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Biodiesel 101

Biofuels…Moving Indiana Forward


Merrillville, Indiana April 28, 2008
Presented by Hoon Ge
Summary of Topics
• General info on biodiesel
• Emissions
• OEM stance on biodiesel
• 2007 Engines
• Biodiesel Supply & Demand
• BQ 9000 – Fuel Quality
• ULSD and Biodiesel; benefits & compatibility
• Filter plugging sources
• Good fuel “housekeeping”
• Useful informational resources
Machinery Exhibit – 1900 World’s Fair
Rudolph Diesel demonstrated his compression ignition
engine, which at the request of the French Government, ran on
peanut oil.

www.bc.edu/bc_org/avp/cas/fnart/arch/1900fair.html - Jeffrey Howe


History of Biodiesel

 Vegetable oils were used


in diesel engines until the
1920's when engines
began using diesel fuel
Biodiesel Defined

 Biodiesel, n. -- a fuel comprised of mono-alkyl


esters of long chain fatty acids derived from
vegetable oils or animal fats, designated B100,
and meeting the requirements of ASTM D 6751.

 Biodiesel blend, n. -- a blend of biodiesel fuel


meeting ASTM D 6751 with petroleum-based
diesel fuel designated BXX, where XX is the
volume percent of biodiesel.
Making Biodiesel
(Catalyst)

100 pounds + 10 pounds = 10 pounds + 100 pounds


Triglyceride Alcohol Glycerin Mono-Alkyl Esters
_____________________________________________________________________________________________________________

Soy oil Methanol Biodiesel

- Raw Vegetable Oil is NOT Biodiesel!


- Other ‘biomass’ products aren’t Biodiesel
- Must meet ASTM D 6751
Biodiesel Raw Materials
Oil or Fat Alcohol
Soybean Methanol (common)
Corn Ethanol
Canola
Cottonseed Catalyst
Sunflower Sodium hydroxide
Beef tallow Potassium hydroxide
Pork lard
Used cooking oils
Biodiesel Attributes
• High Cetane (avg. over 50)
• Ultra Low Sulfur (avg. ~ 2 ppm)
• High Lubricity, even in blends as low at 1-2%
• High Energy Balance (3.2 to 1)
• Low Agriculture Inputs: Soybeans
• 78% Life Cycle CO2 Reduction
• Renewable, Sustainable
• Domestically Produced
• Reduces HC, PM, CO in existing diesel engines
• Reduces NOx in boilers and home heating
Biodiesel ASTM D6751
Property ASTM Method Limits Units

• Calcium & Magnesium, combined EN 14538 5 max ppm (ug/g)


• Flash Point (closed cup) D 93 93 min. Degrees C
• Alcohol Control (One of the following must be met)
• Methanol Content EN14110 0.2 Max % volume
• Flash Point D93 130 Min Degrees
• Water & Sediment D 2709 0.05 max. % vol.
• Kinematic Viscosity, 40 C D 445 1.9 - 6.0 mm2/sec.
• Sulfated Ash D 874 0.02 max. % mass
• Sulfur
• S 15 Grade D 5453 0.0015 max. (15) % mass (ppm)
• S 500 Grade D 5453 0.05 max. (500) % mass (ppm)
• Copper Strip Corrosion D 130 No. 3 max.
• Cetane D 613 47 min.
• Cloud Point D 2500 Report Degrees C
• Carbon Residue 100% sample D 4530* 0.05 max. % mass
• Acid Number D 664 0.50 max. mg KOH/g
• Free Glycerin D 6584 0.020 max. % mass
• Total Glycerin D 6584 0.240 max. % mass
• Phosphorus Content D 4951 0.001 max. % mass
• Distillation, T90 AET D 1160 360 max. Degrees C
• Sodium/Potassium, combined EN 14538 5 max ppm
• Oxidation Stability EN 14112 3 min hours
Materials Compatibility
• B100 may adversely affect some elastomers such as
natural or nitrile rubbers over time.

• Most elastomers used after 1993 are compatible with


B100 (Viton/Teflon).

• Blends (B20) effect is less or non-existent.

• Normal monitoring of hoses and gaskets for leaks is


sufficient with B20.

• Consult with your parts supplier or


mechanical engineering partners.
Materials Compatibility

• Biodiesel and biodiesel blends will form high


sediment levels when in contact with the
following metals:
-Brass, Bronze, Copper, Lead, Tin and
Zinc

• Biodiesel is compatible with:


- Stainless Steel, Aluminum
Emissions
EPA HD Emissions Averages
Emission Type B100 B20 B2
Total Unburned -67% -20% -2.2%
Hydrocarbons

Carbon Monoxide -48% -12% -1.3%

Particulate Matter -47% -12% -1.3%


Oxides of Nitrogen +10% + 2% + .2%
(NOX)
Biodiesel and Global Warming

• Closed Carbon Cycle: CO2 Used to Grow


Feedstock is Put Back Into Air
• 78% Life Cycle Decrease In CO2

• Energy Balance 3.24 to 1

• Compression Ignition Platform 30% to


40% More Efficient Than Spark Ignition
Biodiesel Position with OEM’s
Original Equipment Manufacturers:
• B100 Must Meet ASTM D 6751

• Most OEM HQ’s have B20 experience:


Won’t void warrantee
Problems caused by the fuel are the responsibility
of the fuel supplier
Want to see additional experience in the field

• Higher blends OK’d based on experience of OEM and


their technology
2007 Engines
Engines Produced in 2007
• EPA regulations require reduced sulfur in diesel fuel for
engines built in 2007

• 80% of highway diesel fuel must be ULSD (< 15ppm


sulfur) beginning june1, 2006

• Catalyzed Diesel Particulate Filters


can eliminate 99% of solid particles
(soot & metals) and eliminate
>90% of semi-volatile
hydrocarbons.
Source: EPA
Diesel Particle Filters (DPF)
• Diesel particle filters (DPF) are found in all 2007
model year diesel vehicles.

• What possible advantages or disadvantages may


result from using biodiesel blends in these
engines?

• The National Renewable Energy Laboratory


(NREL) has conducted a study in order to define
these effects on DPFs.
Indicators of DPF Performance
• Filter
regeneration
rate increased
significantly
when using
blends as low
as B5. Lower
particulate
temperature
and less
particulate
input
contributed.

“Biodiesel Effects on Diesel Particle Filter Performance.” National Renewable Energy Laboratory, March 2006.
Biodiesel
Supply and Demand
Demand for Crude
1 barrel (bbl) = 42 gallons (U.S.)
 Globally about 80,000,000 bbl/day
 Over 16,000,000 bbl of crude oil processed
every day in the US (650,000,000 gal/day)
 800,000,000 gal/day total product demand
 360,000,000 gal/day gasoline
 140,000,000 gal/day distillate
 68,000,000 gal/day jet fuel

 Over 5 billion gallons of distillate fuel oil are


imported each year
 150 U.S. refineries with capacities ranging from 15
mbbl/day (600,000 gallons/day) to over 500
mbbl/day (21,000,000 gallons/day and operate at
90+% capacity
Biodiesel Demand
If Every Trucker Used B2

The industry would


utilize 761 million
gallons of B100
annually.
If Everyone Used B2

 If every body using


diesel fuels (on
and off road) and
home heating oil
used 2% biodiesel
then we would use
1.2 billion gallons
of biodiesel each
year.
Fuel Availability

 Fuel available through direct shipment from over 1,956


petroleum distributors nationwide
 Over 1,234 retail filling stations nationwide
 648 locations are semi-truck accessible
 Movement towards biodiesel at the terminal – over 158
terminals nationwide
 Blending is occurring at over 40 terminals nationwide.
 DOE has supported this effort.
Biodiesel Production Capacity
Production Locations (1/25/08)
Biodiesel Plants Under Construction
and Expansion (9/7/07)
Production Capacity by State
(9/7/07)
300,000,000

275,000,000

250,000,000

225,000,000

200,000,000

175,000,000
Gallons

150,000,000

125,000,000

100,000,000

75,000,000

50,000,000

25,000,000

0
AZ
AL

WY
KY

NY
IA
WA

GA

AR

VA
CA

PA

LA

MA
WI
MO

CO
MI

RI

HI

NM
NJ
IL

FL

UT

CT
TX

MS

NE

ME

DE
NV

KS
ND

TN

MN

OH

IN
SC

NC

OK

ID

SD

OR

MD
BQ-9000
Fuel Quality of Biodiesel
Fuel Quality
• Fuel quality is of the utmost concern and importance
to the biodiesel industry.

• ASTM D 6751 is the specification for biodiesel fuels


irrespective of the feedstock source and/or processing
method.
• National Quality Program (BQ-9000) Launched for
Biodiesel Marketers and Producers
• Look for BQ-9000 Certified Marketers: Biodiesel’s
‘Good Housekeeping’ Seal of Approval
• Assures “cradle-to-grave” fuel quality

“cradle” “grave”
BQ-9000
“Quality Assurance Program”
“Specifies requirements for a quality assurance
program where an organization needs to
demonstrate its ability to provide product that
meets ASTM D 6751… and applicable regulatory
requirements, and to address quality assurance
through the effective application of the program…”

HELPS ENSURE THAT END-USER IS


GETTING HIGH-QUALITY BIODIESEL!!
ALWAYS BUY PRODUCT
FROM BQ-9000 CERTIFIED
PRODUCERS OR
MARKETERS!!!
BQ-9000 Information
Through the NBB
www.bq-9000.org www.biodiesel.org www.nbb.org

Find information
on the
requirements for
the program and
a list of
accredited
producers/marke
ters on the NBB
website.
Biodiesel and ULSD
Benefits and Compatibility
Benefits: Biodiesel and ULSD
• Compatible with the compression ignition
platform and with diesel fuel itself
• Greatly enhances lubricity of ULSD
• Compatible with 2007 diesel engine catalysts
• Aids with ULSD conductivity issues
• Reduces harmful emissions
• Power and performance virtually unchanged
• Seamless & transparent with existing petroleum
infrastructure, (liquid not gaseous)
• Promotes national energy security
• Renewable, non-toxic, green blend stock option
Properties of ULSD & Biodiesel Blends
ULSD B2 B5 B20
API Gravity 33.4 33.4 33.2 32.3

Distillation
IBP 326°F 326°F 327°F 336°F
10% 402°F 403°F 404°F 418°F
50% 509°F 510°F 510°F 550°F
90% 605°F 604°F 608°F 638°F
EBP 611°F 610°F 614°F 645°F

Cetane Index 42.7 42.7 42.8 44.4

Cloud Point 0°F 1°F 1°F 3°F


CFPP -26°F -26°F -24°F -20°F
(3-4x Additive)
Lubricity
ULSD & Lubricity
• Sulfur compounds are natural lubricants in diesel.
• ULSD regulations are causing major concerns
with diesel engine performance.
• ASTM lubricity requirement effective Jan 1, 2005
for diesel fuels.
• ASTM D 6079
High Frequency Reciprocating Rig (HFRR) Wear
Scar
Maximum = 520 micrometers
Biodiesel Adds Significant
Lubricity to ULSD
Biodiesel at varying blends
600
HFRR Average Scar

500
400
(µm)

300
200
100
0
er

B1

B2

B5

1
el

.5
#1

#2

B1
s

B0
Diesel
Die

ed

ed
no
as

as
Mo

Diesel plus Additive


rb

rb

Diesel plus Biodiesel


te

te
Es

Es

The average lubricity of Biodiesel blends compare to lubricity additives.


Lubricity
Lubricity Effects of Biodiesel

700
532
HFRR average scar

600
500
343 318
400
262 234
300
191
200
100
0
Diesel B 0.5 B1 B2 B5 B 11
% Biodiesel

Effects of Biodiesel on the Lubricity of Diesel fuel.


Cold Flow Properties
CFPP Testing of ULSD
Bio Blends
Sample Cloud Point °F CFPP °F
Description Base Fuel w/ Additive
ULSD -2 -22
B11 ULSD (3x) +1 -20
B20 ULSD(4x) +3 -17
B5 ULSD -1 -18
B2 ULSD -2 -20
B2 ULSD -2 -22
CFPP Testing of ULSD B2 blends
with No 1 ULSD
Sample Description Cloud Point °F CFPP °F
Base Fuel Base Fuel w/additive
ULSD Sample 1 0 -20

ULSD 90/10 -4 -25


(90% No 1 & 10% No 2)

ULSD 80/20 -7 -30

ULSD 70/30 -11 -34

ULSD 60/40 -15 -38

ULSD 50/50 -18 < -40


Filter Plugging
Sources
Paraffin Wax
 The material on these filters was solid until touched or
warmed to room temperature, then it melted. Laboratory
analysis showed this material was in fact
paraffin/hydrocarbon in nature. The high level of paraffin
material could be from the way ULSD is processed.

 When the temperature of the fuel is at or below its cloud


point, paraffin material will precipitate out and collect on
the bottom of the tank.

 As a point of note, when the heavy paraffin's are


disturbed from the filters, they liquefy. The minor
ingredients associated with biodiesel will not liquefy and
require heat to go back into solution. Paraffin build-up
does not come from biodiesel fuel.
Aromatic compound
Olefin Compound
H2
C6H6

C6H12
Cyclic, double bonds
Straight, double bond
n-Paraffin Compound

C6H14 H2

Straight, single bonds


Structures taken from www.chemfinder.com
Microbial Growth
 Several filters showed high content of live microbial
organisms or a build-up of dead microbial material.
The filters with microbial contamination often had
an odor different from the normal fuel smell.

 MEG Corp believes that the lack of sulfur in biodiesel


and ULSD aids in the build-up of such organisms
since sulfur is a key component of many biocides
and is a natural inhibitor of bacterial and fungal
growth.
Bacteria
 Breakdown all grades of liquid fuel.
 Cause corrosion of metals, especially iron
and steel.
 Different species can survive with oxygen
(aerobic) or without oxygen (anaerobic).
 Plug fuel-system filters and lines, cause
fuel gauge malfunctions, damage pumps
and injectors, and feed on tank linings,
hoses and coatings to obtain additional
nourishment.
Bacteria
 Grow better in warm climates because
they are living organisms.
“Climates” does not just mean the
temperature of the storage structure, but also
heated fuel returns, which means it is warm
all year long.
 Usually present in high quantities.
 Favorable conditions mean they can
double their population every 20 minutes.
Bacteria
 The level of contamination is hard to determine
visually…

 2 MILLION bacteria per milliliter have no


effect on fuel clarity!
Or in other words…

 8 Billion bacteria per gallon have no effect


on fuel clarity!
Fungus
 Hard to detect.
 Fewer in number and less evenly
distributed in the fluid than bacteria.
 Tend to grow on solid surfaces.
- Build up on filters and in piping.
- Once established, the biomass will grow
faster than a bacterial biomass.
 Yeast are unicellular fungi.
Fungus
 Larger than bacteria and do not reproduce as
rapidly.
 However, if only bacteria are killed suddenly
(bactericide) there may be a rapid fungal bloom
that is nearly impossible to control.
 Can grow over a wide range of temperatures.
 Grow quicker in summer with the higher
ambient temperature, increased airborne
contaminants and higher fluid temperature.
Where Do They Come From?
 Air
– Contains airborne microorganisms, yeast and
mold spores, and dirt particles that can enter
through tank vents.

 Water
– Water, unless sterilized, can contain a variety
microorganisms.
Treatment and Prevention
 Biocides
-Three major groups: Fuel soluble, Water soluble,
and Universally soluble.
-Need to be EPA registered and compatible with the
lubricant.
 Preventing Fuel Contamination
- Preventing contamination from air and water
requires proper tank maintenance and cleaning
Icing of the filter
 When there is excess free water in fuel, it can form ice
on the filter and cause filter plugging in cold temps.
When MEG Corp received filters which had been plugged
but were clean and new by the time MEG Corp received
them, it was concluded that the cause was likely icing
which had since dissipated.

 Since the temperatures of engines are warm, any


moisture picked up within the engine can be brought
back to the fuel lines. This moisture can freeze
overnight in low ambient temperatures.
Oxidation
 When MEG Corp received filters
with a black and shiny surface but
no microbial growth odor or gel or
sediment, it was concluded they
may be plugged by oxidation
build-up.

 Because many newer engines run


at higher temperatures, there may
be a black “asphaltene” type
material collecting on the filter.

 This phenomenon has been seen


all around the country, often in
newer engines.
Engines
Hot Fuel Return
New Technology delivers
the unused fuel from the
engine block back to the
fuel tank much faster

This hot fuel will cause


Hot Hot degradation and oxidation
of the fuel, which in turn
will plug filters.

Coking Fuel
Monoglyceride Build-up
 One filter tested positive
for a concentration of
saturated
monoglyceride material.

 Monoglyceride is one
substance that can
precipitate out of fuel if
the glycerin levels are
too high in the biodiesel
used in the blend.
Quality Control
 In 2006:
41% of B100 samples tested passed the D6751
specification
 In 2007:
89.6% of B100 samples tested passed the D6751
specification

100% of BQ-9000 certified fuel


Past all ASTM D6751 specifications
Troubleshooting Checklist

 Paraffin Wax – Temperature at or below cloud


point
 Microbial Growth – Exposure to air and water
 Icing of Filter – Excess water in tank
 Oxidation – Hot fuel return to fuel tank
 Monoglyceride Build Up – Off specification of
Total & Free Glycerin
Tips for
Biodiesel Handling
Tips for Biodiesel Handling

 Buy biodiesel that meets ASTM D 6751.


Buying from a BQ-9000 Accredited
Producer/Marketer will help ensure quality.
 If buying blended biodiesel, buy it pre-
blended from the supplier.
 Fuel tanks should be kept as full as
possible to reduce the amount of air and
water entering the tank.
Tips for Biodiesel Handling

 Storage in on-site tanks should be limited


to less than 6 months. The storage
container should be clean, dry, and dark.
 Copper, brass, lead, tin and zinc should not
be used to store biodiesel.
 Equipment with biodiesel blends in the fuel
system should not be stored for more than
6 months.
Tips for Biodiesel Handling

 In the winter months, it’s important to use


appropriate additives to ensure good
winter-weather operability.

 If any biodiesel is spilled, it is important to


clean it up quickly. Pure biodiesel may
remove paint from equipment.
Tips for Biodiesel Handling

 When switching from diesel fuel to


biodiesel blend, it may be necessary to
change the fuel filter an extra time or two.

 One outcome of improper handling of


biodiesel may be microbial contamination.
Useful Information
Resources
Educational Resources
• BEN: Biodiesel
Education Network
• Web-based resource
specifically for
petroleum marketers
• Partnership between
NBB/PMAA
• www.pmaa.org
• www.biodiesel.org
NBB Resources: www.biodiesel.org

•Technical Library •Technical Resources


•Biodiesel Bulletin •Educational Videos Available
•Informational Resources •On-line Database & Spec Sheets
Other Biodiesel Resources
• www.bbibiofuels.co
m

• Biodiesel Magazine
A ‘MUST HAVE’
magazine

• Biodiesel Industry
Directory On-Line
Biodiesel Help-line

Established to:

 Provide triage for fuel problems


problems not adequately addressed by distributors/producers
 Diagnose/analyze/assist with problems from:
 customers
 fleets
 fuel distributors
 Provide assistance through chemical analysis
 Through the use of third party Lab
 Help provide assistance to users to ensure the
image/integrity of Biodiesel is maintained.
Contact Information

 The National Biodiesel Helpline is:


 For when you cannot get help elsewhere.
 Not meant for general guidance issues.

You should always begin by asking your fuel


supplier, they will most likely be able to answer
your question more accurately.

800-929-3437
952-473-0182
Questions