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

ASTM (BQ-9000) Flash Point93°C min. Water/Sediment0.05% (vol.) max. Sulfur0.0015% (mass) max. Cloud Pointreport only Acid Number0.50mg KOH/g Free Glycerin0.020% (mass) max. Total Glycerin0.240% (mass) max. Oxidation Stability3 hours min. Cold Soak Filtration360 seconds max.

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

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

Sulfur (ASTM D ) 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

Cloud Point (ASTM D ) 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

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

Free & Total Glycerin (D ) 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

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

Cold Soak Filtration (D A1) Cold Soak Filtration Analysis Detects filter plugging tendencies at low temperatures. ~$1,000

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)

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

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

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

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

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

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

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

Quality Testing 3/27 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

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, H 2 O) 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

Biodiesel Storage Correlates 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

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

Biodiesel Systems

SRS Engineering Systems

Xenerga

Custom SEC Dry-washing System