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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’s the recipe for a
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’d be interested in hearing from you about your experience.
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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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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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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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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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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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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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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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

10 of 20 4/16/00 8:11 PM
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
Site Search Advanced
cars. He finds it "far superior" to fossil-based diesel
fuel.
Biofuels
Biofuel mailing list - Mike sent us a full report on how he makes biodiesel.
subscribe
"It's a result of my work over the past three years," he
Biodiesel said. "Pass it along to anyone you please." Here it is.
Make your own
biodiesel
Mike Pelly's recipe Bio-diesel From Used Kitchen Grease or Waste
Biodiesel in Hong Vegetable Oil
Kong
Nitrogen Oxide by Mike Pelly
emissions
Glycerine CAUTION: Wear proper gloves, apron, and eye protection and DO NOT inhale any
Biodiesel resources vapors. Exposure to methanol can lead to blindness and death. Sodium hydroxide can
on the Web cause severe burns and death. Together these two chemicals form sodium methoxide.
Do diesels have a This is an extremely caustic chemical. Do not inhale any vapors. Wear a mask and full
future? 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
Ethanol chemicals -- treat them as such!
Robert Warren's still
Building the Charles Making biodiesel
803 alcohol fuel still
Operation of an This procedure is called transesterification, similar to saponification. Sound familiar?
alcohol still Saponification is soap making. In soap making one takes a transfatty acid or
Fuel ethanol FAQ triglyceride (oil or kitchen grease), blends it with a solution of sodium hydroxide
Vegetable oil to (NaOH or lye) and water. This reaction causes the ester chains to separate away from
replace diesel? 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
Four fuels for the
end and to non-polar molecules like oil on the other end is what makes them effective
future
as soap.
Can you drink it?
Ethanol resources on In transesterification reactions, first a solution of NaOH and methanol (CH3OH) is
the Web mixed, creating sodium methoxide (Na+ CH3O-). This STRONG chemical breaks the
Home transfatty acid into glycerin and also ester chains (biodiesel), along with some soap if
What people are you're not careful (more on that later). The esters become methyl esters. They would
saying about us be ethyl esters if reacted with booze (ethanol).

1 of 9 4/24/00 10:13 AM
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About Handmade
Projects Figures 1-3 show these two reactions. The zigzag lines in the triglyceride diagram
Sitemap (text only) (Figure 1) are shorthand for carbon chains. At both ends of each line segment is a
Projects carbon atom.
Community
Figure 1
development
Why we're doing this
Rural development
Fixing what's broken
City farms
Edible cities
Organic gardening
Everyone can grow their
In Figures 2 and 3 these zigzags are shorthanded as R1, 2 and 3.
own food
Composting
Figure 2
The Wheel of Life
Small farms
The way forward
Biofuels
Fuel for the future
Solar box cookers
Sun power saves lives and
trees
Trees, soil and water
Healthcare for mountains Figure 3
Seeds of the world
No seeds, no food
Appropriate
technology
What works and fits
Project vehicles
The workhorses
Internet
Why it really matters Overview
Internet interaction
Finding your way 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
Schools projects
gets preheated to 120-130 degrees Fahrenheit (48-54 deg C).
Introduction
Biofuels The amount of methanol needed for the reaction is 15-20% of Waste Vegetable Oil
Solar box cookers (WVO) by mass. The densities of these two liquids are fairly close so measuring 15%
Backpack stove of methanol by volume should be about right. To be completely sure, measure out a

2 of 9 4/24/00 10:13 AM
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PicoTurbine half-liter of both fluids, weigh, and calculate exactly what 15% by mass is. Different
Low-tech radio WVOs can have different densities depending on what type of oil it originally was and
What to do with a how long it was used in the deep fryer. If uncertain about densities then it's better to
cardboard carton go heavy on the methanol, say 20%.
Sisters of silk
Example: When transesterifying 100 liters of WVO, include 15 to 20 liters of
Silkworms in a
methanol.
shoebox
School gardens The methanol is mixed into solution with sodium hydroxide, thus creating sodium
School composting methoxide in an exothermic reaction (it gets warm from bonds forming). This sodium
The Beach House fish methoxide is to be treated with extreme caution! Do not inhale any vapors! If any
pond happens to get splashed on skin, it will burn without being felt (killing nerves) so wash
HOMeR immediately.
School and youth
programs on the Sodium methoxide is also very corrosive to paints. The best type of containers for
Web handling it are ones made of stainless steel. Used restaurant equipment supply stores
Education resources are a good place to look for this type of equipment. Braze on plumbing fittings where
on the Web 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 After stirring the reactants at 120-130 deg F for one hour, allow the solution to sit and
for a titration. 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 Figure 4 shows one example of a system for separating two liquids with different
pH. 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.

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.
Lighting burner under A proposed alternative using very little electricity is illustrated in Figure 6. This
transesterifyer vessel. 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
View of sodium methoxide solution, but I can't fit it in all at once, so I measure out three
mixer (left) and separate portions.
transesterifyer vessel (right).

Glycerin
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
View of sodium methoxide often accomplished but glycerin has a high boiling point while under high vacuum
mixer being drained into pressure this method is difficult.
transesterifyer vessel (note
thermometer).
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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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
Valve on bottom of uniform.
transesterifyer vessel user to
decant out more dense
glycerin from less dense Soap
esters.
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
processor: propane tank is acid brings the pH of the solution down closer to neutral.
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
biodiesel prior to pumping
gallon buckets found everywhere these days. If a translucent container
through filters. Pick-up line can't be found one fabricated with a sight tube (#6) ought to work.
for filter pump is inserted into
tank only deep enough to Fill with water until it is halfway between the container's bottom and
siphon esters and not soaps the valve, then fill with esters to be washed. After a gentle stirring (you
on bottom. 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 finished product.
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

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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.
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
Contact us speeds up the settling of the residual lye from the esters. With a short settling time the
oil clears up considerably.
To Keith Addison
gruno@att.net.hk In explaining the process the part on how much NaOH (lye) is used in reaction is left
To Midori Hiraga out. This is the most difficult step in the reaction process and will be explained clearly
mid@attglobal.net at this point.
Homepage
http://jtforever.org
Titration
Handmade Projects
The Beach House To determine the proper amount of NaOH a titration must be performed on the grease
39 Ham Tin Kau Tsuen being transesterified. To do this titration a solution must be made up of one gram of
Pui O NaOH to one liter of distilled water. Put the solution in a blender to assure it dissolves
Lantau Island completely. This sample is then used as a reference tester for the titration process. It's
Hong Kong 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!

8 of 9 4/24/00 10:13 AM
Biodiesel recipe from Mike Pelly: Journey to Forever file:///E|/Tech/Fuels/biodiesel_mike.html

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

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© 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.

9 of 9 4/24/00 10:13 AM
ORGANIC CHEMICAL file:///E|/Tech/Fuels/boocock.html

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).

1 of 1 4/24/00 7:18 PM
Fat of the Land Recipe file:///E|/Tech/Fuels/flrecipe.html

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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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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so 6.0g/1000ml to neutralize the free fatty acids

plus 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) with-
3. 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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