Biodiesel Production: Technology

1. Biodiesel Production: Technology Barry Latham, M.A.Ed. Biodiesel Production & Curriculum Chemistry & Physics Instructor Chicago Heights, Illinois

2. ASTM 6751-08 (BQ-9000) • Flash Point 93°C min. • Water/Sediment 0.05% (vol.) max. • Sulfur 0.0015% (mass) max. • Cloud Point report only • Acid Number 0.50mg KOH/g • Free Glycerin 0.020% (mass) max. • Total Glycerin 0.240% (mass) max. • Oxidation Stability 3 hours min. • Cold Soak Filtration 360 seconds max.

3. Flash Point (ASTM D93-08) • Flash Point by Pensky-Martens Closed Cup Tester • Flash point- tendency of the test specimen to form a flammable mixture with air under controlled laboratory conditions • ~$2,000

4. Water & Sediment (ASTM D2709) • Water and Sediment in Middle Distillate Fuels by Centrifuge • An indication of water and sediment in middle distillate fuels such as Grade Nos. 1-D and 2-D diesel fuel • ~$12,000

5. Sulfur (ASTM D5453-09) • Determination of Total Sulfur in Diesel Engine Fuel by Ultraviolet Fluorescence • Determines sulfur in process feeds, sulfur in finished products and can also be used for purposes of regulatory control. • ~$3,000

6. Cloud Point (ASTM D2500-09) • Cloud Point of Petroleum Products • Cloud Point- temperature at which paraffin wax or other solid substance begins to separate from biodiesel; a cloudy appearance is seen in the oil at this point • ~$12,000

7. Acid Number (ASTM D664) • Acid Number of Petroleum Products by Potentiometric Titration • Biodiesel and blends of biodiesel may contain acidic constituents that are present as additives or as degradation products formed during service, such as oxidation products. • ~$900

8. Free & Total Glycerin (D6584-08) • Determination of Free and Total Glycerin in B-100 Biodiesel Methyl Esters By Gas Chromatography • A high content of free glycerin may cause problems during storage or in the fuel system, due to separation of the glycerin. A high total glycerin content can lead to injector fouling and may also contribute to the formation of deposits at injection nozzles, pistons, and valves. • ~$10k-$50k

9. Oxidation Stability (EN 14112) • Oxidation Stability of Fatty Acid Methyl Esters for Biodiesel • Oxidative degradation is harmful and can deteriorate many physical properties of the biodiesel including viscosity, and acid and peroxide values. • ~$8,000

10. Cold Soak Filtration (D6751-08-A1) • Cold Soak Filtration Analysis • Detects filter plugging tendencies at low temperatures. • ~$1,000

11. Oil Titration (Small Scale)Correlated to Acid Value • Used to measure the amount of Free Fatty Acids in used or virgin oil • Higher titration is less desired, but still usable • More FFA’s mean more catalyst needed means more expense • Performed to check quality of oil • Can be performed at oil collection site • Use disposable syringes and small plastic, re-sealable containers • Indicator Choices • Phenolphthalein, Phenol Red, pH Meter, Tumeric spice • Looking for color change (near pH 7.0)

12. Crackle Test (Small Scale)Correlated to Water/Sediment Test • When heated over a hotplate, water will “crackle” in the pan, indicating its presence • Heat a cup of oil to ~100°C • If the oil sputters, then water is present • More sputtering = more water • Water will have to be removed by heating or settling over time and tested again

13. Centrifuge Test (Small Scale)Correlated to Water/Sediment Test • Oil and water will separate over time • Centrifuging will speed up this process • Fill two appropriate sized test tubes ¾ of the way with your used oil • Spin for 5 minutes • The oil will rise to the top and water will settle to the bottom • The presence of water indicates that your oil will need to be treated further • Heating • Settling

14. Dewatering • Water in your used oil will complicate the formation of biodiesel and must be removed • Heating • Settling

15. Heating to Dewater (Small Scale) • A band heater on a 55-gallon drum will heat your oil sufficiently • Shorter time period (hours-days?) • Consumes electricity • Use gentle agitation • Emersion mixer set on low setting • Stir once or twice a day

16. Settling to Dewater (Small Scale) • Allowing a 55-gallon drum filled with used oil will settle your water to the bottom and can be drained off • Much longer time period (weeks?) • Consumes no electricity • Avoid any agitation

17. Appleseed Processor (Small Scale) • Plumbing w/ Pump ~$550 • 120V Water Heater ~$400 • Lumber ~$25 • No plumbing experience needed • All new parts used • Costs can be reduced by salvaging/recycling

18. Reactor Specifics (Small Scale) • Water heater preferred over steel drum • Pre-insulated • Pre-plumbed • Pre-wired for heating elements • Electrical water heater has less risk of explosion hazard • Internal immersion heaters • Upper heater disabled; it is rarely submerged • Needs to be connected to 120VAC source • Electrical box & switch needs to be installed • Do not compromise temperature regulators • Explosion risk

19. Quality Testing3/27 Test Correlates to Free Glycerin Test • Tests for triglycerides (unreacted oil) • Does not for monoglycerides and diglycerides • Tells you if you must reprocess • Add 1 part biodiesel to 9 parts methanol in a sealable vial (3mL & 27mL, etc.) • Be very precise with measurements if using these small amounts • Look for particles in the vial and/or cloudiness • If present, your sample failed- reprocess • Sample should be clear to pass

20. Biodiesel Size Exclusion Chromatography • Only B100 remains after final glycerin drain • Longer wait-time allows more glycerin to settle out • Residual MeOH may remain • Costly/complicated to distill MeOH out of glycerin • B100 pumped through molecular sieve into storage drum • 4A sieve traps small molecules (MeOH, H2O) and allows larger molecules (biodiesel, glycerin) to pass • Sized-based trap • Based on gas trap designs and drying agents • Because MeOH exists at ppm or ppb levels, sieve may take a very long time to exhaust • No current research available • Can be recharged by heating in an exhaust hood or outside • To vaporize MeOH and “bake-off” biodiesel adhered to surface

21. Biodiesel StorageCorrelates to Oxidation Stability Test • Biodegradable in months to years • Less time than table sugar • No research to support this claim • Only make as much as is needed • Hydroscopic (attracts atmospheric water) • More glycerin falls out over time, regardless of draining or filtering • Fire code regulations

22. Turn-Key Operations • More and more companies have plans for plants ready to purchase to produce ASTM certified biodiesel in a range of scales. • Costs are related to plant size • $1.95M per 5Mgallons/year (Xenerga quote) • Biodiesel Systems • SRS Engineering Corporation • Xenerga

23. Biodiesel Systems

24. SRS Engineering Systems

25. Xenerga

26. Custom SECDry-washing System