Bio-diesel Basics and Quality Standards Presented by: CATHIE JOHNSTON Intertek Caleb Brett Laboratory Business Development 3 April 2006

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Bio-diesel Basics andQuality
StandardsPresented by CATHIE JOHNSTONIntertek
Caleb BrettLaboratory Business Development3
April 2006
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New York Harbor, Regional Laboratory
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MAIN LABORATORY
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Biodiesel What is it?

• A clean burning, oxygenated diesel fuel made from
  vegetable oils or animal fats that is capable of
  replacing part or all of your diesel needs.

Biodiesel How is it made?

• By reacting alcohol with natural fats, oils or
  greases through a conventional chemical process
  known as transesterification.

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Raw Materials


Natural Fats Oils Soybean Rapeseed Cottonseed Ta
llow / Poultry Yellow Grease
Alcohol MethanolEthanol
Catalyst Sodium hydroxide Potassium
hydroxide Sodium Methoxide
End Products

Methyl Ester (a.k.a. biodiesel) Glycerine
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Biodiesel Key Benefits

• Significantly reduces tailpipe emissions
• Reduced dependency on foreign oil
• Significantly reduces carcinogenic pollutants
• B20 significantly reduces visible emissions
• At B2 increases lubricity by up to 60
• The economical option for EPAct

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Commercial Refining and Delivery
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Bio-Diesel HomeBrewFROM THE FRYER TO THE FUEL
TANK
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Biodiesel How is it used?

• As pure (100) B100
• As a blend with petroleum diesel (20) B20
• In low levels (1 - 5) B1 B5
• Any blend concentration requested B1 B99

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Biodiesel Benefits According to the Department
of Energy

• Clean and Renewable

• For every 1 unit of energy needed for production
  3.2 units energy are gained.
• Produced from a renewable agricultural product

Source EPA www.epa.gov/otaq/models/biodsl.htm
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Biodiesel Financial Impact?

• Biodiesel is less costly than other alternative
  fuel options!

Michael Wetzstein of the University of Georgia
concluded that biodiesel is the most cost
effective alternative fuel when considered on a
cost per mile basis, considering factors like
fuel economy, maintenance, engine rebuild
mileage, and fueling infrastructure.
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Fuel Quality
B100 is covered by American Society of
Testing and Materials standard D6751. Blends do
not yet have a standard however experience
indicates that if D2 is D975-compliant, B100 is
D6751-compliant, blends should be acceptable
(poor cold-blending is an exception). Conformity
of B100 to D6751 can be assured through adherence
to industry quality program for producers and
distributors, BQ-9000 however, participation in
this program is low with only two producers to
date. Quality control of biodiesel is not well
documented at this point, however, all producers
certify B100 product conforms to D6751
(otherwise, the product is not eligible for the
blenders tax credit). ( Information as
provided by Virginia Clean Cities)
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Biodiesel Testing Standards and Quality Control
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QUALITY CONTROL TESTING

• Quality Control Testing Importance
• Quality Control Standards-ASTM D6751
• Other Analytical Methods Applicable to
• Biodiesel
• Production Level Quality Control
• 3rd Party C of A Support
• Questions Discussion

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Quality Control Testing Importance

• Feedstock quality
• Production optimization
• Controls by-product production levels
• Controls Feedstock or Raw Material
• Requirements
• Final product control confirmation
• Internal
• External, 3rd party Certificate of Analysis

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ASTM D6751Standard Specification for Biodiesel
Fuel Blendstock (B100) for Middle Distillate Fuels

• Property Test Method Specification
• Flash Point, Closed Cup ASTM D93 130C min
• Water and Sediment ASTM D2709 0.050 Vol. Max
• Kinematic Viscosity, 40C ASTM D445 1.9-6.0
  mm2/s
• Sulfated Ash ASTM D874 0.020 Mass Max
• Sulfur ASTM D5453 0.0015 Mass , Max
• Copper Strip Corrosion ASTM D130 No. 3 Max
• Cetane Number ASTM D613 47 Min
• Cloud Point, C ASTM D2500 Report
• Carbon Residue ASTM D4530 0.050 Mass , Max
• Acid Number ASTM D664 0.80 mg KOH/g Max
• Free Glycerin ASTM D6584 0.020 Mass , Max
• Total Glycerin ASTM D6584 0.240 Mass , Max
• Phosphorous Content ASTM 4951 0.001 Mass ,
  Max
• Distillation Temperature ASTM D1160 360 C Max
• Atmospheric Equivalent Temperature
• 90 Recovered

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ASTM D93 Standard Test Method for Flash Point
by Pensky-Martens Closed Cup Tester

• Performed to define and guarantee the DOT product
  rating of non-hazardous, or non-flammable
• Flash point of Methanol, lt100 deg C
• Flash point of Biodiesel, gt130 deg C min
• Indicates residual alcohol, methanol, left in
  final product
• Methanol residue can cause degradation of
  elastomers and seals within engine
• Important to monitor at the production level

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ASTM D2709 Standard Test Method for Water
Sediment in Middle Distillate Fuels by Centrifuge

• Indicator of the cleanliness of the fuel
• 0.050 Volume Max
• Water Sediment are both contaminant in the fuel
• Water reacts with the esters to produce Free
  Fatty Acids (back reaction)
• Water Supports microbial Growth
• Sediment plugs fuel filters
• Both may be sourced from feedstock, treatment
  during process or storage conditions

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ASTM D445 Standard Test Method for Kinematic
Viscosity of Transparent or Opaque Liquids

• Viscosity of the fuel is considered when OEMs
  design engine specifications, flow and
  lubricating properties
• Specification Established with a Min/Max Range
  1.9-6.0 mm2/s
• Viscosity of Biodiesel considered due to its use
  as a blend component for the diesel product
• Blendstock should not change overall diesel
  properties
• Biodiesel specifications designed to allow for
  optimal blending without compromising overall
  flow properties
• Injector performance can be compromised if
  viscosity is compromised

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ASTM D874 Standard Test Method for Sulfated Ash
from Lubricating Oils and Additives

• Indicator of mineral ash residue left over after
  fuel is burned
• 0.020 Mass Max
• Indicates residual metals from catalyst, spent Na
  or K salts
• Importance is dependent on type of product

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ASTM D5453Standard Test Method for Determination
of Sulfur Content by UV Fluorescence

• Indicator of contamination by protein material of
  feedstock or carryover from the catalyst material
• 0.0015 Mass Max, or 15 ppm
• Sulfur should be measured in feedstock-virgin oil
  versus the rendered product
• Critical as Diesel Specifications will change in
  2006 to Ultra Low Sulfur (500 ppm versus new 15
  ppm as delivered)
• Biodiesel should not be a contributor to the
  overall sulfur of the final blended product
• Biodiesel adds lubricity properties lost by
  reduction in sulfur in diesel product

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ASTM D130Standard Test Method for the
Determination of Copper Corrosion by Copper
Strip Tarnish Test

• Indicator of the relative corrosivity of the
  product
• No. 3 Max Specification (rating on a 1-4, a-c
  scale)
• Also indicator of presence of acids or free fatty
  acids derived from unreacted materials in the
  production process
• Total Sulfur (ASTM D5453) is not always indicator
  of the sulfur species effecting the corrosivity
  of other sulfur species

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ASTM D613Standard Test Method for Cetane Number
in Diesel Fuel

• Indicator of the ignition characteristics of the
  fuel in compression ignition engines, influences
  smoke and combustion roughness
• Specification, 47 min
• Feedstock ultimately determines the cetane number
  obtained in the final product
• Performed on full scale cetane engine, Cetane
  Index Calculated is not applicable to biodiesel
  product
• Not a production level analysis, cost for engine
  extremely high

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ASTM D2500Standard Test Method for Cloud Point
in Petroleum Products

• Indicator of temperature in which cloud or haze
  of crystals appears under prescribed conditions,
  crystal precipitation
• No current specification in place for D2500
• Producers should measure this property internally
  although there is no specification for the
  product
• Consideration to use in cold climates, ie.
  Northeast
• Controlled by blending of feedstocks

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ASTM D4530Standard Test Method for Determination
of Carbon Residue (Micro Method)

• Indicator of the carbon depositing tendencies of
  the fuel
• 0.050 Mass Max
• Performed on the 100 fraction due to the
  distillation characteristics of the fuel
• (ie. Difficult to get the 10 bottoms for
  analysis)

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ASTM D664Standard Test Method for Acid Number
by Potentiometric Titration

• Direct measurement of the FFAs, free fatty
  acids, processing acids or degradation
  by-products in the final product
• 0.80 mg KOH/g Max
• FFAs are unreacted materials
• High Acid characteristics may cause corrosion,
  fuel system deposit or filter plugging problems
• May be a symptom of water in the fuel product

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ASTM D6584Free and Total Glycerin in B100 by
Gas Chromatography

• Free and Total Glycerin Specification and
  Definition
• 0.020 Mass Max Free Glycerin
• 0.240 Mass Max Total Glycerin
• Total Glycerin-the sum of Free and Bonded
  Glycerin
• Free Glycerin-unbound, incomplete esterification
  products
• Bonded Glycerin-includes mono, di and
  triglycerides
• Why is this property important?
• Due to the nature of the glycerides in the final
  product
• Can cause operability problems at low
  temperatures
• Saturates monoglycerides cause filter clogging
• Should be part of production level quality
  control

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ASTM D4951Standard Test Method for
Determination of Additive Elements in
Lubricating Oils by ICP-AES

• Feedstock Driven Property, not typically a
  problem in the US biodiesel production industry
• 0.240 Mass Max
• Phosphorous can damage catalytic converters used
  in emission control systems. Cat Converters
  becoming more common on diesel-powered equipment
• Not a production level quality control parameter

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ASTM D1160Standard Test Method for Distillation
of Petroleum Products at Reduced Pressure

• Indicator of adulterants in the final product
• 360C, 90 recovered Max
• Distillation curve of biodiesel is unique,
  saturated hydrocarbons effect the curve type
• Not a production level quality control parameter

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Product Qualities Important to BiodieselOutside
of the ASTM D6751 Specification

• Lubricity- ASTM D6079, provides indicator of the
  lubricating properties of the fuel
• Biodiesel Content in Blended Middle Distillation
• EN 14078-European Standard Method
• Applies to blends from 1.7-25 Volume
• IR Method
• Methanol Content EN 14110 GC-FID
• Linoleic and Linolenic Methyl Esters
• Oxidation Stability
• Storage Stability-D4245

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QC at the Production Level

• Balance must be attained between testing on site
  and economics that meets product quality and
  production process control needs
• Costs for establishing full ASTM D6751
  capabilities extremely high and cost prohibitive
  to small production facilities
• Costs can be controlled by identifying critical
  properties
• Measure properties onsite that provide
  information as to production status
• Technical Personnel Resources must be available
  to maintain the quality control function of the
  production facility
• Costs for technical personnel high, mitigate
  these costs by minimizing technical depth of
  laboratory on site

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Reduced Slate TestingOptimizing Testing Costs at
Production Site

• Define critical properties to be measured onsite
• Define Costs associated with laboratory set-up
  and maintenance
• Establish reduced slate testing for production
  measurement
• National Biodiesel Boards BQ 9000 program
  incorporates the following analyses in their
  reduced slate program
• D2709 Water and Sediment
• D6584 Free and Total Glycerin
• D664 Acid Number

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Atomic Absorption and ICP for Metals Determination
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Gas Chromatographs with Auto Samplers
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CETANE ENGINES
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Sulfur Analyzers with Auto Sampler
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Intertek Caleb Brettcan help with your quality
issues.

• Cathie Johnston
• Intertek Caleb Brett
• Ph 864-884-300/732-969-5200
• cathie.johnston_at_intertek.com