed or maintained can allow water to infiltrate the storage tank.

Maintaining Your Fuel Quality: 

Maintaining Your Fuel Quality Begin by specifying ASTM designed fuels, 6751 and 975 Reference cold weather performance and other special needs prior to ordering Be proactive with general housekeeping practices Maintain optimum storage conditions Execute a quarterly fuel analysis program to ensure good preventative measures.

Filter Plugging: 

Filter Plugging

Plugged Filter Complaints: 

Plugged Filter Complaints The MPMA and MN Weights and Measures recently submitted numerous plugged fuel filters. The diagnosis of the source of plugging for each filter is based on observations, tests, and the most apparent source of plugging, although many filters likely have more than one source of plugging.

Paraffin Wax (30%): 

Paraffin Wax (30%) 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 paraffins 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.

Microbial Growth (27%): 

Microbial Growth (27%) 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.

Icing of the filter (23%): 

Icing of the filter (23%) 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.

Sediment/Rust build-up (10%): 

Sediment/Rust build-up (10%) Some of the filters had solid sediment within the folds and solid particles in the filter casing. Sediment present in the fuel or rust particles from within the engine can collect over time and plug the filter even when there are not necessarily problems with the fuel. Overall deterioration of the filter and gradual build-up of typical sediment or other materials may be the cause of the plugging. One filter was obviously very old and was plugged due to its extended use.

Oxidation (7%): 

Oxidation (7%) When MEG Corp received filters with a black and shiny surface but did not have microbial growth odor or have 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.

Monoglyceride Build-up (3%): 

Monoglyceride Build-up (3%) 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.

Biodiesel Handling: 

Biodiesel Handling

Tips for Biodiesel Handling: 

Tips for Biodiesel Handling 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 pre-blended 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: 

Tips for Biodiesel Handling 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: 

Tips for Biodiesel Handling 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: 

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. One outcome of improper handling of biodiesel may be microbial contamination.

What Are Microbes?: 

What Are Microbes?

Microbes and Filters: 

Microbes and Filters Build-up containing both live microbial organisms and dead microbial matter has been found on filters Microbes are a significant cause of filter plugging

Where Do They Come From?: 

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: 

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

Biocide: Universally Soluble: 

Biocide: Universally Soluble Stable in both fuel and water. Primarily fuel soluble with sufficient water solubility to perform in both phases. Can be transported throughout the fuel system and be effective against biofilms and bottom water microbes. Contains sulfur. Relatively expensive.

Preventing Contamination: Tank Cleaning: 

Preventing Contamination: Tank Cleaning Can be expensive and disruptive. Needs to be used in conjunction with a biocide treatment. The biocide should be used after the tank is clean, then fuel should be added (to eliminate microbes collected on the bottom of the tank). As a preventative measure, it is important to keep tanks as full of fuel as possible, and to keep the amount of air in the tank minimal.

Educational 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: 

NBB Resources: www.biodiesel.org Technical Library Biodiesel Bulletin Informational Resources Technical Resources Educational Videos Available On-line Database & Spec Sheets

Other Biodiesel Resources: 

Other Biodiesel Resources www.bbibiofuels.com Biodiesel Magazine A ‘MUST HAVE’ magazine Biodiesel Industry Directory On-Line

National Biodiesel Helpline:(800)929-3437(952)473-0182: 

National Biodiesel Helpline: (800)929-3437 (952)473-0182 Filter Plugging Blending w/ ULSD