Randall von Wedel, Ph'D'

1

• Randall von Wedel, Ph.D.
• BioSolar /CytoCulture International Inc.
• Rvwedel_at_gmail.com
• CalACT Monterey, CA November 6, 2008

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Biodiesel benefitsgoing green

• A diesel displacement fuel made from plant oils,
  animal fats or recycled cooking oils through a
  chemical process to remove glycerin and yield
  methyl esters optimized for combustion in modern
  diesel engines e.g., common rail
• Renewable, agriculturally produced replacement
  fuel to displace imported petroleum with local
  domestic biofuel
• Biodiesel itself is non-toxic, non-flammable and
  non-volatile, making it safe to handle store as
  B99/B100
• Biodiesel contains very low sulfur and no
  aromatics
• In US, often blended by big fleets to 20 (B20)
  to achieve significant reductions in PM and
  criteria air emissions
• 17 GHG reduction in CO2 emissions by life cycle
  analysis
• EPACT credits for city-county fleets compliance
  with RFS

3
Other incentives to use Biodiesel

• Public support of reduced exhaust smoke and odors
  in blends of 20 or higher
• Proactive move to reduce GHGs and climate change
• Offset carbon footprint of electric power
  generation
• Flexible fuel for fleets in blends Easily
  reversible
• Relatively low cost (similar to ULSD), no capital
  investments in infrastructure as drop in fuel
• Obvious solution for older diesel engines that
  may not be amenable to modern after-treatment
  retrofits
• Lower impact of accidental spills or leaks

4
Challenges for Biodiesel Today

• Availability to small rural transit fleets in
  remote areas
• Education of local transit agencies and
  distributors
• Perception issues regarding warranties and
  operations
• Pricing of biodiesel in more remote areas
• Biodiesel fuel quality issues when improperly
  stored
• Feedstock (raw material) availability keeping up
  with demand for biodiesel across the
  statedisplacing soy biodiesel with locally
  produced, sustainable biodiesel made from
  recycled oil, animal fats and new oil crops

5
Biodiesel Bus Chassis Dynamometer Testing

• B20 vs. conventional diesel fuel
• 2 in-use buses tested (40,000 lb GVWR)
• City Suburban Heavy Vehicle Cycle (CSHVC) at
  35,000 lb inertia
• Cummins ISM 2000 Engine No EGR
• Fuel economy reduction ? 3
• Emission reductions (g/mile basis)
• PM ? 18
• HC ? 29
• CO ? 24
• NOx ? 4
• statistical confidence gt 99
• Data from Dr. Robert McCormick, NREL

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ENGINE C
ENGINE B
ENGINE A
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Particulate Traps and Oxidative Catalysts

• After treatment reduces PM, CO and HC by 50-90
• Retrofitted to most diesel buses, but not to
  2-stroke and some older engines (or use high
  blend biodiesel)
• Biodiesel is compatible with most devices CARB
  certified traps/filters now operating in CA for
  B20
• Excellent B20 results in SF vehicles equipped
  with the Clearaire Longview PM / NOx reduction
  system
• B20 increases PM reduction by 62 in oxidative
  catalysts (NREL study 2005) so improved
  performance
• B20 extends longevity of traps, lower maintenance

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Using Biodiesel Lowers Greenhouse Gas Emissions
and Carbon Footprint of Fleet Vehicles

• Closed Carbon Cycle CO2 of engine emission can
  be taken up by oil crops in the following season
• 78 life cycle reduction in CO2 from crop to
  tailpipe Midwest B100 translates to about 12-15
  GHG reduction for B20 in California, FL
• Energy Balance 3.5 to 1 for soy, 4.6 1 for
  animal fats, 71 for recycled cooking oil
• Besides reducing idling, retiring old trucks,
  improving engine efficiencies, fleet have few
  options to reduce GHGs

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San Francisco MUNI B20 Buses

• 520 buses in the City consume 6.2 m gallons
  B20/yr, or about 1.25 m gallons of B100 per year
  (1 rail car per wk)
• 86 of those buses are new true hybrid diesel
  electric
• Most of the regular buses equipped with LongView
  NOx / PM reduction after treatment B20 works
  fine
• Program initiated as 6 month pilot study per
  Mayors Executive order in 2006 full compliance
  all B20 now for over a year without ANY vehicle
  problems
• Lessons learned B20 works, but important to have
  good fuel quality clean tanks before
  implementation

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Basic Biodiesel Reaction
Liquid Catalyst 1 kg (Na or K Hydroxide)
Combining
Yields

• Degummed vegetable oil, used cooking oil or
  animal fat
• (100 kg)
• Methanol
• (12 kg)

Biodiesel (95 kg) Glycerin (11 kg)
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Transesterification Reaction (basic)

• H O
• ? ??
• H - C - O - C - CH2 CH2 CH2 CH2 CH2 CH2
  CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3
• ?
• ? O
• ? ??
• H - C - O - C - (CH2)7 -CH CH(CH2)7
  CH3 3 H3 - C -OH ---------------?
• ?
  -OH
• ? O Methanol
  Catalyst
• ? ??
• H - C - O - C - (CH2)7 -CH CHCH2 CH
  CH(CH2)4 CH3
• ?
• H
• Vegetable Oil or Animal Fat Triglyceride
• 80 US Biodiesel today is still made from Soybean
  oil, balance is animal fat, canola, cooking
  oil
• 
  

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Transesterification reaction releases methyl
esters from glycerin

• H O
• ? ??
• H - C - OH CH3 - O - C - (CH2)16 CH3
• ?
• ? Methyl Stearate (saturated ester)
• ? O
• ? ??
• H - C - OH CH3 - O - C - (CH2)7 -CH
  CH(CH2)7 CH3
• ?
• ? Methyl Oleate
  (mono-unsaturated ester)
• ? O
• ? ??
• H - C - OH CH3
  - O - C - (CH2)7 -CH CHCH2 CH CH(CH2)4 CH3
• ?
• H Methyl Linoleate (di-unsaturated
  ester)
•  
• Glycerin
• Range of Biodiesel Methyl Esters
•  

Process Control and Batch Testing is Essential
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Mono di glycerides result from incomplete
transesterification

• H O
• ? ??
• H - C - O - C - CH2 CH2 CH2 CH2 CHCH CH2
  CH2 CH2 CH2 CH CH CH2 CH2 CH2 CH2 CH3
• ?
• ?
• ?
• H - C - O - H
• ?
• ?
• ?
• H - C - O - H
• ?
• H Monoglyceride (Linoleic
  182)

Free fatty acids in oxidized feedstock oil
contribute to incomplete conversion of oil to
esters
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Free fatty acids and polymers result from
oxidation cross linking of unsaturated chains

• O
• ??
• - O - C - CH2 CH2 CH2 CH2 CHCH CH2 CH2
  CH2 CH2 CH CH CH2 CH2 CH2 CH2 CH3
• O
  O
  O
• ??
  / \ /
  \
• - O - C - CH2 CH2 CH2 CH2 CH -- CH C H2
  CH2 CH2 CH2 CH --CH CH2 CH2 CH2 CH2 CH3
• Hydroperoxides form by oxidation
  of double bonds
• Breakdown to smaller fatty acids or cross-link to
  form polymers
• Higher free fatty acids (rancid oil) means lower
  quality biodiesel

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Important Biodiesel Parameters

• Complete conversion avoid partially reacted
  fuel!
• High oxidation stability avoid unwanted
  reactions
• Removal of glycerin residues accumulate in
  engine
• Removal of catalyst destroys gaskets and seals
• Removal of residual carbon polymers from
  oxidation
• Keep low acid number avoid oxidized fuel
• New pending assay to test for potential
  precipitations
• Insured through ASTM D 6751 specs

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ASTM D 6751 2008 Feedstock Neutral

• Property Test Method Limits Units
• Calcium Magnesium EN 14538 5
  max ppm (ug/g)
• Flash Point D 93 130 min.
  degrees C
• Water Sediment D 2709 (4176)
  0.05 max. volume
• Kin. Viscosity, 40C D 445
  1.9 - 6.0 mm²/sec.
• Sulfated Ash D 874
  0.02 max. mass
• Sulfur S15 D 5453 0.0015
  max (15) mass (ppm)
• Copper Corrosion D 130 No. 3
  max.
• Cetane number D 613 47 min.
• Cloud Point D 2500
  Report degrees C
• Carbon Residue D 4530 0.05
  max. mass
• Acid Number D 664 0.50 max.
  mg KOH/g
• Free Glycerin D 6854 0.020
  mass
• Total Glycerin D 6854 0.240
  mass
• Phosphorous content D 4951 0.001
  max mass
• Distillation, T90 AET D 1160 360 max
  degrees C
• Na/K, combined EN 14538
  5 max ppm (ug/g)
• Oxidation Stability EN 14112
  3 min hours

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ASTM D6751 Highlights for QA protocol

• Total glycerin test for incomplete conversion
• (mono, di and triglcyeride residues in fuel)
• Oxidation stability oxidation intermediates
• Acid number fatty acids from oxidation
• Carbon residues polymers from oxidized chains
• ASTM and EU specs are likely to tighten for
• P, Na, K, Ca, Mg oxidation stability
• NEW cold soak filter assay CSFA pending ASTM
  approval as operational test for precipitations
• Recommend also monitoring KF Moisture

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Fuel Quality Control A Mindset at 3 Levels from
Plant to Fleet

• Production at the plant feedstock to fuel
• BQ 9000 or other rigorous QA program
• ASTM 6751 specs and certification
• Distribution, storage, blending and handling
• BQ 9000 or other rigorous QA program
• Protocols, documentation, monitoring
• Consumer storage, dispensing use
• Protocols, documentation, monitoring

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Biodiesel Fuel SpecificationsIts all about
Quality Control

• Most or all problems associated with biodiesel
  use are due to fuel quality issues, not to the
  biodiesel per se
• Quality control problems largely a result of a
  rapidly growing industry, inexperience and lack
  of diligence.
• The problems are NOT caused by inadequate
  specifications or the lack of proper protocols,
  from the plant to the distributor to the user
• Fleet managers can set up their own Quality
  Assurance programs and set requirements for their
  fuel vendors to do the samefrom driver training
  to fuel testing

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Common Problems with Biodiesel in Transit
Storage

• Biodiesel and blends suffer from condensation
  water and contamination from fuel deliveries
• Bacterial growth (not algae) in water layer
  will deteriorate the fuel, generate acids and
  precipitations
• Acids caused by bacterial biodegradation of fuel
  (short free fatty acids) can damage engine
  components
• Anaerobic conditions in damp tanks promote
  sulfate reduction forming traces of corrosive
  sulfuric acid
• Older tanks or tanks accidentally contaminated
  with infected, deteriorated diesel fuel can
  infect biodiesel

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www.biodiesel.org
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Fuel Problems Associated with Increasingly Out
of Spec Biodiesel

• Residues in storage tanks, filters and lines
• Clogged filters can stop vehicles on road
• Dissolved contaminants foul injectors
• Coking of injectors and varnish on valves
• Rough engine operation, smoke, wear
• Catalyst, methanol ruin fuel injection pump
• Crankcase oil deterioration, polymerization
• Long term or catastrophic engine damage

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Some problems get caught

• Sediments, bacterial slime,
• precipitates and free water
• can be trapped by filters
• along with any insoluble
• impurities associated with
• the fuel
• Butdissolved contaminants
• acids that can damage engines
• pass through the filters

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Field Test Kit Developed for checking Biodiesel
B100 Quality pHLip Test

• A Quick Check in the field for detecting traces
  of catalyst, mono/di/triglycerides, soaps, acids
  and oxidized (aged) fuel hydroxyesters,
  peroxides
• 10 min test Simply add B100 to test vial, mix by
  flipping let the fuel float to create two
  phases
• Visual indication only but quantitative
  capability
• Unrelated to ASTM yet surprisingly sensitive for
  dissolved contaminants Now a QC protocol test
• Intended to alert a consumer or operator as a
  firewall, then they can request a formal lab
  test

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pHLip Test Kit Concepts

• Extraction of catalyst or acid from fuel to
  aqueous pH indicator elicits color change from
  neutral red color
• Soluble contaminants in biodiesel can be
• gtExtracted into the aqueous phase
• (fatty acid soaps) as visible
  turbidity
• gtConcentrated at water-fuel interface
• (glycerides, sterols, oxidized esters)
  Lens Effect Signal Amplification
• gtHydrated in the fuel as visible turbidity
• (mono, di triglycerides fatty acids,
  oxidized)
• Endorsed and distributed by the National
  Biodiesel Board

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Detection of catalyst contamination from poorly
washed biodiesel fuels
Clear Bright Reference Fuel
Contaminated Biodiesel samples become turbid
? Mirror Finish
Alkaline pH creates purple color soaps cause
turbidity
Neutral pH Indicator
www.allthingsbiodiesel.com
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Aging Oxidized B100 ExamplesRelative to Fresh
Bright Reference Fuel
Fresh
Bright
Haze
Smoke
Mirror
?Residues
Neutral pH
Acidic
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Detecting near-spec and off-spec fueltop vs.
bottom of rail car tank of B100
Bright Bright B100 reference
Top Sample
Bottom Sample
? Mirror reflection
? Glycerides

• ? Glycerides

0.76 Monoglycerides, 0.38 Diglycerides, 0.62
Triglycerides 0.31 Total Glycerin in composite
of Top and Bottom samples
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Monitoring Biodiesel Quality for Fleet Deliveries
by Truck/Rail to FL Bus Fleet
Bus Fleet Managers Testing B99 on delivery
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Biodiesel Quality Status Report (BQSR)
Typical B100 imported to CA now, similar to NREL
2007 Survey average
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Out-of-spec, incompletely reacted B100
Turbid fuel layer
Top
Middle
Bottom
Note clear and bright B100 samples vs. Turbid
fuel layer in pHLip Tests
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Oxidized (ruined) ASTM spec B100
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Biodiesel Quality Status Report 2008
Excellent quality biodiesel by rail 85 Soy /
15 animal fat B100
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Debunking myths about biodiesel

• Engine conversion needed. No, its a drop in
  fuel blended with ULSD. Most big fleets use B20
  blend
• Biodiesel raises NOx emissions No, B20 blends
  proved to be NOx Neutral on emissions per 2007
  NREL study
• Only pure soy biodiesel is really good quality.
  No, many feedstock result in excellent biodiesel,
  including animal fat, recycled cooking oil
  palm. Process is what varies competence/diligenc
  e in quality control
• Cold flow Biodiesel gels. Not a problem for B20
  made from most feedstock, specify pour
  point/cloud point
• Biodiesel causes increase in food prices. No,
  most grains are not feedstock. Focus on
  industrial crop oils.

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Research on US feedstock options

• Animal fat methyl ester blended into soy
  biodiesel
• Chicken fat, beef tallow, high grade pork fat
• Recycled cooking oil biodiesel all around the
  country
• Trap grease / brown grease pilot studies in CA,
  PA
• Canola and Winter Rapeseed in Northwest
• Mustard, Canola Camelina in Western states
• Cotton seed oil in Texas and Southwest
• Safflower, Sunflower and high oil Mustard in CA
• Sunflower and Jatropha in Florida (test plots)
• Imports Palm oil biodiesel (mostly for cruise
  ships)

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Sustainability now a B100 spec Examples of
evolving GHG policies

• Utility fleets developing Corporate Biofuel
  Policies on both coasts already implemented at
  FPL and enforced
• Dupont set precedent in formalizing Sustainable
  Best Practices as high level management corporate
  policy
• New CA Renewable Fuel Standard will set specific
  criteria for sustainable biofuels, land use
  changes, etc.
• US/EU biofuel policies include mandatory 35 net
  reduction in green house gases (GHG) for biofuels
• Tesco in UK (supermarket chain throughout UK, EU)
  had a PR setback when GreenPeace revealed B50
  fleet was using imported Indonesian palm oil
  biodiesel

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Food (feed) vs. biofuel debate

• On going arguments stemming from papers early
  2008 pointing out land use changes, net energy
  GHG emission reductions good bad cultivation
  practices
• Right now, 16 of total soybean oil in US (2.2 b
  lbs) is used to produce biodiesel, about 10 is
  exported as oil
• Soybean is grown primarily as high protein animal
  feed, same as corn or other feed grains
• 2 lbs grain/lb chicken 4 lbs grain/lb pork, 6
  lbs/lb beef
• Oil is a co-product of soybean meal production
  for feed
• Biofuels accounted for nearly half the world
  demand increase, but only 7 of total vegetable
  oil consumed, while a cut back in subsidies
  reduced oil production

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Food (feed) price increases

• Primary driver for increased food and grain
  prices is rising demand for meat, particularly
  China, India, Asia
• Wheat consumption exceeded production in 7 of 8
  yrs
• Droughts and dropping water tables sharply cut
  back grain production in China, Australia, and
  Northwest
• Price of petroleum fuel pushed up costs of
  transport, fertilizers, herbicides, insecticides
  and processing
• Aggressive commodity markets domestic hoarding
  contributed to sharp spikes in rice, wheat and
  grains
• For yellow corn, the net gain in US production
  acreage cant meet the demand world wide for
  animal feed

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Straining world fuel, food and water

• Population increases have been anticipated.China
  India represent over a third of the world
  inhabitants
• Migration from rural areas to crowded cities 44
  now but expecting 66 by 2030 resource
  intensive shift
• Surge in middle classand their meat consumption,
  with 3 x increase in meat eaten in China since
  1983
• India lagging, but expected to follow China, with
  huge spikes in demand for food, fuel and
  commodities
• Will create 10 New York cities in the next 10
  years, with 30,000 new skyscrapers in China alone
• Water tables are dropping, global warming
  reducing yields and climate changes affecting
  crops world wide

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Biofuel vs. food debate Pendulum swinging back
to center

• Biofuels, like other products, can be produced
  the right way vs. the wrong way, or compare to
  petroleum
• Per Merril Lynch analysis, without biofuel
  programs, price of oil would be 13/BBL higher
  than it is now, so biofuels are saving 65
  billion in foreign oil payments
• EU US Ag Commissions recently reaffirmed
  positive impacts GHG reduction benefits of
  biofuel policies
• Shift to less polluting, more efficient modes of
  transport
• Promote CO2 reduction policies and encourage
  biofuels
• Biofuel are most immediately feasible way to
  lower CO2

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Biodiesel feedstock evolution diversified fuel
sources

• Early development, then commercialization in
  US/EU
• Soybean (US), Rapeseed (EU) recycled cooking
  oil
• Recent trends in US (2007 -2008)
• Transition from pure soy blends with animal fat
  FAME
• Regional plants using local feedstock Chicken
  fat, beef tallow, pork fat, and recycled cooking
  oil (CA)
• Next 3-5 years More local feedstock, recycled
  oils, trap grease and imported palm oil (summer),
  Jatropha oil
• Locally grown crop oils Sunflower, Canola,
  Safflower
• Imported tropical oils Palm (current) then
  Jatropha

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Tropical crop oils are promising feedstock for
biodieseland fleets

• Most new crop oils should make high spec
  biodiesel provided the oil is in good condition
  properly degummed, low in oxidation low in free
  fatty acids
• Oxidation issues require special precautions
• Cold flow properties are encouraging for Jatropha
  but not for palm or coconut blends of the two
  are likely
• Specifications could tighten for future engines
  oxidation stability, trace ions (P, K, Na,
  Mg, Ca)
• Sustainability issues and land use changes
  critical

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Tropical oil plantations/groves
Jatropha at FL test plot
African Red Palm, Central America
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National Biodiesel Expo Conference San
Francisco February 1-4, 2009
www.biodiesel.org
Jatropha fruit opened 3 oil seeds with over 40
oil by weight
Jatropha fruit ripening on tree