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

“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

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

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

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)

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

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

American Society for Testing and Materials International

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 D02.08.0D – Vapor pressure and V/L ratio D02.A0 – Gasoline and oxygenates D02.A0.01 – Oxygenated fuels and components

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 D5501-12(2016) Standard Test Method for Determination of Ethanol and Methanol Content in Fuels Containing Greater than 20% Ethanol by Gas Chromatography ASTM D7795-15 Standard Test Method for Acidity in Ethanol and Ethanol Blends by Titration ASTM D5453-16e1 Standard Test Method for Determination of Total Sulfur in Light Hydrocarbons, Spark Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by Ultraviolet Fluorescence

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”

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”

ASTM D4806-16a 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 % - 1.0 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

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

CURRENT ASTM D02 “ISSUES” Changes to ASTM D4814 - Standard Specification for Automotive Spark-Ignition Engine Fuel

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 % - 1.0 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

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”

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

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

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

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)

INSTRUMENTS

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

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)

MAINTAIN THE ENVIRONMENT Temperature extremes Humidity Electrical Pressure

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)

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

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

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