1. Fuel Ethanol Laboratory Conference
Dr. Jerry King
December 6, 2016
Omaha, Nebraska

2. “If you can’t measure it, you can’t manage it”
INSTRUMENTS AND ASTM
A “famous” quote:
“If you can’t measure it, you can’t manage it”
W. Edward Deming

3. The role of a laboratory is to “measure” a. process control b
The role of a laboratory is to “measure” a. process control b. trouble shoot c. innovation Your role is to MANAGE/CONTROL the laboratory

4. TOOLS OF THE TRADE Management/owners Industry standards/regulations
Facility
Instruments
Personnel you work with and over see
Methods
Peers
Professional organizations (e.g. ASTM)
Conferences, webinars, technical reps

5. DRIVING FORCE(S) The consumer Industry Government
EPA (environment – air pollution)
TTB (treasury – denaturants)
COMMERCE (international trade)
FDA (Food and Drug – FSMA)
DOT (department of transportation)

6. A CASCADE EFFECT Regulatory to Industry to ASTM to Plant to
Laboratory to
YOU (buck stops here)

7. Ultimately, where do you (we) have an impact???

8. American Society for Testing and Materials International

9. TECHNICAL COMMITTEES ABOUT 155 technical committees Relevant ones
D02 - Petroleum Products, Liquid Fuels, and Lubricants
E48 on Bioenergy and Industrial Chemicals from Biomass
Subcommittees
DO2.03 – Elemental analysis
D02.04 – Hydrocarbon analysis
D02.04C – Liquid chromatography
D02.04C – Gas chromatography
D D – Vapor pressure and V/L ratio
D02.A0 – Gasoline and oxygenates
D02.A0.01 – Oxygenated fuels and components

10. ASTM SUBCOMMITTEES Standards Methods
D4806 – Standard Specification for Denatured Fuel Ethanol for Blending with Gasolines for Use as Automotive Spark-Ignition Engine Fuel
D5798 – Standard Specification for Ethanol Fuel Blends for Flexible-Fuel Automotive Spark-Ignition Engines
Methods
ASTM D (2016) Standard Test Method for Determination of Ethanol and Methanol Content in Fuels Containing Greater than 20% Ethanol by Gas Chromatography
ASTM D Standard Test Method for Acidity in Ethanol and Ethanol Blends by Titration
ASTM D e1 Standard Test Method for Determination of Total Sulfur in Light Hydrocarbons, Spark Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by Ultraviolet Fluorescence

11. METHOD INFORMATION 1. The guide on “how-to”
a. specifies the apparatus (instruments)
b. Specifies reagents and materials
c. Specifies to prepare the sample
d. Specifies how to process (analyze) the sample
e. Provides the calculation(s)
f. Specifies the quality control requirements
1) the precision
2) the repeatability
3) the reproducibility
4) the bias
2. Some methods are identified as the “gold standard”

12. PERFORMANCE BASED METHODS
New approach followed by EPA
Identifies/specifies a “gold standard” method (e.g. ASTM D7039)
Method selected by the laboratory must meet or exceed the QC requirements of the “gold standard”

13. ASTM D a
Standard Specification for Denatured Fuel Ethanol for Blending with Gasolines for Use as Automotive Spark-Ignition Engine Fuel
Ethanol – 92.1% by volume minimum
Methanol – 0.5% by volume - max
Solvent washed gum – 5.0 mg/100 mL max
Water, volume % max
Inorganic chloride – 6.7 mg/kg max
Copper – 0.1 mg/kg max
Acidity – 70 mg/kg max
pHe – 6.5 – 9.0 SU
Sulfur – 30 (down to 10 ppm max in denaturant)
Existent sulfate – 4 mg/kg max

14. NONE OF THE PARAMETERS IDENTIFIED IN D4806 FALL UNDER PERFORMANCE BASED METHODS

15. CURRENT ASTM D02 “ISSUES”
Changes to ASTM D Standard Specification for Automotive Spark-Ignition Engine Fuel

16. ASTM D4814
Section 5.4 reads:
The denatured fuel ethanol used in gasoline-ethanol blends shall conform to the requirements of Specification D4806
Ethanol – 92.1% by volume minimum
Solvent washed gum – 5.0 mg/100 mL max
Water, volume % max
Inorganic chloride – 6.7 mg/kg max
Copper – 0.1 mg/kg max
Acidity – 70 mg/kg max
pHe – 6.5 – 9.0 SU
Sulfur – 30 (down to 10 ppm max in denaturant)
Existent sulfate – 4 mg/kg max

17. ASTM D4814 CONTENTS AND IMPLICATIONS
Very far reaching and significant requirements in this standard
Impacts any automotive spark-ignition engine (cars, boats, motor cycles, lawn mowers, etc.)
Product (gasoline) is used around the world
Must be functional in a engines with a wide manufacture date
Must be compatible with many old and new alloys (corrosion and deposits)
Functional in different climates/seasons (temperatures) and different altitudes
Reduce pollution (lead, sulfur, “smog”)
Prevent “knocking” and “vapor lock”

18. CRITICAL ASTM D4814 ISSUES
Volatility – move from liquid phase to gaseous phase (distillation curve)
Vapor-liquid ratio
Air-fuel ratio (cold start)
Vapor lock
Driveability
Anti-knock additives
Phases
Gasoline is non-polar
Ethanol is polar
Combustion and water are not compatible
Corrosion
Formation of deposits
Blockages and mechanical failures

19. PETROLEUM INDUSTRY AND ETHANOL INDUSTRY
Ethanol blended fuels (RFS – renewable fuels standard) mandated by congress (the law)
Ethanol-blended fuels have different properties than natural gasoline
Performance must meet ASTM D4814 requirements
Oxygenate requirements must be met (reduce pollution)
Different states have different requirements for ethanol-blended gasoline

20. OTHER IMPACTED INDUSTRIES
Pipelines
Anti-corrosion
Anti-drag
Truck/rail/tanker transport
Previous cargos
Fuel stations (gas stations)
Storage and delivery
comingling
Refineries
Crude oil source
Social/economical ramifications
Storage facilities
Fuel comingling

21. THE DESIRED IMPACT This (ASTM) is where YOU have an impact
1. determine what works and what does not work
2. identify innovations and suggestions
3. identify new methods or standards
Work with your industry (RFA, Growth Energy, corn growers)

22. INSTRUMENTS

23. IMPORTANCE OF INSTRUMENTS
The Deming quote: “If you can’t measure it, you can’t manage it”
Must “measure” accurately and precisely (anybody can “measure” with anything

24. FUNDAMENTALS Get good equipment (don’t skimp)
This does not pertain to just analytical equipment (e.g. HPLC, GC, LC, etc.)
a. Glassware (class A)
b. Balances
c. pipettors
d. weights
e. Ovens
Take care of it!!! (maintenance)

25. MAINTAIN THE ENVIRONMENT
Temperature extremes
Humidity
Electrical
Pressure

26. PREVENTIVE MAINTENANCE - PRINCIPLES
Generally specified in operator manuals
Resistance to PM
1. why fix it if it is working???
2. too much down time – need to analyze samples
3. introduces interruptions in workflow
4. choice between running samples or PM
5. expensive
I JUST DON’T HAVE THE TIME (aka I don’t want to make the time)

27. PRINCIPLES (cont.)
1. Make sure you have an inventory of spare parts for the maintenance
2. Make sure you have the training and expertise
3. Be careful not to break something else while fixing
4. Take pictures while you repair
5. Safety (lock out tag out, chemicals, etc.)
6. after making repairs, conduct a validation study to show instrument is functional and operational
a. Run a new standard curve
b. run an LCS or a number of LCS samples
c. run some comparative samples
7. Redundancy (instruments or methods)
8. Keep records: who, what, when, why

28. RECORDS – CRITICAL COMPONENT IN GOOD LABORATORY PRACTICES Seeing this in FSMA

29. THE TAKE AWAYS
Know the fuel industry – what you do is an integral part of the industry
What is gasoline
How does ethanol affect the performance of finished fuels
Keep current on the activities in the industry
Active participation in ASTM
Get involved with D4806, D5798, D4814
Understand and manage a laboratory
Manage people
Understand instruments (theory of operation)
Implement quality control procedures
Implement training
Instrument preventive maintenance
What you do (provide a “measurement”) is critical in performance and management