ASTM Testing for Biodiesel

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ASTM Testing for Biodiesel

• Becky Solano Team Leader
• Collin Matsumoto Operations Manager
• Noel Winegar-Thurston Safety Coordinator

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Agenda

• Project Objectives
• Background Information
• Project Planning
• Experimental Methods and Equipment
• Results and Conclusions
• Recommendations for Future Work

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Objectives and Background Information
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Initial Project Objectives

• Demonstrate ASTM testing of Biodiesel and Diesel
  Fuels
• Determine adequate tests to certify Biodiesel
• Optimize testing procedure

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Definitive Project Objectives

• Find a way to determine the amount of glycerin
  and oil in biodiesel
• Qualitative (Is it there?)
• Quantitative (How much?)

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Project Background

• What is an ASTM?
• American Society for Testing and Materials
• Non-profit Organization
• Established in 1898 in an effort to standardize
  steel used in building railroads
• Minimal requirements to meet consensus
• Technical Committees develop standards for
  products from Amusement park rides and Activated
  carbon to Vacuum cleaners and Waterproof Roofing

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Project Background

• What is Biodiesel?

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Project Planning
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Project Planning

• Roles and responsibility
• Safety
• Experimental work
• Noel - Rheometer
• Collin - GC
• Becky - Density and Cloud Point
• Analysis

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Project Planning

• Research and determine relevant ASTMs
• Read and understand ASTM principles
• Find appropriate materials and equipment to run
  ASTM test
• Cooling Bath Compounds
• Oil Standard
• Biodiesel Standard
• Ect.
• Achieve ASTM results
• Minimize time required to find results

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Project Planning

• What ASTMs are listed for Biodiesel?
• ASTM D 6751-03 Standard Specification for
  Biodiesel Fuel (B100) Blend Stock for Distillate
  Fuels
• Kinematic Viscosity D 445-03
• Acid Number D 664-01
• Cloud Point D 2500-02
• Water and Sediment D 2709-96
• Gas Chromatography D 6584-00
• Density D 1298-99

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Project Planning

• Viscosity
• Find the viscosity of ASTM Certified Biodiesel
  and Standard Canola Oil and several mixes
• Cloud Point
• Find the viscosity of ASTM Certified Biodiesel
  and Standard Canola Oil and several mixes
• Gas Chromatography
• Mimic the GC from the ASTM standard and then
  increase the rate of temperature increase to
  minimize time while still achieving known peaks
• Density

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Key Lessons Audits

• We could not foresee what obstacles we would face
  and this caused setbacks

• Learned the importance of making decisions that
  rely on relevance to project objectives
• ASTM Standards vs. THE ENGINEERING WAY!

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Experimental Methods and Equipment
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Rheometer

• Two plates in parallel with fluid between them
• Rotational rate is adjusted to find several
  measurements determining Newtonian
  characteristics
• Machine determines viscosity from torque and
  shear rate
• Important because of required pumping to supply
  and move fuel

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Rheometer
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Rheometer Equations

• Weight of Biodiesel 100
• Biodiesel Biodiesel Oil

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Rheometer Results
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Rheometer Results
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Cloud Point

• Chill fluid slowly in a controlled apparatus
  until wax crystals form in the liquid
• Cloudy appearance of bottom-most fluid
• Important because of the ability of fuel to clog
  filter at low temperatures

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ASTM Cloud Point Appartus
ASTM Specified Apparatus for Cloud Point
Determination
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Actual Apparatus
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Cloud Point Results
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ASTM Density Equipment

• Hydrometer and Thermometer

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Actual Density Equipment

• Gram scale
• Graduated Cylinder

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Density Results
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Recommended GC Materials

• Carrier Gas - Helium
• Standards
• N-Methyl-N-trimethylsilyltrifluorocaetamide
  (MSTFA)
• n-Heptane
• Inject 1 microliter

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GC Apparatus
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GC Basics
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Recommended Settings

• Initial hold time and temperature
• Medium ramp deg C/minute
• Slow ramp
• Fast ramp
• Final hold time - burn off
• Flame setting
• Helium flow rate

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ASTM GC Reference
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Actual GC Materials

• No MSTFA
• n-Heptane is WAY more expensive than Hexanes
• No internal standards

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What We Tried

• Tried to get a peak on the GC printouts that
  would indicate glycerin but none came out
• Ran our different mixes on the GC to see if we
  could find peaks relating oil content to
  biodiesel content

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GC Results
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Other Stuff We Tried

• Reaction of Glycerin with Acetic Anhydride
• Immiscible Could not get the glycerin suspended
  in a solvent solution
• Ethyl Acetate
• Hexanes

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Key Results
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What Went Right

• Viscosity
• We found a definite relationship between
  viscosity and oil content
• Cloud Point
• We found a linear relationship between cloud
  point and oil content
• Density
• There appears to be something going on with the
  density

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What Went Wrong

• GC Determination of Glycerin or Oil
• We did not have the MSTFA or four listed
  standards. There was a step given where MSTFA
  should have silyated the free glycerin and
  allowed it to be detected by the GC

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Recommendations

• Future work could include mixing of glycerin with
  biodiesel and finding cloud point and viscosity
• ASTM recommended mixing materials for GC
  determination of glycerin in biodiesel
• MSTFA
• Mono, Di, and Triglyceride standards

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References

• ASTM Website
• www.astm.org
• ASTM Standards Edition 2004
• D 6751 Specification for Biodiesel
• D 6584-00 Determination of Free and Total
  Glycerin in B-100 Biodiesel Methyl Esters By Gas
  Chromatography
• D 2500-02 Standard Test Method for Cloud Point of
  Petroleum Products
• Canola Oil Council of Canada, Updated Feb. 8,
  2005. http//www.canola-council.org/about/thetrut
  h.html

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References

• Saifuddin, N. and K.H.Chua Production of Ethyl
  Ester (Biodiesel) from used Frying Oil
  Optimization of Transesterification Process using
  Microwave Irradiation. Malaysian Journal of
  Chemistry. Vol 6, No 1, pgs 077-082, 2004.
• Williamson, Kenneth L. Macroscale and Microscale
  Organic Experiments 3rd Ed. Houghton Mifflin,
  Boston. 1999
• Bruice, Paula Y. Organic Chemistry 3rd Ed.
  Prentice Hall, New Jersey. 2001.

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Questions Comments
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25 Biodiesel GC
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Biodiesel 50
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Biodiesel 75
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Canola Oil GC
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ENOVA GC
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Acetic Anhydride Reaction

• What may have happened