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Biodiesel

Biodiesel

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BIODIESEL

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file:///E|/Tech/Fuels/biodies.htm

BIODIESEL -

BIODIESEL - McDIESEL - EEA In Summer, 1989, I learned about the conversion of animal fats and vegetable oils to their methyl esters for fuel purposes. The process is called "Transesterification", and is quite simple. Being interested in alternate fuels, I mulled this over in my subconscious and in November, 1989, I wondered what happened to all that good oil/fat when it was "used up". I found that there are about a billion gallons a year under the heading "yellow grease" which are used for soap, cattle feed, but has a very low value (<$1/gallon) relative to new oil/fat. I wondered if it could be used to make the esters for fuel. I went to our local McDonalds and got a gallon of "waste grease" from their grease dumpster in back. (UGH!) I took it in my lab, made minor adjustments in the recipe and made a gallon of beautiful fuel from (UGH) grease. Wow! As a chemist I had a wonderful time for the next few months making "transesterified waste vegetable oil" from many feedstocks. Even made it from bacon grease at Christmas in my daughter in laws kitchen from grocery store components. At that time the DENVER RTD bus company was considering alternate bus fuels. We approached the bus company to see if they were interested in this alternative clean fuel. Sure, but they needed more than a gallon to test. I went to our UNIT OPS laboratory at the Colorado School of Mines and made 100 gallons (2 drums) for testing by RTD. I didn't think "transesterified waste vegetable oil" was a very good name, so, considering the source, I decided to call it MCDIESEL. I applied for a copyright. I even approached McDonalds to see if they were interested. They were, but said they would sue me if I used that name. Later people came to call these fuels "BIODIESEL", and I now live with that. However, I would love to have had McDonalds sue me—what publicity! I formed a company with Prof. Mike Graboski (at CSM) and Ed Names (lawyer type) to make and promote MCDIESEL. We published a number of papers, talked to many people, entered into an agreement with a Chemical Engineering Mfg. Co., (later a source of much grief). We discovered that there was NO political base for using low cost waste grease for an alternate fuel. There was a tremendous base for spending much more money to make Biodiesel from Soy Oil. Now biodiesel is highly political and there is a newsletter telling of test results and new companies hoping for government subsidies courtesy of global warming. Check them out at www.biodiesel.org. In February 1990 we tested the fuel on a bus and it ran fine and had low emissions. We have published a number of papers on Biodiesel from waste grease, but no one is particularly interested. Meanwhile biodiesel from soy is still $3-4/gal. If you are interested in making some biodiesel, here is our recipe for making it in the kitchen with easily available materials:

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May 20, 1997 TO: People interested in making Biodiesel FROM: Thomas B. Reed SUBJECT: Making Bio-diesel in the kitchen BIODIESEL FROM VEGETABLE OILS AND ANIMAL FATS Thank you for your inquiry concerning making biodiesel. Biodiesel is a new, alternative, renewable, clean diesel fuel made from triglycerides (oils, fats, waste cooking oils, ....). Making biodiesel on a large scale is a task for chemical engineers. It is a relatively simple process, but requires purification and washing to make a commercial fuel, especially if you use waste vegetable oil. However, if you would like to try the reaction in your kitchen, here’ the recipe for a s simple demonstration using common household chemicals. REMEMBER TO HANDLE ALL CHEMICALS WITH CARE! While these are common "household" chemicals, the methanol will burn with an almost invisible flame, so extinguish all fires; the lye can burn your fingers or blind you. Read the warnings on the can! The reaction (transesterification) substitutes methanol (wood alcohol, dri-gas, ....) for the Glycerine in triglycerides (fats, oils) to make the methyl esters called biodiesel. It uses lye as a catalyst. A junior chemist might write it: Triglyceride (fats or oils) + Methanol =====> Biodiesel + Glycerine (Lye catalyst) The lye converts a small amount of the oil to soap. After the reaction is over, the Glycerine and soap settle to the bottom of the vessel and the biodiesel floats on top. Measure 500 ml (1 cup) of vegetable oil (cooking oils such as Mazola, New Maid etc.) into a blender (or mixing bowl). (Most modern measuring cups show both ml and cups.) Heat the oil to 120 F (not critical) using a cooking thermometer while carrying out the next step. In a separate cup measure 85 ml of methanol. (The easiest source of methanol is Dri-Gas, obtainable from any automotive store. Be sure to get the cheap one - contains methanol -,, not the one containing iso-propyl alcohol.) To this add 1/4 level tsp. of lye (sodium hydroxide). (Red Devil lye is carried by most grocery and hardware stores.) Stir well with a wooden spoon, crushing as needed until all the flakes disappear. (The mixture will be slightly cloudy and is called "sodium methoxide".) Add the methanol-lye mixture to the warm oil while vigorously stirring, using a mixer, paint stirrer (electric drill with propeller) or blender. Stir for 30 minutes. The mixture at first thickens, then becomes thinner than the original oil.

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Allow the mixture to settle for a day in a tall thin vessel. The biodiesel floats to the top and can be poured off into a container for display. The glycerine and soap go to the bottom and can be discarded, (but can make a high glycerine soap). You have now made biodiesel on a small scale and can appreciate the use of renewable fuels from farms. This clear biodiesel contains a very small amount of soap. If you want to use it in your diesel vehicle it would be of no consequence. However, if you want to make large quantities or for sale, European specifications require removal of the soap by washing or other effective means. If you try this successfully, I’ be interested in hearing from you about your experience. d Please send a picture. BIODIESEL FROM WASTE VEGETABLE OILS Waste vegetable oils used for cooking are an attractive source of biodiesel, but are more difficult to convert because they contain 2-10% free fatty acids (the cause of the rancid taste) and can make a big mess. First it is necessary to remove any water present in the waste oil. Heat in the oven at 220°F for an hour or until no bubbles can be seen. It is then necessary to titrate the oil to determine how much free fatty acids they contain. To Measure Free Fatty Acid content of your oil: mix 1 ml oil with 10 ml isopropyl alcohol (available as the other dry-gas) + 2 drops phenolthalien solution (available in a hobby shop or toy store selling chemistry set supplies). Dropwise add 0.1% lye solution (1 g lye in 1 liter water) with vigorous stirring until the solution stays pink for 10 seconds. (20 drops = 1 ml) Record the milliliters of 0.1% lye solution used. For each liter of waste vegetable oil you will need one gram of granular solid lye for each ml of 0.1% lye solution used to titrate the free fatty acids, plus the 3.5 grams required as a catalyst as described above for new oil. Completely dissolve the proper amount of Lye in the methanol. This combined mixture makes the sodium methoxide. Add the alcohol-lye to the oil, stir VIGOROUSLY, and separate, as in instructions above for new oil . If not, these are jobs for professional chemists and chemical engineers. If you would like to learn more, please take a course in chemical engineering at the Colorado School of Mines or your nearest technical college first. USING TRIGLYCERIDES FOR FUEL Unprocessed oils and fats can also be used in diesel engines, but require adjustment to the engines and driving habits. They are too thick, so do not inject well. They become solid below about 50 °F. If the engine is started on conventional diesel and converted to heated vegetable oils after it is thoroughly warmed up, then switched back to diesel for cooling, engine life is greatly extended. A Mr. Louis Wichinsky claims to have developed engine modifications that permit direct combustion of waste vegetable oils. If you are mechanically inclined, rather than chemically inclined you may prefer this route. Reach him at 914 434 5067; 702 873 2772

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Biodiesel Projects

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Project Management, Market Development, and Public Outreach for Biodiesel
Directing Organization: U.S. Department of Energy (DOE), 1000 Independence Avenue, SW, Washington, DC 20585 Project Manager: J.J. Sheehan, (303) 275-4420 Contractor: National Renewable Energy Laboratory (NREL), 1617 Cole Boulevard, Golden, CO 80401-3393 Principal Investigator: J.J. Sheehan, (303) 275-4420 Contract Number: DE-AC02-83CH10093 Contract Period: 10/94–9/95 Contract Funding (Source): FY 1995: $70,900 (DOE) Objective: Establish strategic and operational plans for biodiesel, coordinate and support market development activities in the biodiesel industry and DOE, and increase public awareness of and support for biodiesel technology. Approach/Background: Biodiesel is a renewable diesel fuel substitute produced by chemically reacting an alcohol with a natural oil. The approach to DOE's biodiesel project has changed dramatically during the past 2 years. DOE's focus was on long-term research for biodiesel produced via microalgal conversion of waste CO2 from fossil- fueled power plants to natural oils. This research is necessary in the long run to provide a resource base of natural oils sufficient to meet the needs of the transportation sector. The current project has both a short-term and a long- term focus. The near-term focus is on opportunities for biodiesel made from vegetable oil and animal fats. Status/Accomplishments: We have made great strides in developing a coordi- nated strategy for establishing a U.S. biodiesel indus- try. For the first time, we have a strategic plan that identifies several critical paths for biodiesel, and thus focuses our limited resources on activities most critical to achieving our goals. Public support for biodiesel is increasing exponentially. Two years ago, biodiesel was virtually unheard of in the United States. Today, it is being tested in environmentally sensitive areas, and in niche markets such as mining, buses, government fleets, and marine use. Much of the increased interest is due to the efforts of the National Biodiesel Board (NBB). NREL has developed a working relationship with the NBB that allows each to leverage the other's limited R&D, market development, and outreach funds. Major Project Reports: See bibliography. Summary Date: September 1995

Existing Technology Options for Production of Biodiesel from Low-Cost Feedstocks

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Directing Organization: U.S. Department of Energy (DOE), through the National Renewable Energy Laboratory (NREL), 1617 Cole Boulevard, Golden, CO 80401-3393 Project Manager: J.J. Sheehan, (303) 275-4420 Contractor: MARC-IV, 6807 W. 202nd Terrace, Bucyrus, KS 66013 Principal Investigator: S. Howell, (913) 681-0400 Contract Number: ACF-5-14418-01 Contract Period: 1/95–12/95 Contract Funding (Source): FY 1994: $25,000 (DOE) Objective: Determine technology options for producing and evaluating biodiesel from low-cost feedstocks at the pilot scale. Approach/Background: The cost of biodiesel produced from virgin soybean oil in the United States is $2.50 to $3.50 per gallon. This high cost remains the greatest obstacle to market penetration for biodiesel in blends or as a neat fuel. Three-quarters of the production cost is associated with the feedstock itself. Our work focuses on determining the feasibility of using lower-cost feedstocks, such as recycled cooking oils and waste from animal processing operations. We have joined forces with the Fats and Proteins Research Foundation and the National Biodiesel Board to conduct a technoeconomic analysis of conventional (off-the-shelf) technologies available today for processing these low-cost feedstocks, which have special processing issues. The greatest issue is the increased level of free fatty acids found in recycled materials. Once we identify technologies that can handle higher levels of free fatty acids, we will establish a plan to produce pilot-scale quantities of biodiesel made from these feedstocks. We will also test to establish the fuel's physical and chemical characteristics and their impact on engine and fuel performance. Status/Accomplishments: Preliminary results indicate a variety of technology options that can handle 10%–15% levels of free fatty acids in the feedstock. We would like to be able to handle higher levels of free fatty acid, but these technologies offer the opportunity to process waste restaurant grease and other materials. We have determined that pilot-scale operations, which negating the need for constructing our pilot plant, are available for producing biodiesel from these feedstocks. A final report from MARC-IV, which will be the basis for negotiating a subcontract for the next phase of research, is anticipated in early FY 1996. This will include producing and testing fuel. Major Reports: None. Summary Date: September 1995

New Process Options for Biodiesel Conversion and Glycerol Utilization
Directing Organization: U.S. Department of Energy (DOE), 1000 Independence Avenue, SW, Washington, DC 20585 Project Manager: J.J. Sheehan, (303) 275-4420

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Biodiesel Projects

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Contractor: National Renewable Energy Laboratory (NREL), 1617 Cole Boulevard, Golden, CO 80401-3393 Principal Investigator: J.J. Sheehan, (303) 275-4420 Contract Number: DE-AC02-83CH10093 Contract Period: 10/94–9/95 Contract Funding (Source): FY 1995: $57,900 (DOE) Objective: Assess alternative process technologies for converting natural oils to biodiesel and using the glycerol by- product. Approach/Background: Biodiesel is a renewable diesel fuel substitute produced by chemically reacting an alcohol with a natural oil. When the natural oils are in the form of triglycerides, this reaction is known as transesterification, and is carried out today using basic catalysts such as NaOH or methoxide. Most transesterification processes do not work well with feedstocks that contain high levels of free fatty acids. The intent of this work is to identify processes that are more efficient than current conven- tional catalyst processes, and less sensitive to free fatty acid content. A more flexible process allows the use of a range of lower-cost feedstocks. The other major economic factor in converting natural oils to biodiesel is using glycerol. Even for niche applications, the volume of biodiesel production required to meet these small markets will result in a level of glycerol production that far exceeds current market demands. New, high-volume markets for glycerol are needed if it is to retain any value as a credit in the process. Status/Accomplishments: We have focused on developing enzymatic catalysts to improve the flexibility of the transesterification process. To this end, we are putting in place a three-way CRADA with the USDA's Agricultural Research Service and the Fats and Proteins Research Foundation (FPRF) to collaborate on the initial evaluation of lipase enzymes as catalysts for transesterification. Researchers at USDA's Eastern Regional Research Center are conducting bench-scale experiments on biodiesel production using a variety of commercial lipase preparations. They have demonstrated that lipases exhibit much greater flexibility in handling a range of feedstocks that contain as much as 50% free fatty acids. FPRF, a nonprofit, private research organization, is supplying expertise on and samples from waste restaurant grease collection operations. NREL will use this information to establish the economic viability of enzymatic esterification with current commercial lipases. We have also established a partnership with ARCO Chemical to evaluate the production of di-tert-butyl glycerol (DTBG) as a complementary fuel additive product derived from the glycerol by-product. ARCO has tested DTBG as an oxygenate for diesel fuel. We will analyze DTBG production, coupled with biodiesel production. Major Project Reports: None. Summary Date: September 1995

Life-Cycle Assessment of Biodiesel
Directing Organization: U.S. Department of Energy (DOE), through the National Renewable Energy Laboratory (NREL), 1617 Cole Boulevard, Golden, CO 80401-3393 Project Manager: J.J. Sheehan, (303) 275-4420

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Biodiesel Projects

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Contractor: Ecobalance, Inc., 1 Church Street, Rockville, MD 20850 Principal Investigator: J. Besnainou, (301) 309-0800 Contract Number: ACG-5-15297-01 Contract Period: 8/95–5/96 Contract Funding (Source): FY 1995: $50,000 (DOE) FY 1995: $50,000 (USDA) Objective: Produce an analytical tool for evaluating the energy, environmental, and economic benefits of producing biodiesel in the United States from lipid sources. Approach/Background: Life-cycle analysis (LCA) (first used by the Coca Cola Company 20 years ago) is now gaining world-wide prominence as a valuable tool for understanding the impacts of new products and processes on the environment and on corporate bottom lines. Such an analysis forces an assessment of the impacts of a given product from the extraction of any and all raw materials from the earth to the processing, distribution, and use of the product. The definition of renewable fuels should be based on an LCA. The approach for this study is based on an exciting new set of software tools for LCA developed by Ecobalance. Thus, rather than simply producing a report on the life-cycle benefits of biodiesel, we will produce licensable software tools that companies and government entities can use to evaluate specific scenarios or product and process improvements for biodiesel. Because of the near-term opportunities for biodiesel, this analysis will first focus on producing biodiesel from sources of natural oils. In the future, it will be expanded to include biodiesel via microalgal conversion of waste CO2 to natural oils. Status/Accomplishments: To be worthwhile, an LCA must have broad-based input from all stakeholders. Thus, we built a consortium of biodiesel stakeholders to provide input on all assumptions, approaches, and system boundaries for the analysis. We have established a Biodiesel Working Group, an unprecedented collection of private and government interests that includes USDA, DOE, EPA, the City of Chicago, the National Biodiesel Board, Exxon, ARCO Chemical, Cargill, Twin Rivers Technologies, the Energy and Environmental Studies Institute, and the American Petroleum Institute. A scoping document has been drafted. We encourage anyone interested in providing input to contact the project manager. Major Project Reports: None. Summary Date: September 1995

CO2 Mitigation in Fossil Fueled Power Plants Using Microalgae with Coproduction of Biodiesel
Directing Organization: U.S. Department of Energy (DOE), 1000 Independence Avenue, SW, Washington, DC 20585

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Project Leader: J.J. Sheehan, (303) 275-4420 Contractor: National Renewable Energy Laboratory, 1617 Cole Boulevard, Golden, CO 80401-3393 Principal Investigators: K.L. Kadam and K. Zeiler, (303) 384-6866 Contract Number: DE-AC02-83CH10093 Contract Period: 10/94–9/95 Contract Funding (Source): FY 1995: $67,000 (DOE) Objective: Establish a technoeconomic model of microalgae technology for CO2 mitigation with coproduction of biodiesel. Approach/Background: Microalgae are unique photosynthetic organisms in that they accumulate high levels of natural oils, thrive in high-salinity water, and use CO2 (an important green- house gas) as their sole carbon source. Microalgae grown in ponds can be used to trap CO2 from power- plant flue gas while producing a feedstock for biodiesel. Status/Accomplishments: A spreadsheet-based economic model was developed for microalgae production using CO2 from flue gases. This model predicts costs within 2% of those predicted by an earlier FORTRAN model, but is much easier to use. It has been used to assess targets for lipid content and growth rate of genetically engineered algae. Because CO2 collection is the single largest cost factor, we developed a model that predicts costs for recovering and delivering CO2 from flue gas, in lieu of using market costs for CO2. The process steps include monoethanolamine (MEA) extraction, compression, dehydration, and transportation to the ponds. This approach yields a delivered CO2 cost of $41/mt, versus a market price of $66/mt of CO2. The model has also shown that MEA extraction is 40% less expensive than the simpler route of direct flue gas utilization. We have used our models to establish mid- and long-term targets for this technology. An improved process in the mid-term will result in a net cost $20/mt of CO2 mitigated. This is very competitive with other mitigation technologies. In the long term, we hope to identify process goals that reduce mitigation costs to zero, by reducing process costs and increasing biodiesel yields as a by-product credit. Major Project Reports: See bibliography. Summary Date: September 1995

Genetic Transformation of Microalgae for Enhanced Production of Natural Oils as a Feedstock for Biodiesel
Directing Organization: U.S. Department of Energy (DOE), 1000 Independence Avenue, SW, Washington, DC 20585 Project Manager: J.J. Sheehan, (303) 275-4420 Contractor: National Renewable Energy Laboratory (NREL), 1617 Cole Boulevard, Golden, CO

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Biodiesel Projects

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80401-3393 Principal Investigators: T. Dunahay and P. Roessler, (303) 384-6280/384-6253 Contract Number: DE-AC02-83CH10093 Contract Period: 10/94–9/95 Contract Funding (Source): FY 1995: $167,000 (DOE) Objective: Develop genetic transformation systems for microalgae as tools for creating genetically engineered microalgae capable of enhanced natural oil production. Approach/Background: When grown in mass culture, microalgae can accumulate storage oil. They may therefore be an excellent feedstock for producing biodiesel fuel. The economics of producing biodiesel from microalgae would be significantly improved if microalgal strains with improved oil production characteristics could be developed. Genetic engineering can introduce these desirable characteristics into microalgae, but genetic transformation systems are not available for most microalgal species. Status/Accomplishments: We have developed a genetic transformation system for diatoms, an abundant group of microalgae with excellent potential for biodiesel production. This system is based on expressing a bacterial antibiotic resistance marker gene under the control of regulatory regions from an algal gene. Genetically transformed cells can be identified by their ability to grow in the presence of certain antibiotics. We have used this system to introduce additional native and foreign genes into the diatoms Cyclotella and Navicula. This represents a major advance in the field of algal biotechnology. Major Project Reports: See bibliography. Summary Date: September 1995

Isolation of a Polyubiquitin Gene Promoter for Expression of Foreign Genes in Microalgae
Directing Organization: U.S. Department of Energy (DOE), through the National Renewable Energy Laboratory (NREL), 1617 Cole Boulevard, Golden, CO 80401-3393 Project Manager: J.J. Sheehan, (303) 275-4420 Contractor: George Mason University, 4400 University Drive, Fairfax, VA 22030-4444 Principal Investigator: A. Christensen, (703) 993-1025 Contract Number: XCH-4-14406-01 Contract Period: 10/94–9/96 Contract Funding (Source): FY 1995: $44,698 (DOE) Objective: Isolate an algal ubiquitin gene and assess the ability of its regulatory regions to mediate foreign gene expression in microalgae. Approach/Background: A major focus of the biodiesel project at NREL is to investigate the use of

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Biodiesel Projects

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microalgal lipids for producing biodiesel fuel. One goal is to optimize lipid production in microalgae by manipulating the flow of carbon into lipids via genetic engineering. The availability of promoters and other regulatory regions from a variety of algal genes will enhance our ability to accomplish this goal. Ubiquitin, a highly conserved protein, is expressed at high levels in many kinds of cells. The focus of this project is to isolate and characterize the regulatory regions from a microalgal ubiquitin gene and assess the ability of these gene sequences to mediate the expression of foreign genes in oil-producing microalgae. Status/Accomplishments: We screened a gene library from the diatom Cyclotella cryptica for the presence of ubiquitin gene sequences using a maize ubiquitin gene as a probe. We isolated and characterized a clone via restriction mapping and nucleotide sequencing. Preliminary results from the sequence analysis confirm the presence of an algal ubiquitin gene. We will analyze this clone to characterize the promoter and terminator regulatory regions for use in microalgal gene expression systems. Major Project Reports: None. Summary Date: September 1995

Biochemistry and Metabolic Engineering of Microalgae for Enhanced Biodiesel Production
Directing Organization: U.S. Department of Energy (DOE), 1000 Independence Avenue, SW, Washington, DC 20585 Project Manager: J.J. Sheehan, (303) 275-4420 Contractor: National Renewable Energy Laboratory (NREL), 1617 Cole Boulevard, Golden, CO 80401-3393 Principal Investigators: P. Roessler and E. Jarvis, (303) 384-6253/384-6147 Contract Number: DE-AC02-83CH10093 Contract Period: 10/94–9/95 Contract Funding (Source): FY 1995: $358,000 (DOE) Objective: Elucidate the biochemistry of microalgal lipid synthesis and develop metabolic engineering strategies for optimizing their production. Approach/Background: Creating genetically engineered microalgae with enhanced capabilities for producing biodiesel requires knowledge of the biochemical pathways that affect lipid accumulation. We hope to manipulate these pathways to alter the quantity and quality of lipids synthesized. Status/Accomplishments: We are investigating two approaches to enhance lipid production rates in microalgae: 1. Introduce additional copies of the gene that encodes acetyl-CoA carboxylase (ACCase), an enzyme that plays a key role in lipid synthesis (preliminary results show that microalgal cells genetically

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Biodiesel Projects

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engineered in this manner have enhanced ACCase activity) 2. Reduce the rates of synthesis of other compounds, such as storage carbohydrates, to provide more substrate for lipid synthesis. We have cloned an important gene involved in microalgal carbohydrate metabolism, which may be a target for inactivation. Major Project Reports: See bibliography. Summary Date: September 1995

Return to the Table of Contents
File Modified: October 15, 1996

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Bibliography (by Project)

file:///E|/Tech/Fuels/bibproj.html

Biodiesel
Project Management, Market Development, and Public Outreach for Biodiesel Brown, L.M.; Sprague, S.; Jarvis, E.E.; Dunahay, T.G.; Roessler, P.G.; Zeiler, K.G. 1994. Biodiesel from Aquatic Species Project Report: FY 1993. NREL/TP-422-5726. Golden, CO: National Renewable Energy Laboratory. Sheehan, J. 1994. "Bioconversion for Production of Renewable Transportation Fuels in the United States: A Strategic Perspective." Bioconversion for Fuels. Edited by M. Himmel, J. Baker, and R. Overend,, Washington, DC: American Chemical Society, pp. 1-52. "FY 1995 Strategic Plan for Biodiesel (Draft)." U.S. Department of Energy. 1995. FY 1995 Strategic Plan for Biodiesel (Draft). Washington, DC: Office of Transportation Technologies: Biofuels Systems Division. CO2 Mitigation in Fossil Fueled Power Plants Using Microalgae with Coproduction of Biodiesel Kadam, K.L. 1994. "Engineering Analysis of Microalgal Technology with Recommendations for Laboratory Research." Milestone Report, December. Kadam, K.L. 1995. Power Plant Flue Gas as a Source of CO2 for Microalgae Cultivation: Technology and Economics of CO2 Recovery and Delivery. Genetic Transformation of Microalgae for Enhanced Production of Natural Oils as a Feedstock for Biodiesel Brown, L.M.; Sprague, S.; Jarvis, E.E.; Dunahay, T.G.; Roessler, P.G.; Zeiler, K.G. 1994. Biodiesel from Aquatic Species Project Report: FY 1993. NREL/TP-422-5726, January. Dunahay, T.G.; Jarvis, E.E.; Roessler, P.G. (in press). "Genetic Transformation of the Diatoms Cyclotella cryptica and Navicula saprophila." Journal of Phycology. Roessler, P.G.; Brown, L.M.; Dunahay, T.G.; Heacox, D.A.; Jarvis, E.E.; Schneider, J.C.; Talbot, S.G.; Zeiler, K.G. 1994. "Genetic Engineering Approaches for Enhanced Production of Biodiesel Fuel from Microalgae." Bioconversion for Fuels. Edited by M. Himmel, J. Baker, and R. Overend, Washington, DC: American Chemical Society, pp. 255-270. Dunahay, T.G. 1993. "Transformation of Chlamydomonas reinhardtii with Silicon Carbide Whiskers." Biotechniques 15(3):452-454. Jarvis, E.E.; Brown, L.M. (1991). "Transient Expression of Firefly Luciferase in Protoplasts of the Green Alga Chlorella ellipsoidea." Current Genetics 19:317-321. Biochemistry and Metabolic Engineering of Microalgae for Enhanced Biodiesel Production Brown, L.M.; Sprague, S.; Jarvis, E.E.; Dunahay, T.G.; Roessler, P.G.; Zeiler, K.G. 1994. Biodiesel from Aquatic Species Project Report: FY 1993. NREL/TP-422-5726. Golden, CO: National Renewable

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Bibliography (by Project)

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Energy Laboratory. Roessler, P.G.; Ohlrogge, J.B. 1993. "Cloning and Characterization of the Acetyl-coa Carboxylase Gene from the Diatom Cyclotella cryptica." Journal of Biological Chemistry 268:19254-19259. Roessler, P.G.; Brown, L.M.; Dunahay, T.G.; Heacox, D.A.; Jarvis, E.E.; Schneider, J.C.; Talbot, S.G.; Zeiler, K.G. 1994. "Genetic Engineering Approaches for Enhanced Production of Biodiesel Fuel from Microalgae." Bioconversion for Fuels. Edited by M. Himmel, J. Baker, and R. Overend, Washington, DC: American Chemical Society, pp. 255-270. Schneider, J.C.; Roessler, P. 1994. "Radiolabeling Studies of Lipids and Fatty Acids in Nannochloropsis (Eustigmatophyceae), an Oleaginous Marine Alga." Journal of Phycology 30:594-598. Schneider, J.C.; Roessler, P.G. (in press). "A Mutant of Nannochloropsis Deficient in Eicosapentaenoic Acid Production." Phytochemistry.

Wiselogel, A. (ed.) 1995. Terrestrial Biomass Interface Feedstock Project Guidance Committee Charter. Wiselogel. A. 1995. Testimony to U.S. House of Representatives Agriculture Committee. Rethinking U.S. Agricultural Policy from an Energy Perspective. Akron, CO, April 17. Wiselogel, A. 1995. " Production of Biomass Crops on CRP Land." National Association of

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Biodiesel recipe from Mike Pelly: Journey to Forever

file:///E|/Tech/Fuels/biodiesel_mike.html

Mike Pelly's recipe
Mike Pelly lives in the US North West. He has much more knowledge and experience of biofuels than we do. "I live for renewable energy projects," he says. Mike's been making his own biodiesel fuel from waste cooking oil for the last three years, using it in several different cars. He finds it "far superior" to fossil-based diesel fuel. Mike sent us a full report on how he makes biodiesel. "It's a result of my work over the past three years," he said. "Pass it along to anyone you please." Here it is.

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Bio-diesel From Used Kitchen Grease or Waste Vegetable Oil
by Mike Pelly
CAUTION: Wear proper gloves, apron, and eye protection and DO NOT inhale any vapors. Exposure to methanol can lead to blindness and death. Sodium hydroxide can cause severe burns and death. Together these two chemicals form sodium methoxide. This is an extremely caustic chemical. Do not inhale any vapors. Wear a mask and full body covering for safety, this means chemical-proof gloves with cuffs that can be pulled up over long sleeves -- no shorts or sandals. These are strong and caustic chemicals -- treat them as such!

Ethanol Robert Warren's still Building the Charles 803 alcohol fuel still Operation of an alcohol still Fuel ethanol FAQ Vegetable oil to replace diesel? Four fuels for the future Can you drink it? Ethanol resources on the Web Home What people are saying about us

Making biodiesel
This procedure is called transesterification, similar to saponification. Sound familiar? Saponification is soap making. In soap making one takes a transfatty acid or triglyceride (oil or kitchen grease), blends it with a solution of sodium hydroxide (NaOH or lye) and water. This reaction causes the ester chains to separate away from the glycerin. These ester chains are what becomes the soap. They're also called lipids. Their unique characteristic of being attracted to polar molecules such as water on one end and to non-polar molecules like oil on the other end is what makes them effective as soap. In transesterification reactions, first a solution of NaOH and methanol (CH3OH) is mixed, creating sodium methoxide (Na+ CH3O-). This STRONG chemical breaks the transfatty acid into glycerin and also ester chains (biodiesel), along with some soap if you're not careful (more on that later). The esters become methyl esters. They would be ethyl esters if reacted with booze (ethanol).

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Figures 1-3 show these two reactions. The zigzag lines in the triglyceride diagram (Figure 1) are shorthand for carbon chains. At both ends of each line segment is a carbon atom.
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Overview
This description starts with an overview of all the steps and goes into more detail when needed. The solution of WVO reclaimed from a restaurant's waste grease barrel gets preheated to 120-130 degrees Fahrenheit (48-54 deg C). The amount of methanol needed for the reaction is 15-20% of Waste Vegetable Oil (WVO) by mass. The densities of these two liquids are fairly close so measuring 15% of methanol by volume should be about right. To be completely sure, measure out a

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half-liter of both fluids, weigh, and calculate exactly what 15% by mass is. Different WVOs can have different densities depending on what type of oil it originally was and how long it was used in the deep fryer. If uncertain about densities then it's better to go heavy on the methanol, say 20%. Example: When transesterifying 100 liters of WVO, include 15 to 20 liters of methanol.

The methanol is mixed into solution with sodium hydroxide, thus creating sodium methoxide in an exothermic reaction (it gets warm from bonds forming). This sodium methoxide is to be treated with extreme caution! Do not inhale any vapors! If any happens to get splashed on skin, it will burn without being felt (killing nerves) so wash immediately. Sodium methoxide is also very corrosive to paints. The best type of containers for handling it are ones made of stainless steel. Used restaurant equipment supply stores are a good place to look for this type of equipment. Braze on plumbing fittings where needed.

Mixing

Any propeller or paint stirrer coupled to a 1/2-inch drill securely positioned in a jig works fine as a mixer. The sodium methoxide is added and stirred together with WVO for 50 minutes to an hour. Over the course of this hour the transesterification process separates the methyl esters from the glycerol. The CH30 of the methanol then caps off the ester chains and OH from the NaOH stabilizes the glycerol.
Scale for measuring out lye and chemical supplies used for a titration.

After stirring the reactants at 120-130 deg F for one hour, allow the solution to sit and cool for eight or more hours. The less dense methyl esters float to the top and the denser glycerin congeals on the container's bottom into a hard gelatinous mass.

Separation
An alternative way of doing this is to allow the reactants to sit for about an hour after mixing, keeping the brew at least 100 deg F, carefully separate the esters while the glycerol is still a semi-liquid.
Sample of used oil about to be titrated.

This can be done by draining the reactants out the bottom of the container through a transparent hose. As soon as less dense and dark esters appear in the hose divert the contents to a separate container.

The glycerin (though not yet solidified) will have a dark brown color and the esters honey colored. Keep a watch on what flows through the sight tube: when the lighter colored esters appear divert this fluid to a separate container. If any is missed it is easy to later retrieve from the solidified glycerin container. This glycerin sets up around 100 deg F.
Color of titrated liquid

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Color of titrated liquid sample when at the correct pH.

Figure 4 shows one example of a system for separating two liquids with different densities. This could make a good pre-filter or be used to separate oils, soap and glycerin/esters goop. Marine/boat fuel cleaning systems do a good job providing filter needs.
Figure 4 Figure 5

Weighing correct amount of lye.

Lighting burner under transesterifyer vessel.

Figure 5 shows the reaction vessel (#1) where WVO is mixed and heated. Heating is accomplished by (#2) hotplate, propane-burner, a diesel stove would work well. A proposed alternative using very little electricity is illustrated in Figure 6. This system would use a furnace type burner run on reclaimed esters to heat its reaction vessel. The vessel's stirring action is created by thermo inversion currents generated by the vessel's external cooling tubes and a baffled exhaust vent that runs up through its center. Figure 5 also shows a blender (#3) used to mix up the sodium methoxide. When making 16 liter (5 gal) batches, I use a yard sale glass blender designated for the sodium methoxide solution, but I can't fit it in all at once, so I measure out three separate portions.

View of sodium methoxide mixer (left) and transesterifyer vessel (right).

Glycerin

View of sodium methoxide mixer being drained into transesterifyer vessel (note thermometer).

Reclaimed glycerin can be composted after being vented for three weeks to allow residual methanol to evaporate off. Another way of disposal, though a great bit more complicated, would be to separate up its components. The majority of its components are methanol, pure glycerin (a valuable product for medicines, tinctures, hand lotions, dried plant arrangements along with other uses) and wax. Distillation is one way this is often accomplished but glycerin has a high boiling point while under high vacuum pressure this method is difficult.

I was able to find someone who could use my glycerin (for dried flower arrangements) through the Industrial Materials Exchange (IMEX). IMEX has a publication that comes out every other month with listings, looking for and offering all types of materials. This glycerin also makes an excellent industrial type degreaser/soap. A good way to

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Valve on bottom of transesterifyer vessel user to decant out more dense glycerin from less dense esters.

This glycerin also makes an excellent industrial type degreaser/soap. A good way to purify it is to heat it back to a liquid in a double boiler. Once it is back to a liquid the impurities (french fry chunks) will sink to the bottom and its color will become more uniform.

Soap
Suspended in the reclaimed methyl esters will also be some soapy residues. These are the result of Na+ ions from the sodium hydroxide (NaOH) reacting with some water that's created from methanol bonding with the ester chains. If the reaction has more than its usual amount of soap this is because some of the lye came in contact with water before it had any chance of reacting with the methanol.

It's important to keep blender and all utensils the lye comes in contact with as dry as possible. The possibility of having a good clean splitting of esters from glycerin with Fuel pump and filters -little soap by-product is much better on a warm dry summer day than a damp winter these are used last, after soapy residues and lye have day.
had time to settle out of biodiesel.

There is more than one school of thought on getting the esters from this stage to the fuel tank. One is to let it sit for a while (about a week) allowing the majority of the soap residues to settle before running the esters through a filtration system then into vehicle/home fuel tank.

Washing

Another system is to water wash the soaps out of fuel. When washing esters the first Overview of trailer-mounted time it's best to add to the water a small amount of acetic acid (vinegar). The acetic acid brings the pH of the solution down closer to neutral. processor: propane tank is for heating grease, PVC Figure 7 shows simple way of washing using a translucent PVC type container with a containers on either side are valve 3-4 inches from bottom. For 5 gallon batches use those 5-7 soap settling tanks for gallon buckets found everywhere these days. If a translucent container biodiesel prior to pumping can't be found one fabricated with a sight tube (#6) ought to work. through filters. Pick-up line
for filter pump is inserted into tank only deep enough to siphon esters and not soaps on bottom.

Fill with water until it is halfway between the container's bottom and the valve, then fill with esters to be washed. After a gentle stirring (you don't want to agitate up soaps) followed by 12-24 hours of settling, the oil and water will separate, the cleaned oil can be decanted out the valve, leaving the denser soapy water to be drained out the bottom (#5). This process might have to be repeated 2-3 times to remove very close to100% of soaps. The 2nd and 3rd washings can be done with water alone. After the third washing any remaining water gets removed by re-heating the oil slowly (Figure 8), the water and other impurities sink to bottom. The finished product should be pH 7. The impurities can be left in the re-heater for the next batch or removed if in high accumulations. The soaps can be concentrated, left over esters can be decanted out and what's left is a bio-degradable soap good for any industrial type uses (degreasers

The finished product.

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bio-degradable soap good for any industrial type uses (degreasers etc.). Transesterified and washed esters will become clearer over time as any remaining soaps drop out of solution.
Mike's original 5 gallon biodiesel mill.

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Another idea I have been working with is chilling down the esters thus allowing the soaps to condense and settle out faster. When the oil gets chilled it speeds up the settling of the residual lye from the esters. With a short settling time the oil clears up considerably. In explaining the process the part on how much NaOH (lye) is used in reaction is left out. This is the most difficult step in the reaction process and will be explained clearly at this point.

Titration

To determine the proper amount of NaOH a titration must be performed on the grease being transesterified. To do this titration a solution must be made up of one gram of NaOH to one liter of distilled water. Put the solution in a blender to assure it dissolves completely. This sample is then used as a reference tester for the titration process. It's important not to let the sample get contaminated, it can be used for many titrations. To set up the titration, mix 10 milliliters of isopropyl alcohol (rubbing alcohol) in a small container with a 1 milliliter sample of WVO. Take the WVO titration sample from the reaction vessel (Figure 5 #1) after having been warmed up and stirred. Add to this solution 10 drops of phenolphthalein, an acid-base indicator that's colorless in acid and red in base. Phenolphthalein can be bought from swimming pool or hot tub supply stores. An important note is that it has a shelf life of about a year, it is very sensitive to degradation by light so after a while it will start giving erroneous readings.

Using a graduated eye dropper (with increments marked in tenths of milliliters) or some other calibrated instrument (from medical supply outlets), while carefully keeping track of thje amounts, drop measured amounts of the NaOH/water solution (a couple of tenths of millimeters at a time), into the WVO/isopropyl/phenolphthalein solution.

Follow each drop with vigorous stirring of the solution. In cold weather the WVO might congeal and not work so titration might need to be performed in a heated space. If conditions are right eventually the solution will turn bright purple. This is the indicator color for a pH range of 8-9. Its important to find the exact amount, to just reach this pH without dropping in too much!

It's a good idea to do this entire process a few times over, as a way of assuring your number is correct. I've found that depending on the type of grease, how hot it's gotten in the fryer, what was cooked in it and how long it was used, the amount of NaOH/water solution needed to titrate it was usually between 1.5 to 3 milliliters. The phenolphthalein can also be substituted with litmus paper. Try it with fresh cooking oil from your kitchen too, it should need much less lye to reach pH 8-9.

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The calculation

With this number the next step is to determine the amount of NaOH needed to catalyze the reaction into happening. Take the number of milliliters derived from the titration, multiply this by the number of liters of grease to be transesterified and (what I have been finding works best) multiply that number again by 1.15. This trick was realized after doing a multitude of batches and finding a little extra NaOH gave a more complete splitting of esters from glycerol. I recommend trying it both this way and also not adding the extra 15% NaOH, to see what works best. There is still one more thing to be calculated in. Every liter of neat vegetable oil (fresh -- never been cooked) needs usually 3.5 grams of NaOH to catalyze the reaction into happening. So again for every liter of WVO to be transesterified add an additional 3.5 grams of NaOH. Example: The titration determined that it took 2.4 milliliters to reach a pH of 8.5 and this reaction will be transesterifying 150 liters of oil. 2.4 grams times 1.15 (this is optional) times 150 liters equals 414 grams NaOH Plus 3.5 grams times 150 liters equals 525 grams NaOH 414 + 525 = 939 grams NaOH If a different titration (for example) came out to read 1.8 milliliters to reach the needed pH of 8.5, the final amount of NaOH needed for the reaction would be 836 grams NaOH. Over time the number of grams of lye per liter of WVO has generally been between 6-7 depending on its shape.

Quality
The quality of this fuel can be checked by visually examining it and checking its pH. The pH of the finished product can be checked with pH paper: it needs to be neutral (pH 7). When visually examining it, it should look like clear vegetable oil with a light brown tint, similar to filtered apple cider. There are not supposed to be any films, particles or cloudiness to it. Films would be remaining soapy residue, re-wash it. Cloudiness would be water still in it, re-heat it. Particles could be anything and indicates the filter is failing. Any oils will clear up considerably when heated but the test is, when it cools back down is it still clear? If it is not yet clear than allowing it to settle out for an additional week or two should be enough to clear it up.

For final filtering it is best to use a marine type fuel filter -- the ones with a transparent

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canister so it is possible to keep an eye on the fuel's clarity. I used to trust when I washed it to just pouring fuel into the tank through folded cheesecloth in a funnel. After running into an increased number of dirty fuel filters I've become more careful.

Ethyl esters
I long to do this reaction with ethanol instead of methanol and to understand how it is done that way. The water problem with ethanol (CH3CH2OH) can be worked out. I understand that to do the process with ethanol means it has to be 200-proof or it needs to be transesterified twice or for twice as long. This might also be because the ethanol molecule (a larger molecule than the methanol) is more limited and would therefore need more time to find its covalent bonds with the transfatty acids (steric hindrance).

Limitations
Everything about biodiesel is not perfect. It has some limitations. First it has cold weather starting problems. Around 40 deg F degrees it starts to solidify. Remedy: mix with higher concentrations of fossil diesel or in extreme cases cautiously add minute amounts of gasoline to make it more volatile. Heated garages are nice too. Another problem is increased rate of corrosion of rubber parts from the alcohol. And also emissions go down significantly on everything but Nitric Oxides (NOx), these go up a little. Nitric Oxides occur in engines because of burning oxygen under compression, a diesel engine is nothing but compression, add to that the increased oxygen count of the fuel and you see why NOx must go up.

Emissions
Burning this fuel, like any fossil fuel, takes a toll on accumulations in the atmosphere of global warming gasses. But as a fuel it has a negative net gain in greenhouse global warming carbon dioxide (CO2) gas emissions. The growing of the plants used to produce the oil claims (through photosynthesis) more carbon dioxide then is later emitted out the tailpipe when burning the fuel in an internal combustion engine. Tailpipe emissions, except NOx, are quite noticeably improved over running with straight diesel fuel. Biodiesel does not blow out the thick black smoke common with diesels. A pleasant addition is a 10% boost in horsepower as well. These two improvements are attributed to the nature of biodiesel having oxygen atoms locked up in its ester chains. These additional oxygen atoms are available for a more complete combustion. The two phenomena are seen in the clean emissions. These ester molecules with their locked-in oxygen atoms make what the oil companies would call an oxygenated fuel. And sell more of in smoggy cities. This fuel also makes a good substitute for home furnace fuel oil as it's being used in many parts of Europe and elsewhere. Have fun with it. And be safe!

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For any questions or comments on how this is project works out for you I can be reached at Y2K_ad@hotmail.com. © 1999 Mike Pelly

Biofuels
Biodiesel Make your own biodiesel Mike Pelly's recipe Biodiesel in Hong Kong Nitrogen Oxide emissions Glycerine Biodiesel resources on the Web Do diesels have a future? Ethanol Robert Warren's still Building the Charles 803 alcohol fuel still Operation of an alcohol still Fuel ethanol FAQ Vegetable oil to replace diesel? Four fuels for the future Can you drink it? Ethanol resources on the Web

Community development | Rural development City farms | Organic gardening | Composting | Small farms | Biofuel | Solar box cookers Trees, soil and water | Seeds of the world | Appropriate technology | Project vehicles Home | What people are saying about us | About Handmade Projects | Friends of Journey to Forever Projects | Internet | Schools projects | Sitemap | Site Search | Contact us © Copyright of all original material on this website is the property of Keith Addison, unless otherwise stated, and may be copied and distributed for non-commercial education purposes only as long as the source of the material is stated and a reference to the Journey to Forever website URL is included (http://jtforever.org). All material is provided “as is” without guarantees or warranty of any kind, either expressed or implied.

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ORGANIC CHEMICAL

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ORGANIC CHEMICAL/ENVIRONMENTAL ENGINEERING: THE CONVERSION OF BIOMASS AND WASTES TO FUELS AND CHEMICALS Directed by Professor David G. B. Boocock
Tel.: 978-4020; e-mail: boocock@chem-eng.utoronto.ca

In a chemical process it is important to consider both the chemistry of the reactions as well as the chemical engineering principles involved. Two examples of our research from the environmental area are given below. There is significant international interest in the production of fuels, chemicals and other materials from solid wastes and renewable materials such as lipids. We have shown that vegetable oils and fatty acids are converted to liquid hydrocarbons (mainly mono-olefines) in high yields when passed over activated alumina at 450(C. These liquids are excellent diesel fuel substitutes as well as chemical intermediates. The major functional group pathways for the conversion of the substrates to hydrocarbons have been elucidated. This information is vital for understanding the mechanisms involved. The deoxygenation pathways are also relevant to possible mechanisms for petroleum biogenesis. The process is also applicable to vegetable oil methyl esters (see below). We have also examined the base-catalysed transesterification of vegetable oils to produce Biodiesel methyl esters. These esters have one third the molecular size of vegetable oils and, therefore, may be used as fuel in diesel engines. Unfortunately, the reaction, which uses methanol and sodium hydroxide, takes from one to eight focus at 65(C. We have shown that the methanolysis is slow because the initial reaction mixture consists of two phases, and the reaction is, therefore, mass transfer limited. The problem has been solved by the selection of inert cosolvents which generate an oil-rich one-phase system. Under the new conditions, this reaction is over 99% complete in one to seven minutes at ambient temperatures. Continuous processes are now feasible. The acid catalysed process which is required when the substrate contains significant fatty acids is complete in 7 hours rather than the usual 70. Other areas of research in the environmental area include the investigation of improved methods for predicting the partitioning of organic chemicals between lipids and water phases. This information is required to model and predict the fate of organic chemicals in the environment. In particular, we are testing liquids which might be superior to 1-octanol as a lipid surrogate for the measurement of partition coefficients.

D.G.B. Boocock, S.K. Konar and A. Leung, 1995, "Pathways for the Deoxygenation of Triglycerides to Aliphatic Hydrocarbons over Activated Alumina", J. Energy and Fuel, 9, 1090-1096, (1995). Nisheeth P. Bahadur, Wan-Yin Shiu, David G.B. Boocock, and Donald Mackay, "Temperature Dependence of Octanol-Water Partition Coefficients for Selected Chlorobenzene", 42, 685-688, (1997). D.G.B. Boocock, S.K. Konar, Vinnie Mao, C. Lee, and Sonia Buligan, "Fast Formation of High Purity Oil Methyl Esters", J. Am. Oil. Chem. Soc., (in press, 1998).

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Fat of the Land Recipe

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HOME MIXING OF USED VEGETABLE OIL INTO FUEL FOR DIESEL ENGINES
Vegetable oil will react very similarly to diesel fuel under the conditions inside a diesel engine; i.e. when it is highly compressed, it will heat up and ignite, causing the air in the cylinder to expand, and to push the pistons, in time. If you burned straight unprocessed vegetable oil, however, the fatty acids in the oil would start to congeal and harden (coke up) on the inside of your engine as well as in your fuel injectors, eventually leading to big, expensive engine problems. Therefore, it is necessary to process your oil to remove the fatty acids-- making the oil more similar to diesel compositionally, or to otherwise devise a system to keep your engine clean of residues from unprocessed oil. Following is our procedure for edible waste oil transesterification, which we used on our cross country trip. Please always use extreme caution when working with these ingredients.

WARNINGS AND DISCLAIMERS!!!!!!!!!!!
-We are not automotive engineers, chemists nor scientists of any type so this information is still in a crude, explorative stage. Experiment to find what works for you. -This information was collected from various individuals and has been used by us BUT by no means do we hold any responsibility for anyone attempting to do this process. Essentially this is public information to be used at your own discretion and risk. There is information available regarding transesterification and biodiesel. It is highly recommended to cross-reference and /or to contact someone in the organic chemistry department at a local university. -This information shall not be resold to any individual but given freely to all who may inquire about this procedure. -Methanol is toxic. It can be absorbed by the skin and cause nerve deterioration with prolonged usage. If splashed in eyes it can cause blindness and could be fatal if swallowed. Take necessary precautions when using methanol! A good respirator and decent rubber gloves are recommended. -Lye is also very toxic and burns the skin upon touch. It is also extremely damaging if ingested. It is possible, however to set up a safe means of being able to mix fuel. An outdoor area is preferable or a space with plenty of ventilation. Access to electricity and water are both necessary. Have lots of newspapers and detergent on hand. -Always mix a small batch first in an old blender to test your ratios. If successful the amounts can be multiplied directly. NEVER EVER USE ANY OF THE UTENSILS, POTS NOR BLENDER FOR LIQUID NOR FOOD CONSUMPTION AGAIN!!!

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Fat of the Land Recipe

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Production of Biodiesel for Diesel fuel use
You will need: Used or fresh vegetable oil (strained with a coffee filter or cloth) Red Devil Lye Methanol (dry gas methanol-- we found it at automotive racing stores) Isopropyl Alcohol (for tests-- use 99% IPA) eyedropper- or other type of 1 milliliter dropper PH paper-- available at drug stores-- to test for acidity an old blender plastic or glass measuring cups or beakers, with metric measures-- and/or a gram scale plastic, glass or stainless stirrers and spoons, plastic buckets rubber gloves, safety glasses, plastic apron

Titration Process to determine how much Lye to use
Free fatty acids will increase with the amount of time vegetable oil has been heated-- oil which has been used for cooking will require more of the reactive agents-- lye and methanol-- than fresh oil. The presence of too many free fatty acids will retard or stop the reaction which produces biodiesel, so it is necessary to detect the exact amount of LYE (Sodium Hydroxide-- or NaOH) needed to neutralize the acids. Adding too much or too little NaOH will just make excessive amounts of bi-product (soap). 1. Dissolve 1 gram NaOH (Sodium Hydroxide- Red Devil Lye) in 1000 ml. of water. This is your NaOH solution. 2. Dissolve 1ml. of Wasted Vegetable Oil (WVO) in 10 ml. Isopropyl Alcohol(IPA). This is your WVO solution. 3. With an eyedropper, drop the diluted NaOH into WVO mixture a milliliter at a time. Count the drops. After each ml drop check the ph level of the WVO solution with standard ph paper-- you will see an eventual rise in the ph level. Continue to add the NaOH solution into the WVO solution, a drop at a time, until it reaches a ph of 8-9. To determine your proportions, figure: The number of drops of NaOH needed for the WVO solution to reach a ph of 8-9 1 ml. plus 3.5 g. NaOH to catalyze the oil An example formula used with one particular batch of WVO-wasted vegetable oil.
1 ml of oil was titrated with a 1g NaOH/1000 ml H2O solution.

It required 6.0 ml to raise the ph level to 8 = .006g

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Fat of the Land Recipe

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so plus =

6.0g/1000ml to neutralize the free fatty acids 3.5 g NaOH as catalyst 9.5 g per 1000ml oil or 9.5g/915g oil=103% by wt.

Transesterification For Wasted Vegetable Oil (WVO)
Vegetable Oil: Diesel has a chain of 11-13 carbons, and new vegetable oil has a chain of about 18--but wasted vegetable oil-- which has been heated--has chains of up to 32 carbons. To burn in an engine, the chain needs to be broken down to be similar in length to diesel Lye: (Sodium Hydroxide ((NaOH)-- or potassium hydroxide also works) is the catalyst for transesterification. It works by "cracking" the vegetable oil molecules, splitting the triglycerides from the hydrocarbons and shortening the carbon chain. (3.5g or .35% is the standard amount of lye necessary to create a reaction, when using fresh vegetable oil, so you can figure that used vegetable oil will always use more.) Methanol: The amount of methanol needed will also vary, but the ideal is to use the least amount of methanol necessary in order to get the highest yield. The yield is related to completion; so if you get a 90% yield that means that 90% of the fatty acids have been eliminated from the vegetable oil. We have found that the best is to use 15% to 20% methanol, based upon the total weight of your batch of oil. *it is best to use dry gas methanol (we found methanol at an automotive racing store) A hydrometer can also be used to check the amount of completion according to density Vegetable Oil has a specific density of .910 Biodiesel has a specific density of .850-.870

Recipe for Colorado Gold example test
-- using WVO we got in Colorado 1. Weigh 4kg of WVO heated in a stock pot on a hot plate up to 120F degrees 2. In separate container mix-15%of 4Kg=600g Methanol (MeOH)* (or 17.2% by volume=750ml) with3. 40g (1%) of NaOH until the NaOH dissolves. Add the NaOH slowly! It will become extremely hot, and on a larger scale potentially dangerous. This combined mixture makes Sodium Methoxide. Add this to the WVO and mix for 40-60 minutes. We used a dry wall mixer bit attached to a 1/2 foot drill to do the mixing NOW---Draw out samples every 5-10 minutes to check the rate of separation. The cloudy looking free fatty acids, called glycerine, will sink to the bottom and the methyl esters--a translucent liquid, will remain on top. When the separation appears not to be advancing any more, stop mixing. Let the mixture settle for at least 8 hours. The liquid you have on top now is methyl ester, but before using it you have to remove any remaining soaps or salts which could cause engine damage . The glycerin which has sunk to

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the bottom should be disposed at your local toxic waste disposal site. RINSING METHYL ESTER: Pour off the methyl ester into a separate clean container, so it can be washed free of any remaining soaps, salts or free fatty acids. Add water to the methyl ester. Stir slightly and then allow mix to settle. When the water has cleanly separated from the methyl esters, drain or pump the water out from the bottom. Repeat until the discarded rinse water reaches ph level of 6-7 -- and no soap bubbles appear. If the liquid is cloudy, there is water being retained in the fuel, and it will need to be reheated slowly to evaporate out the water. Any white substances forming at the bottom or any bubbles forming at the surface is a sign of soaps and should be removed or the liquid should be re-washed. The cleaned methyl esters are now a homemade version of biodiesel and are ready to go into your diesel tank. ONE MORE WARNING: To use 100% Biodiesel for longer than 4 weeks straight will cause complications to any rubber components of the engine that the fuel might come into contact with-fuel pump, hoses, o-rings, etc. These can either be replaced with steel or heavy duty rubber or.. it is recommended to use a percentage of diesel with your homemade fuel- at least 20%. HAPPY MOTORING!

Biodiesel Home --- Making Biodiesel -- Resources Veggie Van -- Dancing Rabbit Home

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