The Sidestreams of Biodiesel Production A Curriculum for Agricultural Producers

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1 The Sidestreams of Biodiesel Production A Curriculum for Agricultural Producers Prepared by For the National Center for Appropriate Technology With funding and cooperation from the USDA Risk Management Agency

2 What Side streams? Glycerin Wash water Excess Methanol Absorbents Glop and/or bad batches WVO Sludge

3 Glycerin Important to have a plan Product of the process Can shut production down Environmental consciousness EPA s definition of hazardous waste your glycerol must have a flash point under 140 ºF and ph less than 12.5.

4 Glycerin How much glycerin do we get? About 18% of the finished product is crude glycerin before methanol recovery. Must remove methanol before doing anything with glycerin.

5 Glycerin Soap making Animal feed Vermiculture composting Aerobic Composting Anaerobic biodigesters Burning glycerin for process heat

6 Glycerin Soap NOT a real solution - Glycerin soap with a lot of glycerin tends to sweat and get slimy We used about 1/4 gallon of glycerin in our soap batch along with virgin oils. We followed a recipe from The Transparent Soap book. UtahBiodieselSupply.com A liquid pumice for washing your hands in the lab can be made from 100% glycerin.

7 Glycerin Soap Vanilla Oatmeal, Almond, Spiced Fig, Lavender and Unscented!

8 Glycerol and Animal Feed GRAS: General Recognized as Safe Maximum:150 ppm of methanol content University of Arkansas research: Poultry Feed University of Missouri: Cattle Feed Iowa State University: Pig feed

9 Vermiculture Composting

10 Plant Vermiculture Composting Ideal Conditions: Moist, o F, 6-8pH, no aerobic activity (turn if smells). Food - Waste vegetable produce (no meat, dairy, citrus or oil). Bedding - Shredded paper Glycerin diluted in H 2 O, applied to bedding, then added to pile.

11 Co-op Vermiculture Composting 4 bins, all approximately 4 cu ft. Weekly they receive 1/2 qt. - 2 qts glycerin each. Bedding is leaves. Food and garden produce waste added weekly. We track amount of glycerin added and worm castings produced Nothing to report yet

12 Vermiculture Composting Relatively slow (5-6 months) compared to aerobic decomposition (6-8 weeks) Need bedding material and nitrogen input (coffee grinds, leaves, shredded paper, farm produce waste) Worm castings = high value product Future worm tractor experiment

13 Aerobic Decomposition (Composting) NOT just throwing all your organic waste into one place Using bacteria and microorganisms to break down wastes to reach a C:N ratio of 15:1 (finished compost) Need to add both carbon and nitrogen inputs to start feeding the compost.

14 Aerobic Decomposition Small Scale Composting

15 Aerobic Decomposition Small Scale Composting We add about 20 gallons of glycerin to each pile (3 cu yds). Too carbon rich to add much more as it lowers our compost temperature. We need to maintain the compost temperature over 130 o F for 90 days(?) to obtain organic certification. Not a sustainable solution: 1 pile roughly equals 1 batch biodiesel. We only need about 4-5 piles per season for our 0.85 acre farm.

16 Medium Scale Composting Burlington Biodiesel Co-op

17 Medium Scale Composting Pile composed of 40 tons of wood chips, started with a load of chicken manure. Tree service drops truck loads of wood chips for free. 160ºF and still burning after 5 ½ months. Co-op disposes of all glycerin (after methanol removal) and magnesol in compost. Magnesol does not break down.

18 Large scale/industrial Composting Piedmont disposes its unusable oil and glop batches at an industrial compost site. The Pit Industrial compost operations may allow free dump of waste grease and/or glycerin for small scale producers.

19 Biodigesters - Anaerobic Decomposition Biodigesters can be used to turn animal and food waste into methane gas Biodigesters might be able to break down glycerin Methane gas can be reused as process heat Normally you add 25% animal waste, 25% vegetable waste, 50% water. Very difficult to store the gas in cylinders Extreme caution to not breath Hydrogen Sulfide (H 2 S), which is HIGHLY toxic and also produced in anaerobic digestion

20 Biodigester

21 If you start to see a smoldering black flame you are producing acrolein (carcinogen found in cigarette smoke). Add oxygen and heat. (<300 o F) Burning Glycerin Guatebiodiesel is packing a PVC tube with: 1 part shredded newspaper, 1 part sawdust, 1 part glycerin Fire is started in a wood burning stove with wood, and glycerin logs are added when hot. Burns very hot with a clear blue flame.

22 AUGI Research on Glycerin Combustion 1. High levels or particulate matter (via the ash analysis), chlorine, and water contents in combination with the low energy value indicated that crude glycerin is not sufficient for consideration as a sole source fuel in an industrial triple pass fire tube boiler application. 2. Even with specialized modifications made to the boiler, the energy value in crude glycerin is inadequate for successful start-up and continuous boiler operation. 3. The high level of residual chlorine contained in the crude glycerin sample is too high for long term boiler operation and can adversely affect internal mechanisms of the boiler. 4. The high level of particulate matter (ash content) contained in the crude glycerin samples is too high for safe boiler operation. 5. In order to maintain a flame in the industrial fire tube boiler, a small amount of crude glycerin (10% V/V) was co-fired with yellow grease (90% V/V). 6. Pump mixing was not adequate to maintain a consistently blended fuel. Differences in the densities of crude glycerin and yellow grease require an advanced mixing mechanism in order to maintain a homogeneous fuel mixture. 7. Higher boiler maintenance costs and excessive clean-up schedules reduce the favorable economical consideration that crude glycerin low market values proffer 8. Changes in the boiler fuel from that which the boiler was originally designed to burn can reduce boiler efficiency and negatively impact the load. 9. The current estimated cost per million Btu for the fuel blend (10% crude glycerin / 90% yellow grease) was calculated at $ The higher market prices for yellow grease does not make this a competitive fuel in comparison with natural gas costs at the industrial level.

23 AG Solutions Boiler Has the ability to be fueled with new or used vegetable oils off all types and with some of the glycerin byproduct from the biodiesel production. We have several customers who currently utilize their glycerin as part of their fuel.

24 Wash water A biodiesel wash will typically be 30-50% water by volume. Very high biological oxygen demand (BOD) Water from a first wash can contain around 6% BOD and less than 1% oil, biodiesel, free fatty acids, glycerol, soap, and catalyst. 3-4 washes -> water used is 2-4x the amount of biodiesel batch Reverse osmosis, ultra filtration, and ozone generators can effectively reduce BOD High ph (must soften water)

25 Wash Water BOD is an indicator of organic water pollution BOD in wash water is around 12,000 mg/l - OFF THE CHARTS HIGH For reference, a pristine river has a BOD of about 1 mg/l, treated sewage is about 20, influent coming into most waste water treatment facilities is about 200, untreated sewage is about 600 To lower BOD: Dilute and Oxygenate High BOD leads to slime

26 Wash water constructed wetlands

27 Excess Methanol Methanol recovery systems through distillation (boils at 148.5º F at 1 atm) For methanol recovery see Biodiesel Safety and Best Management Practices for Small- Scale Noncommercial Use and Production : pubs.cas.psu.edu/freepubs/pdfs/agrs103.pdf Watch out for VERY DANGEROUS methanol vapor that is toxic and can flash (requires 4x the density of gasoline vapors).

28 Methanol Recovery

29 Absorbents (e.g. Amberlite and Magnesol)

30 Magnesol Does not break down

31 Bad Batches / Glop / WVO Sludge Waste Oil Burner- Bad Batches can either be re-reacted, or used in a waste oil burner for process heat, along with some amount of WVO. Pilot light issue with oil burners and biodiesel We ship out serious glop/sludge to industrial compost site

32 Resources Agricultural Utilization Research Institute al.pdf International Journal of Poultry Science 5 (11): , 2006 ISSN Asian Network for Scientific Information, 2006 Evaluation of Glycerine from Biodiesel Production as a Feed Ingredient for Broilers S. Cerrate, F. Yan, Z. Wang, C. Coto, P. Sacakli and P.W. Waldroup2 Department of Poultry Science, University of Arkansas, Fayetteville AR 72701, USA

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