Fuel Ethanol Laboratory Conference

Fuel Ethanol Laboratory Conference
Dr. Jerry KingDecember 6, 2016Omaha, Nebraska
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 controlb. trouble shootc. innovationYour role is to MANAGE/CONTROL the laboratory
TOOLS OF THE TRADE
Management/ownersIndustry standards/regulationsFacilityInstrumentsPersonnel you work with and over seeMethodsPeersProfessional organizations (e.g. ASTM)Conferences, webinars, technical reps
DRIVING FORCE(S)
The consumerIndustryGovernmentEPA (environment – air pollution)TTB (treasury – denaturants)COMMERCE (international trade)FDA (Food and Drug – FSMA)DOT (department of transportation)
A CASCADE EFFECT
Regulatory toIndustry toASTM toPlant toLaboratory toYOU (buck stops here)
Ultimately, where do you (we) have an impact???
AmericanSocietyforTestingandMaterialsInternational
TECHNICAL COMMITTEES
ABOUT 155 technical committeesRelevant onesD02 - Petroleum Products, Liquid Fuels, and LubricantsE48 on Bioenergy and Industrial Chemicals from BiomassSubcommitteesDO2.03 – Elemental analysisD02.04 – Hydrocarbon analysisD02.04C – Liquid chromatographyD02.04C – Gas chromatographyD02.08.0D – Vapor pressure and V/L ratioD02.A0 – Gasoline and oxygenatesD02.A0.01 – Oxygenated fuelsand components
ASTM SUBCOMMITTEES
StandardsD4806 – Standard Specification for Denatured Fuel Ethanol for Blending with Gasolines for Use as Automotive Spark-Ignition Engine FuelD5798 – Standard Specification for Ethanol Fuel Blends for Flexible-Fuel Automotive Spark-Ignition EnginesMethodsASTM D5501-12(2016) Standard Test Method for Determination of Ethanol and Methanol Content in Fuels Containing Greater than 20% Ethanol by Gas ChromatographyASTM D7795-15 Standard Test Method for Acidity in Ethanol and Ethanol Blends by TitrationASTM 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 materialsc. Specifies to prepare the sampled. Specifies how to process (analyze) the samplee. Provides the calculation(s)f. Specifies the quality control requirements1) the precision2) the repeatability3) the reproducibility4) the bias2. Some methods are identified as the “gold standard”
PERFORMANCE BASED METHODS
New approach followed by EPAIdentifies/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 FuelEthanol – 92.1% by volume minimumMethanol – 0.5% by volume - maxSolvent washed gum – 5.0 mg/100 mL maxWater, volume % - 1.0 maxInorganic chloride – 6.7 mg/kg maxCopper – 0.1 mg/kg maxAcidity – 70 mg/kg maxpHe – 6.5 – 9.0 SUSulfur – 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 D4806Ethanol – 92.1% by volume minimumSolvent washed gum – 5.0 mg/100 mL maxWater, volume % - 1.0 maxInorganic chloride – 6.7 mg/kg maxCopper – 0.1 mg/kg maxAcidity – 70 mg/kg maxpHe – 6.5 – 9.0 SUSulfur – 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 standardImpacts any automotive spark-ignition engine (cars, boats, motor cycles, lawn mowers, etc.)Product (gasoline) is used around the worldMust be functional in a engines with a wide manufacture dateMust be compatible with many old and new alloys (corrosion and deposits)Functional in different climates/seasons (temperatures) and different altitudesReduce 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 ratioAir-fuel ratio (cold start)Vapor lockDriveabilityAnti-knock additivesPhasesGasoline is non-polarEthanol is polarCombustion and water are not compatibleCorrosionFormation of depositsBlockages 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 gasolinePerformance must meet ASTM D4814 requirementsOxygenate requirements must be met (reduce pollution)Different states have different requirements for ethanol-blended gasoline
OTHER IMPACTED INDUSTRIES
PipelinesAnti-corrosionAnti-dragTruck/rail/tanker transportPrevious cargosFuel stations (gas stations)Storage and deliverycominglingRefineriesCrude oil sourceSocial/economical ramificationsStorage facilitiesFuel comingling
THE DESIRED IMPACT
This (ASTM) is whereYOUhave an impact1. determine what works and what does not work2. identify innovations and suggestions3. identify new methods or standardsWork 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. Balancesc. pipettorsd. weightse. OvensTake care of it!!! (maintenance)
MAINTAIN THE ENVIRONMENT
Temperature extremesHumidityElectricalPressure
PREVENTIVE MAINTENANCE - PRINCIPLES
Generally specified in operator manualsResistance to PM1. why fix it if it is working???2. too much down time – need to analyze samples3. introduces interruptions in workflow4. choice between running samples or PM5. expensiveI 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 maintenance2. Make sure you have the training and expertise3. Be careful not to break something else while fixing4. Take pictures while you repair5. Safety (lock out tag out, chemicals, etc.)6. after making repairs, conduct a validation study to show instrument is functional and operationala. Run a new standard curveb. run an LCS or a number of LCS samplesc. run some comparative samples7. Redundancy (instruments or methods)8. Keep records: who, what, when, why
RECORDS – CRITICAL COMPONENT IN GOOD LABORATORY PRACTICESSeeing this in FSMA
THE TAKE AWAYS
Know the fuel industry – what you do is an integral part of the industryWhat is gasolineHow does ethanol affect the performance of finished fuelsKeep current on the activities in the industryActive participation in ASTMGet involved with D4806, D5798, D4814Understand and manage a laboratoryManage peopleUnderstand instruments (theory of operation)Implement quality control proceduresImplement trainingInstrument preventive maintenanceWhat you do (provide a “measurement”) is critical in performance and management