Transcript Biodiesel in the Classroom

Biodiesel in the
Classroom
Barry Latham, M.A.Ed., B.S.
Chemistry & Physics Instructor
Bloom High School
Chicago Heights, Illinois
Funding Information
• A+ for Energy $40,000 awarded for 2007-2010 by BP, Inc.
– Biodiesel, Photovoltaic Power, Fuel Cell, Wind, Efficiency projects
– Ethanol Research, Alternative Energy Fairs
• $1,450 awarded 2006-2008 by Bloom Foundation
– Analytical balances for research lab
– Supplemented purchase 6.5kW (bio)diesel generator
– Momentum carts for physics course
• $3,500 Earth Day Network awarded October 2008
– Field trip to Eco-House at Museum of Science & Industry
– 1982 Mercedes Benz 300SD Turbo Diesel
• $5,000 DonorsChoose.com awarded April-December 2008
– Digital Video camera, Molecular models, LCD Projector
– Model rockets, Soap making supplies
Biodiesel Terminology, 1
• Biodiesel- fuel made from vegetable oils or animal fats
– Transesterification (veg oils)- the process of exchanging an alkoxy
group of an ester compound with another alcohol
– Saponification (animal fats)- the hydrolysis of an ester under basic
conditions to form an alcohol and the salt of the carboxylic acid
• Alcohol- any carbon chain which includes an –OH group
– Methanol (MeOH)
– Ethanol (EtOH)
Biodiesel Terminology, 2
• Catalyst- a substance that is used in a chemical
reaction, but not consumed
– Potassium Hydroxide (KOH)
– Sodium Hydroxide (NaOH)
• FAME- Fatty Acid Methyl Esters (<1 g/mL)
– Biodiesel
• B100- 100% biodiesel
• B20- 20% biodiesel, 80% traditional diesel
• Glycerin- co-product of biodiesel (~1.173 g/mL)
– Can be made into liquid (KOH) or bar (NaOH) soap
Vegetable Oil Sources
• In the U.S., most biodiesel is made from soybean oil or
recycled cooking oils
– Typically collected as waste oil from restaurants
– Restaurants pay to have it removed, but you remove it for free:
everybody wins!
– Times are changing, though, and waste oil is getting expensive
(regionally dependent)
• Animals fats, other vegetable oils, and other recycled oils can
also be used to produce biodiesel
• Blends of all kinds of fats and oils may be used to produce
biodiesel
Catalyst Choice
• Potassium Hydroxide (KOH)
– Most used by homebrewers
– Dissolves faster as flakes than NaOH pellets
– Glycerin produced can be easily made into liquid soap
• Sodium Hydroxide (NaOH)
– Typically causes more complications with soap formation
– Used more in the industry
– Glycerin produced can be easily made into bar soap
• Both have a high pH (caustic)
• Both are dangerous- can burn skin, eyes, respiratory system
Alcohol Choice
• Methanol (MeOH)
– Shortest-chain alcohol
– Most used by both homebrewers and in the industry
– Biological effects similar to consuming ethanol, but more severe
• Can cause nervous system failure, blindness if ingested or absorbed through the skin
or breathed in great quantities
• Ethanol
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2-carbon chain alcohol
More restrictions on purchasing, storage and use
Higher rate of complications in reaction
Can cause inebriation
• Both highly flammable and must be respected
• Store only as much as you need in a safe area
– Obey local fire codes
Safety Issues
• Methanol
– Flammable
– Can be absorbed through the skin
– Can cause blindness and death
• Potassium Hydroxide
– Burns
– Do not allow to touch your skin
• Personal Protection Equipment (PPE)
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Operate in a well-ventilated area
Wear safety goggles
Protective gloves
Do not directly inhale any vapors
Tie lose hair back
Wear closed toe shoes and long pants
Oil Titration
• Used to measure the amount of Free Fatty Acids in used or virgin oil
– Higher titration is less desired, but still usable
– More FFA’s mean more catalyst needed means more expense
• Performed to check quality of oil
– Can be performed at oil collection site
– Use disposable syringes and small plastic, re-sealable containers
• Indicator Choices
– Phenolphthalein, Phenol Red, pH Meter, Tumeric spice
– Looking for color change (near pH 7.0)
Water Testing
• When using used oil, it MUST be water-free to
react properly
– Qualitative Heating Test (Crackle test)
– Centrifuge Test
Crackle Test
• When heated over a hotplate,
water will “crackle” in the pan,
indicating its presence
• Heat a cup of oil to ~100°C
• If the oil sputters, then water is
present
– More sputtering = more water
• Water will have to be removed
by heating or settling over time
and tested again
Centrifuge Test
• Oil and water will separate over time
• Centrifuging will speed up this process
• Fill two appropriate sized test tubes ¾
of the way with your used oil
• Spin for 5 minutes
• The oil will rise to the top and water will
settle to the bottom
• The presence of water indicates that
your oil will need to be treated further
– Heating
– Settling
Dewatering
• Water in your used oil will
complicate the formation of
biodiesel and must be
removed
• Heating
• Settling
Heating to Dewater
• A band heater on a 55-gallon
drum will heat your oil sufficiently
– Shorter time period (hours-days?)
– Consumes electricity
• Use gentle agitation
– Emersion mixer set on low setting
– Stir once or twice a day
Settling to Dewater
• Allowing a 55-gallon
drum filled with used
oil will settle your
water to the bottom
and can be drained off
– Much longer time
period (weeks?)
– Consumes no
electricity
• Avoid any agitation
FAME Equation
“Fatty Acid Methyl Ester”
Incomplete Reactions
monoglyceride
(2/3 reaction)
diglyceride
(1/3 reaction)
Triglyceride
(no reaction)
“Dr. Pepper” Method
Single-Stage Process
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Is typically used before a large batch
Results indicate how well the method will
work on this specific oil
Must be done in the lab, not at oil collection
site
Takes 12-24 hours for results
•
Performed in plastic pop bottle
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MeOH will start to eat plastic after 24-36 hours
Appleseed Processor
• Plumbing w/ Pump ~$550
• 120V Water Heater ~$400
• Lumber ~$25
• No plumbing experience needed
• All new parts used
• Costs can be reduced by
salvaging/recycling
Reactor Specifics
• Water heater preferred over steel drum
– Pre-insulated
– Pre-plumbed
– Pre-wired for heating elements
• Electrical water heater has less risk of explosion hazard
– Internal immersion heaters
– Upper heater disabled; it is rarely submerged
• Needs to be connected to 120VAC source
– Electrical box & switch needs to be installed
• Do not compromise temperature regulators
– Explosion risk
Reactor Assembly
• Clear instructions
– Easy for students to assemble
• New water heater used
– No internal calcium scaling
– Not inheriting other people’s
problems
Cheap Schematic
16%BOOST Method
100L, 16% MeOH, 2-Stage Process
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Perform titration
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Add 89% of KOH needed into 16L MeOH
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Our oil titrates at 0.44 (August 28, 2008, 34 trials)
0.45 (March 27, 2009, 5 trials)
Mix thoroughly (will mix overnight)
Add 14L of mixture to heated oil (55°C)
Circulate for 1 hr. and settle overnight
Add remaining KOH to remaining KOH/MeOH
Drain glycerin and add remaining KOH/MeOH mixture
Circulate for 3 hr. and settle overnight
Drain glycerin
80/20 Method
100L, 18% MeOH, 2-Stage Process
• Perform titration
– Our oil titrates at 0.44 (August 28, 2008, 34 trials)
• Add all KOH needed into 18L MeOH
– Mix thoroughly (will mix overnight)
• Add 14.4L of mixture to heated oil (55°C)
• Circulate for 1 hr. and settle overnight
• Drain glycerin and add remaining KOH/MeOH
mixture
• Circulate for 3 hr. and settle overnight
• Drain glycerin
22% Method
100L, 22% MeOH, Single-Stage Process
• Perform titration
– Our oil titrates at 0.44 (August 28, 2008, 34 trials)
• Add all KOH needed into 22L MeOH
– Mix thoroughly (will mix overnight)
• Add all of the mixture to heated oil (55°C)
• Circulate for 3 hr. and settle overnight
• Drain glycerin
Methods Summary
• %MeOH needs to be at least 13%
– More MeOH ensure greater completion of
reaction
– Too much can be wasteful, though
• Circulation times can vary
– 1-3 hours per batch seems to work for most
• Batch sizes of 100L used for simplicity in
calculations (scaling up or down)
Glycerin Removal
• Drain the bottom layer of
glycerin
• Dr. Pepper Method
– Invert pop bottle and gently
squeeze while using your
thumb as a valve
• It is better to overflow and
lose some biodiesel, than to
leave some glycerin in your
biodiesel
Biodiesel Size Exclusion
Chromatography
• Only B100 remains after final glycerin drain
– Longer wait-time allows more glycerin to settle out
• Residual MeOH may remain
– Costly/complicated to distill MeOH out of glycerin
• B100 pumped through molecular sieve into storage drum
– 4A sieve traps small molecules (MeOH, H2O) and allows larger molecules
(biodiesel, glycerin) to pass
– Sized-based trap
– Based on gas trap designs and drying agents
• Because MeOH exists at ppm or ppb levels, sieve may take a very
long time to exhaust
– No current research available
– Can be recharged by heating in an exhaust hood or outside
• To vaporize MeOH and “bake-off” biodiesel adhered to surface
Custom SEC
Dry-washing System
Water Washing (optional)
•
Mist washing- a fine mist of water onto
surface of biodiesel
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Water needs to be small droplets and hit the
surface at a low velocity
Drain water as misting continues
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Water droplets pick up impurities on their
way through the biodiesel
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Fuel will eventually get clear as water drains
out
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Turn off water and allow the fuel to settle
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Water is a contaminant in biodiesel and is
sometimes difficult to remove
Bubble Washing (optional)
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Gently add 1 part water to 2-3 parts biodiesel
Add an aquarium air stone with air pump
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Can use copper tubing with pin-sized holes drilled all over
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Bubble air through the water
Batch-based, not continuous flow
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Air bubbles allow indirect agitation of the two fluids
Tiny amounts of water picked up and carried through
the biodiesel, picking up contaminants
Bubble bursts at the surface and drops the water,
which picks up more of the soaps and contaminants
on it’s way back down
After about 6 hours of this ‘washing’, the air is
stopped, water is drained, more fresh water is added,
and the process repeats
Repeated 3 times until the water measures the same
pH of your tap water and is perfectly clear
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Still water-based washing
Waste Water Disposal
• When water-washing, the water needs to be disposed of
• Treat with a mild acid until neutralized
– Acids- vinegar, citric acid, ascorbic acid
– Use pH indicator from titration
– Neutralized water can be safely dumped down the drain
• Creates lots of waste, depending on how you water
wash
• Tests performed August 2008 indicated that although the
biodiesel does appear clearer after water-washing, it
passes the 3/27 test without it
Emulsions
• Emulsions are a mixture that occur
when a water layer and an oil layer
refuse to separate
• Can occur during the water-wash
phase
– Cause- aggressive washing
– Biodiesel becomes "imprisoned" in
soap spheres
– Relating to un-reacted oils, poorly
separated biodiesel/by-product, etc.
Emulsion Corrections
• Soap spheres can be broken
apart
– Freezing the whole emulsion
– Lowering the surface tension using
a solvent like alcohol
– The alcohols (methanol in glycerin)
are a readily available solvent
• Much easier than freezing a large
emulsion solid.
– Drawback- Expensive to freeze 55
gallons
• Heating batch to 50-60°C
– Expensive to heat 55 gallons
• Adding ordinary table-salt,
sodium chloride can work
– Dilute the salt in water first
– Salt is an impurity that you should
be washing out instead of washing
in
– Adds halogens to water supply
• An acid-quench will also break
an emulsion or prevent it
forming
– Might disguise a processing
problem that the emulsion would
reveal
– Always do a wash-test first
Quality Testing
3/27 Test
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Tests for triglycerides (unreacted oil)
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Does not for monoglycerides and diglycerides
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Tells you if you must reprocess
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Add 1 part biodiesel to 9 parts methanol in a
sealable vial (3mL & 27mL, etc.)
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Look for particles in the vial and/or
cloudiness
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Be very precise with measurements if using these
small amounts
If present, your sample failed- reprocess
Sample should be clear to pass
Biodiesel Storage
• Biodegradable in months to years
– Less time than table sugar
– No research to support this claim
• Only make as much as is needed
• Hydroscopic (attracts atmospheric
water)
• More glycerin falls out over time,
regardless of draining or filtering
• Fire code regulations
Biodiesel Uses
Beyond Diesel Vehicles
– a corrosion
preventative
– a parts cleaner and
degreaser
– a graffiti remover
– a paint and resin
cleanup
– a hand cleaner
– a crop adjuvant
– a metal working
lubricant
– a screen printing ink
remover
– aircraft fuel
– home heating oil
– a lubricity additive
for diesel fuel
– an adhesive
remover
– a mold release
agent
– an asphalt cleanup
agent
– an oil spill cleanup
and
bioremediation
agent
– an auto wax
remover
Biodiesel Use Cautions
• Biodiesel as an excellent solvent
– All natural rubber will eventually be dissolved
• Use Viton, or other synthetic rubber hoses, seals and
gaskets
– Breaks down petroleum “grit” that builds up over time
in the combustion chamber
• Grit is dissolved by biodiesel and can clog fuel and exhaust
filters
– Starting with a lower % of biodiesel slows this process
• Can increase % over time while replacing rubber material
and filters
Benefits of Biodiesel
• Operates in conventional diesel engines
• Does not require special storage
• Exhaust is less offensive
– Smells like food that it was used for
• Safer to use than dino-diesel
• Reduced greenhouse gases emissions
– 30-80%, depending on %B
• Improves domestic energy security
Closed-Carbon Cycle
Glycerin Treatment
MeOH Removal
• MeOH is still present and needs to be removed
before it can be used
– NOT a co-product, just used in excess
– Common misconception that MeOH is produced
• Distillation- separation of liquids based on
boiling points
– MeOH has a lower boiling point than glycerin
• Turns to vapor first
• Can be condensed, collected and reused
– Glycerin turns thicker and darker
– Heating element, not flame, is used
Glycerin Co-Product
Soap (1L batch)
• Remove the residual (toxic) methanol first
• Fragrances and dyes can be added
• KOH-based biodiesel makes liquid soap
glycerin
– NaOH-based production makes bar soap
• At 50°C, preheat any of the following
ratios before mixing for 5 minutes
– Glycerin
– Water
– KOH
33mL
7mL
1g
47mL
5mL
1g
54mL
5mL
1g
– Can not use KOH and NaOH interchangeably
– D-limonene smells like oranges and is
cheaply made/purchased
– Most dyes muddy the dark brown
color
Glycerin Co-Product
Other Uses
• Health supplement
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Increases blood volume
Enhances temperature regulation
Improves exercise performance in the heat
Helps "hyperhydrate" the body by increasing blood volume levels and
helping to delay dehydration
• Other uses
– Glycerine is also a source of lecithin
• fat emulsifier and a vital component of all cell membranes in the body
– Tocopherol (vitamin E)
– Skin moisturizer, lotion, deodorant, makeup, toothpaste, sweets and
cakes, pharmaceuticals and patent medicines, paper manufacturing,
printing ink, textiles, plastics, and electronic components
Glycerin Co-Product
Other Uses
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Paint brush cleaner
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Rinse brush as much as possible with water
Work brush in a small container with about 20 mL of glycerin
Rinse brush under water until all milky-ness is removed
Repeat glycerin stage with fresh glycerin as needed
Check that brush doesn't smell of paint and store brush as usual.
Safe sweetener:
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Glycerin is an alcohol and is used as a preservative
It is very sweet, yet it contains no sugar
This makes it an ideal sweetener for patients who cannot take sugar
Cross-Curricular Opportunities
for Biodiesel & Soap
• Art Class
– Dispensing Container Design
– Brand name & Label graphics
• Economics
– Cost Analysis of Biodiesel & Glycerin Soap
– Marketing of product
• Fundraiser
Web Resources
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blatham.multiply.com
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– Personal biodiesel website
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www.localb100.com
– Material Handling Equipment
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– For small scale producers
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utahbiodieselsupply.com
– Produce, Promote and use Biodiesel
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journeytoforever.org/biodiesel.html
– Information & tutorials
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www.biodiesel.org
– National Biodiesel Board
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www.mcmaster.com
– Industrial equipment
www.bloomhs.org
– Bloom High School, Chicago Heights,
IL
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www.biodieselcommunity.org
– Collaborative Biodiesel Tutorial
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www.ucsusa.org
– Union of Concerned Scientists
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BiodieselAmerica.org
– Resources, Information, Community &
News
www.spill911.com
– Safety, Spill Containment & Industrial
Supply
www.globalindustrial.com
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www.B100Supply.com
– Appleseed Reactor
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www.graingercom
– Industrial equipment
Grants, 1
• A+ for Energy
– www.aplusforenergy.com
• Earth Day Network
– www.earthday.net
• Donors Choose
– www.donorschoose.com
• American Honda Foundation
– corporate.honda.com/america/philanthropy.aspx?id=philanthropy_overview
• National Science Teachers Association
– www.nsta.org/academy/2009/FellowApplication.aspx
• Bristol-Meyers Squibb
– www.bms.com/responsibility/grantsandgiving/medical_science_education/Pages/
default.aspx
Grants, 2
• Motorola Enterprises Mobility Business and Symbol Technologies
– www.symbol.com/category.php/?category=736
• Toshiba
– www.toshiba.com/tafpub/upload/page/100045/25964_Executive.pdf
• The Charles A. and Anne Morrow Lindbergh Foundation
– www.lindberghfoundation.org/grants/index.php
• Albertson’s
– www.albertsons.com/abs_inthecommunity/
• Green School Project
– greenschoolproject.com/default.aspx
• Jewel-Osco
– www.jewelosco.com/eCommerceWeb/CommunityAction.do?action=beginComm
unity