National Biodiesel Troubleshooting Hotline Webinar Seriesgorgeanalytical.com/wp/wp-content/uploads/2012/06/NBB_Troubleshooting_Hotline_Webinar...• ASTM D975 and D396 for blends up

National BiodieselNational BiodieselTroubleshooting HotlineTroubleshooting Hotline

Webinar SeriesWebinar Series

Final WebinarFinal Webinar

Fuel Quality Considerations Fuel Quality Considerations –– In ReviewIn Review

February 2, 2010February 2, 2010

Host: Jordan Thaeler, NBBHost: Jordan Thaeler, NBB

Today’s WebinarToday’s Webinar

• Review biodiesel fuel quality specifications.

• Recap key points from the webinar series.

• Provide a few minutes at the end for some feedback, questions, and answers.

Identify Your RoleIdentify Your Role

• Good quality management practices are necessary to maintain fuel quality.

• Diagnostic testing is necessary to monitor fuel quality for contamination, degradation, or stability problems.

• Validate fuel meets quality specifications.• Track unique production lots.• Monitor and document fuel quality is maintained.

Petroleum Distribution Chain

TruckRail

BargePipeline

Production FacilityOr

Refinery

SupplyTerminals

WholesaleMarketers

BreakoutTerminals

Distributors

End Users

Resource: Biodiesel Troubleshooting Decision Tree

LIFECYCLE

LIFECYCLE

Meet ASTM SpecificationMeet ASTM Specification

• Biodiesel expected to perform within desired operability conditions must meet ASTM specifications; ASTM D6751 sets the specifications for biodiesel (i.e., mono-alkyl esters) intended for blending with petroleum diesel.

• The biodiesel material used for blending must satisfy ASTM D6751 to qualify the blended product as a “biodiesel” blend.

• Out-of-spec materials (i.e. those that do not satisfy the ASTM D6751 specification) can cause unexpected filter clogging above the cloud point.

• Manage and monitor to maintain ASTM grade biodiesel and biodiesel blends.

• Sequester out-of-spec material and materials that do not meet the specification for biodiesel to isolate quality related operability problems.

• Limit biodiesel distribution to well-characterized and tested materials.

Start with Reliable ProductStart with Reliable Product

• 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)

• Establish consistent “Control Points”

Resource: http://www.sustainableportland.org

Production LotProduction Lot

Photo Resource: http://www.ageratec.com

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.wisconsinbiofuels.comEstablish objective evidence validating the quality of a discrete quantity of fuel.

Lot # 09-304 Tk1

Lot volume – 10,000 gallons

Production LotProduction Lot

• 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– 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.

Upper layer

Middle layer

Lower layer

Composite

Also, check homogeneity when blending biodiesel made from different feedstock that where not pre-blended; particularly if cloud points are different by 5oC or more.

10,000 gallons

All

Leve

l Sam

ple

Production Lot – “Significant Process Change”

Production Lot – “Significant Process Change”

Upper layer

Middle layer

Lower layer

Composite

Also, check homogeneity when blending biodiesel made from different feedstock that where not pre-blended; particularly if cloud points are different by 5oC or more.

10,000 gallons

All

Leve

l Sam

ple

• A “significant” process change:– Use of different raw materials– Use of new or modified equipment– Refurbishment of existing equipment– Change in equipment location– Use of previously inactive equipment– Change in catalyst technology

Production Lot - Traceability Production Lot - Traceability

• Traceability – The ability to correlate test results to a specific production lot with objective evidence.

Upper layer

Middle layer

Lower layer

10,000 gallons

All

Leve

l Sam

ple

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

Composite

Keep a Retain (1-2 liters)

Obtaining A Fuel SampleObtaining A Fuel Sample

• Sample in accordance with ASTM D4057, if possible– All level samples, composite sample, line samples

• Use clean sampling equipment and containers• Collect a minimum of 2 liters (fill 80 to 90%)• Record sample collection information

– Sample Location (QA Hold Tank #001, Production Tank, Storage Tank)– Sample Identification– Lot #, and Lot size (gallons)– Collection Date and Time– Person Collecting Sample– Volume of sample and type of container (e.g. “2 x 1 quart clear glass”)– Type of sample collected (e.g. all level, composite, in-line, etc.)

• Purpose For Sample Collection– Product quality validation– Routine maintenance and process control testing– Investigative - troubleshooting

• Sampling Technique– Bacon bomb, thief, in-line, drain valve, dedicated sample port

Very Important To Obtain A Representative Sample

Fuel Quality Standards -Specifications and Methods

Fuel Quality Standards -Specifications and Methods

• 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 D6584 for Free and Total Glycerin• ASTM D664 for Total Acid Number• EN 14112 for Oxidation Stability• ASTM D7501 for Cold Soak Filterability

“Full” Specification Testing“Full” Specification Testing

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 EN 14110 or D93

Free Glycerin D6584

Total Glycerin D6584

Visual Appearance D4176

Tank Homogeneity D4052

Let’s boil this list down

Specification TestingSpecification Testing

Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584




You have 500 gallons5,000 gallons10,000 gallons

In a tank…..

How do you know that the 2-liter sample you collect for testing is “representative” of the entire tank volume?


Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584




1. Clarity or “Haze Rating” (max of 2)

2. Free of Particulate

Two Parts to AssessingVisual Appearance


Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584




Total Glycerin is the combination of

Free Glycerin + Bound Glycerides____________________________

Bound Glycerides include:• monoglyceride• diglyceride• triglyceride

Are you getting a complete reaction?


Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584




Settling…..

Centrifuge…..

Water wash…..

Dry filtration media…..

Are you adequately removing the byproduct?- Free Glycerin -


Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584




Are you adequately removing or recovering your Methanol?


Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584




Are you controlling Free Fatty Acids and other organic acid formation?


Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584




Does your process preserve enough inherent stability or do you need an antioxidant?


Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584




Does your product recover homogeneity if re-heated after temperature drops to 4.5 degrees C?


Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584




Will your product support the ULSD requirements when blended with petroleum diesel?


Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584




Is your process adequately removing water and sediment?


Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584




How well will your product support low temperature performance?

“Critical Specification”Testing


Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584




These tests are to be performed on every “production lot” if you wish to meet the BQ-9000 quality program expectations.

“Monthly Specification”Testing

“Monthly Specification”Testing

Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584




Every “production lot”

Monthly

“Full Specification” Testing“Full Specification” Testing

Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584





Monthly

Every six months

“Full Specification” Testing“Full Specification” Testing

Cetane Number D613




Sulfated Ash D874


Phosphorus D4951



Cloud Point D2500


Sulfur D5453



Acid Number D664


Free Glycerin D6584





Monthly

Every six months

Once per year



Cloud Point D2500


Sulfur D5453



Acid Number D664

Alchohol Content EN 14110 or D93

Free Glycerin D6584




“Other” Testing“Other” Testing

– Commingling• Unique production lots that meet the critical specifications may be

combined• The worst case result for the following tests is carried forward unless a

representative sample of the blend is collected and tested– Cloud Point– Oxidation Stability– Cold Soak Filtration Test (only relevant to B100)

– Storage Tank Inactivity• No activity for 30 days• Collect outlet sample and test

– Water and Sediment– Oxidation Stability

– Non-conforming Product• Re-process and re-inspect to meet specification• Re-classify to another application• Reject or destroy

Cold Weather HandlingCold Weather Handling

• Success in cold temperatures requires a combination of– Fuel Quality — meet ASTM D6751

• Water content meeting spec• Free and total glycerin meeting spec• CSFT meeting spec

– Fuel Blending• Blend ratios (e.g., B5, B20) with appropriate Cloud

point or CFPP for local conditions in use• Blending with No. 1 Diesel or Kerosene

– Cold Flow Additives• Ethylene vinyl acetate copolymers• Interfere with crystal growth

– Heated Transfer and Storage Capabilities• Maintain fuel temperature above cloud point by at

least 15oF

Tests for the ColdTests for the Cold

Resource: National Biodiesel Board and the Cold Flow Consortium

Cold Weather - Standard Test Methods

• Cloud Point – ASTM D2500• Required by Standard Specifications

• ASTM D975• ASTM D7467• ASTM D6751

• Cold Filter Plugging Point – ASTM D6371• Alternative to ASTM D2500• Simulates rapid cooling conditions• Not a referee method

• Low Temperature Flow Test – ASTM D4539• Alternative to ASTM D2500• Simulates slow cooling conditions• Not a referee method

• Pour Point – ASTM D97• Determines lowest temperature fuel will flow• Primarily used for handling and storage

considerations• Not required for Biodiesel or Biodiesel Blends

Cloud Point …Cloud Point …

– Most commonly used measure of low-temperature operability– Must be reported per ASTM specification

• no particular pass/fail value criteria

– The temperature at which small solid crystals are first visuallyobserved as the fuel is cooled. Below the cloud point, these crystals might plug filters or settle at the bottom of storage tanks.

– Typically, the crystals that form at low-temperatures return to solution when the fuel warms.

– If B100 has gelled completely, the fuel should be heated to 100 to 110oF to melt the most highly saturated biodiesel components.

Resource: “Biodiesel Handling and Use Guide: Fourth Edition”. National Renewable Energy Laboratory, January 2009

Cloud Point is…

Cold Soak Filtration Test…Cold Soak Filtration Test…

• Additional filter plugging issues are now “screened”with the new cold soak filtration test.

• Under conditions prescribed by ASTM D7501, a 300mL test sample is:– Chilled– Warmed– Filtered

• The time required to pass through the filter is measured.

• The entire sample volume must pass through the filter within 360 seconds.

• If vehicle performance is expected at or below -12o C, then a max of 200 seconds must not be exceeded.

Blending Issues for BiodieselBlending Issues for Biodiesel

• Cold Weather Considerations:– When blending, the temperature of

the biodiesel should be a minimum of 60oF or…

15oF above the cloud point.– In-line blending ensures the best

mixing– If in-line blending for loading trucks

is not available in cold weather, first add half the diesel (warm if possible). Then, as quickly as possible, add warm biodiesel at high pressure and volume to enhance thorough mixing followed by the other half of the diesel.

– Avoid introducing biodiesel directly into a cold and empty tank.

Resource: “A Biodiesel Blend Handling Guide”. Minnesota Department of Agriculture.

Common Cloud Pointsfor B100

Water Freezes

Recycled Grease (UCO, WVO)

Animal Fat

Plant Oils

“Room” Temperature

Safe blend temp 60oF

CP depends on feedstock

What plugs filters?What plugs filters?

Plugging Material Source of Problem

Paraffin (“wax”) Low temperature properties

Precipitates Low temperature properties;Blending practices that affect solubility

Microbial Biomass / Biofilm Water contamination

Particulates (Rust, Dirt) Poor housekeeping;Water contamination

Sediment / Sludge Contamination (e.g. glycerin)

Surfactants that promote fuel/water emulsions

Refinery treatment chemicals;Naturally occurring;Lube oil picked up during distribution

Material that does not pass through the filter media………or any substance that reduces the efficacy of the filter material.

Types of Contamination“20,000 foot view”


• Raw Materials – “Did we mix veggie oil in to the good stuff…?”

• Incompatibles – “Did the B100 come in contact with reactive materials….?”

• Particulates / Sediments – “Did it blow in or did we forget to clean house….?”

• Microbes – “Do we have bugs growing……?”

• “Off-Spec” Fuel – “Did the material fail to meet ASTM specifications……?”

• Water – “Did the hatch get left open on a rainy day…..?



Production Blending Transport and Distribution

Storage

Raw materials Raw materials Raw materials

Incompatibles Incompatibles Incompatibles

Particulates / Sediments

Particulates / Sediments

Microbes Microbes

“Off-Spec” Fuel “Off-Spec” Fuel

Water Water Water Water

Particulates as Contaminants

Particulates as Contaminants

• The most commonly recognized particulate contaminants found in diesel fuel are– Rust– Dirt– Sludge

• Particulates become trapped in filter surfaces, tank walls, and fuel lines and result in– Shorter fuel filter life, – Dirty fuel tanks,– Clogged lines and plugged screens

Sediment ContaminationSediment Contamination

• If tanks and fuel systems are not maintained or are neglected, sediment can accumulate.

• Sediment can be caused by rust, tank scale, microbial biomass and other contaminants.– Metabolic waste and dead cells accumulate as sludge or biofilm

The solvency effect of B100 is distinct from sediment contamination• however B100, as a mild solvent, may liberate deposits and

sediments previously accumulated in poorly maintained systems.

Microbial ContaminationMicrobial Contamination

• Microbial contamination has become a more common problem associated with diesel fuel since the introduction of ULSD in 2006.– Formerly present microbial inhibitors are removed in ULSD

• Previously, higher sulfur levels acted as a natural antimicrobial.

• Bacteria and fungus grow at the water/fuel interface.• They can be present in both supply tanks and vehicle

tanks, as well as supply lines and fuel system components.

• If microbial contamination is present, biocides are used.

Water as a Contaminant

Water as a Contaminant

• Icing– At temperatures less than 32oF, water contamination freezes

• The ice plugs filters and also nucleates crystal formation

• Filter Swelling and Distortion– Hydrophilic (water-liking) materials such as free glycerin are

attracted to the water on the filter media and the build-up plugs flow

• Fuel/water emulsions form – Stress water separators

• Corrosion and Rust– Long-term water contamination contributes to corrosion and

formation of particles that break away and collect in filters

• Provides environment for microbial activity

Water EvaluationWater Evaluation

• Dissolved Water– Not visible to the eye– Low part per million (ppm) levels– ASTM D6304 Karl Fisher 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

47 ppm 705 ppm

Haze Rating = 1

Haze Rating > 6

Water Concentration

Tank ManagementRecommendationsTank ManagementRecommendations

• Keep fuel tanks as full as possible to reduce the amount of air and water entering the tank.

• Use desiccant driers in tank vent openings.• Monitor hoses, fill/vapor caps, gaskets for leaks.• Visually check tanks monthly for free water by obtaining a

tank bottom sample.• Check fuel containment area for water regularly.• Always install a dispenser filter on a storage tank to

protect vehicle tanks from cross-contamination.• Check tanks for water concentration and microbial

contamination in the fall and spring.

SafeguardsSafeguards

• Dedicated Tanks (Storage and Transportation)– Reduce risk of cross contamination– The cleanliness specifications must include consideration of common

contaminants such as gasoline, ethanol and raw materials such asmethanol, raw oils or animal fats as well as diesel fuel in excess of 15 ppm sulfur when the biodiesel is destined for ULSD applications.

– The BOL should be accompanied by a certificate that the tank wascleaned.

• Frequent tank inspections– Bi-annual microbial contamination testing for fuel tanks– Tank vents

• Desiccant drier highly recommended– Water check

• Prior to each fuel delivery• Pull bottom sample at least monthly

• Dispenser filters (to avoid cross-contamination of vehicle tanks)– Side filtration loop– In-line with fuel pump

Safeguards –Sequester “Off-Spec” Material

Safeguards –Sequester “Off-Spec” Material

• Identify - Tag the inventory with relevant information such as date, lot number, product identification, location, and name of the individual who determined the product was nonconforming.

• Document - Records are the organization's evidence that a required process has occurred. It is a best management practice to initiate a record that will be used to track the material as it is evaluated for disposition.

• Evaluate - Trace the lot’s history; collect documentation.

• Segregate - Prevent unintended use. Unintended use applies to shipment, mixing nonconforming product with finished product that is within specifications, or further use in the process of manufacturing (if related to raw materials or materials in process).

• Disposition - Reprocess, re-classify, or destroy.

Resource: http://www.bq-9000.org/documents

Key Points for SuccessKey Points for Success

• Resource Awareness– NBB Hotline– ASTM Standard Specifications and Methods– BQ9000 Quality Program Guidance– Published Research by reliable laboratories and institutes– National Conferences and Trade Shows

• Understanding the information provided by ASTM Tests– As it pertains to your role

• Understanding low temperature operability conditions• Understanding considerations for blending biodiesel• Identifying contamination sources and associated

safeguards.

Technical ResourcesTechnical Resources

• “Maintaining Biodiesel Quality Throughout the Supply Chain”. Copyright 2009, National Biodiesel Board. Troubleshooting Hotline.

• “A Biodiesel Blend Handling Guide”. Minnesota Department of Agriculture. A publication of the Minnesota Biodiesel Technical Cold Weather Issues Team Handling Subcommittee.

• “Biodiesel Fuel Management Best Practices for Transit”. Department of Transportation, November 2007.

• “Fuel Quality and Performance Guide: A Troubleshooting Checklist for Diesel Fuel, Biodiesel and Bioheat Fuel Users”. A publication of the National Biodiesel Board and the United Soybean Board.

• “Biodiesel Handling and Use Guide: Fourth Edition”. National Renewable Energy Laboratory, January 2009. A publication of the Department of Energy.

• TDI Club Troubleshooting Guide.

You Can Find These Documents on the National Biodiesel Hotline’s Websitehttp://www.biodiesel.org/hotline/

Resource AwarenessResource Awareness

• The National Biodiesel Board provides biodiesel users with a toll free 1-800 number to help troubleshoot fuel issues.

• The 1-800 number routes the caller to the national call center.

• The caller may then be forwarded to a regional center to enable enhanced responsiveness.

• Alternatively, the caller may dial their regional center directly.

1-800-929-3437

Need Help With Fuel Quality?

• Determine where your fuel is in the fuel’s lifecycle

• Production• Distribution• Storage• Use

• Answer some initial questions to prepare for the hotline call

• Gather contact information for involved producers, distributors, and fleets

• Determine the expected blend level of the fuel in question

• Gather any certificates of analysis documenting fuel quality

• Identify the initial “symptoms”• Use our “Decision Tree”

http://www.biodiesel.org/hotline

Make The Hotline CallMake The Hotline Call

…but before you call

http://www.biodiesel.org/hotline

National Biodiesel HotlineRegional Troubleshooting Centers

National Biodiesel HotlineRegional Troubleshooting Centers

East Coast:Advanced Fuel Solutions (978) 664-5923162 Park Street, Suite 301North Reading, MA 01864http://www.yourfuelsolution.com/

Midwest:MEG Corp 1-800-929-3437 1710 Douglas Drive N #210Golden Valley, MN 55422http://www.megcorpmn.com/

West Coast:Gorge Analytical, LLC (541) 716-61661107 13th StreetHood River, OR 97031http://www.gorgeanalytical.com/

National Call Center 1-800-929-3437

http://www.yourfuelsolution.com/

http://www.megcorpmn.com/

http://www.gorgeanalytical.com/