4. CONTRIBUTOR
Gary M. Parsons | Global OEM and Industry Liaison Manager
Chevron Oronite LLC
Products and Technology
Gary joined Chevron in 1981 after obtaining his Bachelor of Science and
Master of Science degrees in Mechanical Engineering from the University of
California at Berkeley. From 1981 through 1985, Gary worked as a Research
Engineer in the Fuels Division at Chevron Research and Technology
Company. From 1986 through 1995, Gary was the Oronite Additives Fuels
Product Manager in three different assignments in Europe, North America,
and Asia. In 1995, Gary took the role of Asia Paci c Region Lubricants
Specialist for Oronite Additives. In 1999, Gary joined Chevron Products
Company as an Account Manager in the Strategic Accounts Group. In
October 2000, Gary was selected as a Market Manager in the Commercial
Automotive Group of Chevron Products Company. Since the merger between
Chevron and Texaco in 2001, Gary has served as the Global Consumer
Transport Segment Director and as Commercial Automotive Business Unit
Manager. Gary was named Global OEM and Industry Liaison Manager,
Chevron Oronite LLC in January 2005. Gary has been a member of the
Society of Automotive Engineers (SAE) since 1981.
Acknowledgements
We would like to acknowledge the following subject matter experts who
contributed valuable input and content for this article.
Isabele Araujo, Technology Support Manager – Texaco Brazil
Richard van den Bulk, Chevron Oronite Europe Passenger Car OEM
representative
Arnoud de Vries Feyens, Chevron Oronite Europe Heavy-Duty OEM
representative
Roger Organ, Chevron Products Company Technical Advisor
Rajesh Paulose, Global Product Line Manager, Biofuels – Chevron
Products Company
Frank Stunnenburg, Managing Director, Chevron Oronite Technology
Netherlands
Jan Peters, Automotive Engine Oil Research Engineer, Chevron
Oronite Technology Netherlands
Mark Cooper, Automotive Engine Oil Development Engineer,
Chevron Oronite San Antonio
1
5. Part I part of the solution for complying with
worldwide federal mandates to prevent and
This is the rst part of a two-issue series
on biodiesel. Part I contains background reduce pollution, diversify fuel sources and
information on biodiesel feedstocks, increase energy ef ciency and sustainability.
production and properties, plus Original What is Biodiesel?
Equipment Manufacturers’ concerns regarding
According to the U.S. National Biodiesel
biodiesel use. Part II will provide laboratory
Board (NBB), the terms “biodiesel” and
and engine test data in which certain aspects
“biodiesel blend” have speci c technical
of biodiesel use are evaluated with respect to
de nitions approved by ASTM International.
engine lubrication.
Biodiesel, n—a fuel comprised of mono-
Why All the Buzz About Biodiesel?
alkyl esters of long chain fatty acids derived
Today, countries worldwide are actively from vegetable oils or animal fats, designated
pursuing the development of programs to B100, and meeting the requirements of
promote the production and use of biodiesel, ASTM D 6751.
a renewable fuel for diesel engines derived
Biodiesel Blend, n—a blend of biodiesel fuel
from a variety of plant oils and/or animal
meeting ASTM D 6751 with petroleum-
fats, or recycled cooking oils. Common
based diesel fuel, designated BXX, where XX
plant-based feedstocks for biodiesel include
represents the volume percentage of biodiesel
soybeans, rapeseed, palm, corn, coconut and
fuel in the blend.
jatropha. Animal fats include pork lard, beef
tallow, sh oil and poultry fat. The third Biodiesel blends may contain biodiesel in
source of feedstocks includes “ oat grease” varying concentrations from one volume
from wastewater treatment plants and trap percent (B1) to 100 volume percent (B100).
grease from restaurants, in addition to used Diesel engines are capable of running on
cooking oils. By some de nitions, biodiesel is B100, although the practice is strongly
considered to be biodegradable and suitable discouraged by engine manufacturers, for
for sensitive environments. Biodiesel is a reasons that will be explained later in this
signi cant energy resource that may provide article. Typically dependent on blend credits
Emissions
Biodiesel System
Specifications Durability
Government
Regulations
OEM
Warranty Tax
Coverage Incentives
Process
Impact Quality
on Drain Certification
Intervals
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Emerging Biodiesel Market: Solving the Puzzle to Allow a Smooth Introduction
2
6. CO2
Well-to-Tank Tank-to-Wheels
Well-to-Wheels Analysis-Petroleum System. Hydrocarbons Extracted from the Earth are Burned, Creating CO2 Emissions
and taxation, the most popular biodiesel a country’s trade balance and enables funds
blends currently used in the U.S. are B2, B5, spent on imported petroleum to be reserved
B11 and B20. within the national economy. According to the
In addition to “biodiesel,” there is “renewable International Energy Agency (IEA), the U.S.
diesel,” which perhaps holds greater promise in consumes approximately 20 million barrels of
the long term. The above represents the ASTM oil a day (or 840,000,000 gallons), more than
de nition for biodiesel produced through a half of which is imported. By 2025, demand
transesteri cation process to create a Fatty Acid is expected to rise to 26 million barrels a day,
Methyl Ester (FAME). However, it is important of which 60 percent will be imported, states
to understand that biomass can be handled the U.S. Energy Information Administration
and treated differently in other processes to (EIA). Annual expenditure on imported oil
create products that are not fatty acid methyl is now approximately 250 billion dollars.
esters (FAME and mono alkyl methyl esters are Moreover, this gure is increasing with the
identical). These other processes do not produce steady rise of oil prices to the $90/barrel range.
mono alkyl methyl esters, and are described In addition to trade issues, fossil fuel alone
later in this paper. They create products that are cannot meet the projected global demand for
essentially straight chain saturated C15 and C17 liquid transportation fuels, meaning there
alkyl chains, and are referred to as “renewable is a shortfall. To make up for this shortfall,
diesel.” There are on-going debates regarding all forms of alternative sources are needed,
whether or not renewable diesel should also including biofuels.
enjoy the incentives and subsidies designated
speci cally for mono alkyl ester biodiesel. The An additional motivation for the focus on
following discussion will, however, focus on biodiesel is the need to conserve the world’s
biodiesel in the fatty acid methyl ester form. existing conventional fuel supply, which is
currently being depleted at escalating levels
So why is biodiesel of such global interest each year. Fossil fuels such as diesel are non-
and importance? renewable, meaning that once their existing
Political and Economic Bene ts – Biodiesel supplies are exhausted, they are gone forever.
promotes a nation’s energy security by making Biodiesel, on the other hand, is created
the nation more self-reliant and helps expand from renewable resources that continue
indigenous supplies of fossil fuels. Whether to be cultivated season after season, such
factual or not, there is also the common as oils generated by plants from sunlight
belief that use of renewable fuels can improve and air and fats produced by animals when
3
7. CO2
CO2
CO2
CO2
Solar Energy Biodiesel
CO2 Harvesting Processing Distribution Use as Fuel
Photosynthesis Biodiesel Facility Converts Vehicles Burn
Converts CO2 Feedstock to Biodiesel to
to Feedstock Biodiesel & CO2 Release CO2,
Which is Recycled
Well-to-Wheels Analysis – Biodiesel System CO2 is consumed during Photosynthesis, Offsetting Some CO2 Emissions
they consume food. Renewable fuels are However, some studies have shown that the use
considered more sustainable, as long as of biodiesel does increase the oxides of nitrogen
they are manufactured in an ecologically (NOx) emissions in most cases.
and environmentally acceptable way. Agricultural Bene ts – Biodiesel’s primary
Emissions and Environmental Bene ts feedstocks are soybean oil in the U.S. and
– Biodiesel reduces global warming gas Brazil, rapeseed oil in Europe and palm oil
emissions such as carbon dioxide (CO2) due in Asia. With this important new end-use for
to its closed carbon cycle. When biodiesel these and other crops (such as jatropha, corn,
is harvested, processed and burned, some cottonseed, etc.), there is enormous potential
of the CO2 released into the atmosphere is to stimulate global agricultural economies.
recycled by growing plants. These plants are Conversely, there are growing concerns
later themselves processed into biodiesel, and regarding competing applications of edible
the cycle continues. With fossil fuels, on the feedstocks for food versus renewable fuels.
other hand, 100 percent of CO2 generated These concerns will be addressed further in
escapes into the atmosphere. According to a this paper, in the section on feedstocks.
1998 biodiesel lifecycle study sponsored by Health Bene ts – Scienti c research has
the U.S. Department of Energy (DOE) and shown that compared to petroleum diesel
the U.S. Department of Agriculture (USDA), exhaust, biodiesel emissions have lower levels
biodiesel reduces net CO2 emissions by 78 of harmful polycyclic aromatic hydrocarbons
percent compared to petroleum diesel. The (PAH) and nitrated PAH compounds. These
reason it does not reduce CO2 emissions by compounds have been identi ed as potential
100 percent is that fossil fuels are utilized in carcinogens that can adversely affect
biodiesel production. Based on these results, reproductive, developmental, immunological
the NBB has deemed biodiesel an effective and endocrine systems in both humans and
greenhouse gas mitigation strategy for wildlife. According to the DOE, using B100
medium and heavy-duty vehicles. can help to lower these toxins by up to 90
According to the NBB, compared to emissions percent, whereas using B20 can eliminate
from diesel fuel, biodiesel also helps reduce ozone 20-40 percent of them.
forming hydrocarbon (HC), poisonous carbon Furthermore, in 2000, biodiesel became the
monoxide (CO) and hazardous diesel particulate only alternative fuel to have successfully
matter (PM). Plus, biodiesel virtually eliminates completed the Tier I and Tier II health
acid rain-causing sulfur dioxide emissions. effects testing of the 1990 Clean Air Act
4
8. Amendments. Test results demonstrated that aggressive towards certain elastomers and
biodiesel has a non-toxic effect on health. seals. Therefore, older fuel systems and
distribution systems need to be inspected
Fuel System Lubricity Bene ts – As an
and modi ed before biodiesel can truly be
ester, Biodiesel possesses favorable lubricity
considered a “drop in” technology.
properties, which is important since all diesel
fuel injection equipment relies somewhat on fuel Biodiesel Production Process
as a lubricant, especially rotary and distributor The two ASTM technical de nitions limit
type fuel injection pumps. Low lubricity fuel the use of the term “biodiesel” to fuel that
causes increased wear and consequently is produced when a plant oil or animal fat
reduced component life. Biodiesel also contains is subjected to a transesteri cation process,
less than 15 parts per million (ppm) of sulfur. resulting in Fatty Acid Methyl Ester (FAME)
The introduction of ultra-low sulfur diesel with combustion properties very similar to
fuel (ULSD) renders biodiesel’s lubricity of those of petroleum-based diesel fuel. This
even greater signi cance, since ULSD as FAME constitutes biodiesel. A byproduct of
produced in the re nery can sometimes have this process is glycerin, which is removed.
poor lubricating properties, although this is Transesteri cation requires mixing the oil
easily recti ed in terminals by the addition or fat with an alcohol in the presence of a
of lubricity additive. According to the NBB, catalyst. Alcohol choices include methyl,
bench scale testing has shown that even low- ethyl, propyl or butyl alcohols. Since methyl
level biodiesel blends such as B1 and B2 can alcohol (methanol) is the most cost-ef cient,
improve lubricity up to 65 percent without the it is the most popular choice. It also enables
need for additional lubricity additives. easier separation of the nished product
Ease of Use and Safety Bene ts – Biodiesel from reaction byproducts. Depending on
blends of B20 or less are literally a “drop in” the alcohol used, the resulting biodiesel
technology, according to the DOE. However, will be a methyl ester, ethyl ester, propyl or
not all Original Equipment Manufacturers butyl ester respectively. Common catalysts
(OEMs) agree with this assessment, as will include sodium hydroxide and potassium
be noted later. Biodiesel blends can be used hydroxide. In the U.S., the main form of
in most diesel equipment with few, if any, biodiesel is methyl soyate or soydiesel, formed
modi cations, and can also be used in the by reacting methanol with soybean oil. The
existing diesel fuel storage and distribution transesteri cation process reacts 100 units
infrastructure. Plus, biodiesel is safer to (by weight) of feedstock with 20 units of
use than petroleum diesel; the ashpoint short-chain alcohol such as methanol in the
for pure biodiesel (B100) is at least 260˚F presence of a catalyst, yielding approximately
(130˚C), versus a minimum of 125˚F (52˚C) 100 units of biodiesel, 10 units of methanol
for standard diesel. On the other hand, it (recovered from reaction) and 10 units of
must be noted that biodiesel (B100) is more crude glycerin.
Typical Biodiesel Transesteri cation Process
5
9. Biodiesel Standards values for properties such as viscosity and
In 2001, the ASTM approved the standard ash point, the most important distinction
for biodiesel, designated ASTM D 6751. This between the two is the measurement of
standard pertains to pure biodiesel, known oxidation and polymerization. Unsaturated
as B100, for use with petroleum diesel blends oils oxidize faster and polymerize more
up to 20 percent by volume. Currently, work rapidly than saturated oils. The Iodine Value
is underway to incorporate B5 into D 975, (IV) measures the level of unsaturation
the petroleum diesel speci cation, as well in biodiesel. Consequently, a higher IV
as to develop separate speci cations for indicates a higher level of unsaturates, which
biodiesel blends between B6 and B20. Not in turn indicates an increased tendency to
wanting to wait for an of cial ASTM B20 oxidize and polymerize. While EN 14214
speci cation, on May 31, 2006, the Engine establishes a maximum IV of 120 as well
Manufacturer’s Association issued a “Test as an additional oxidation parameter called
Speci cation for Biodiesel Fuel” and has an Oxidative Stability Index, ASTM D 6751
encouraged producers and users to follow does not incorporate an IV. However, it has
it until an of cial ASTM speci cation is recently been revised to include a three-
issued. The federal government has made hour oxidation stability requirement. EN
ASTM D 6751 part of the of cial de nition 14214 incorporates a more severe six-hour
of biodiesel in the Energy Policy Act of 2005. requirement. Since the soy methyl ester
Additionally, biodiesel, as de ned in D 6751, produced in the U.S. has a higher IV than
is registered with the EPA as a fuel and a fuel the rape methyl ester in Europe, 130 versus
additive under Section 211(b) of the Clean 100 approximately, pure soybean oil methyl
Air Act. ester does not meet the requirements of EN
14214. With the looming shortage in Europe
The European standards organization,
of rapeseed for biodiesel, EN 14214 may be
Comité Européen de Normalisation (CEN)
relaxed to allow for the import of a wider
has also developed a performance standard
range of biodiesel feedstocks, such as soy
for biodiesel fuel, EN 14214, which is
methyl ester. Currently, however, palm oil is
considered to be stricter than ASTM D
being imported from Asia to make up for the
6751. Its criteria are most easily met by
shortfall in rapeseed.
methyl esters manufactured from rapeseed,
which is the most common biodiesel Across the globe, many countries have
feedstock in Europe. Although EN 14214 either simply adopted the U.S. or European
and ASTM D 6751 establish different speci cations, or adjusted them to t their
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Biodiesel is a Global Phenomenon
6
10. needs. For instance, although Canada supports 84 million metric tons (mt) of soybeans.
ASTM D 6751, it has established a speci cation Brazil was a close second with 57 million
for biodiesel blends B1 through B5 called CAN/ mt. These gures are projected to increase
CGSB – 3.520 “Automotive Low Sulphur Diesel yearly as additional acreage is devoted to soy
Fuel Containing Low Levels of Biodiesel Esters production to meet the rapidly rising demand
(B1-B5).” Australia, Indonesia and Brazil’s for biodiesel. However, a potential issue here
biodiesel standards are a combination of is that both the U.S. and Brazil also have
ASTM D 6751 and EN 14214. Japan’s biodiesel competing needs for ethanol, which requires
standard, JASO M360, is based on EN 14214, the cultivation of arable land for corn and
but with a more severe oxidation requirement. sugarcane instead of soybeans.
Thailand’s biodiesel standard is also similar Rapeseed /Ca nola:
to EN 14214. In addition, Taiwan and Hong Rapeseed and canola
Kong are discussing standards similar to EN is essentially the same
14214. The Philippines’ standard is speci cally crop, but canola is a
for B100 for CME (coconut methyl esters). version of rapeseed
Biodiesel Feedstocks developed to lower
the eruic acid to make
A burning question today is how to supply
the product safer for
the feedstocks necessary to produce the
human consumption.
biodiesel mandated and/or subsidized by
According to the USDA, in 2006, the EU
governments internationally. One concern
produced 15.41 mt of rapeseed, while the U.S
is whether there is adequate arable land and
and Canada produced approximately 0.7
water available to meet the growing demand.
and 9.66 million mt of canola respectively.
Additionally, there is a growing debate as to
A large part of Canada’s canola crop is
whether renewable fuels are being promoted
exported to the U.S., and Europe is another
at the expense of food.
potential export market due to its current
In most regions, the primary feedstock for rapeseed shortage. However, a problem for
biodiesel is also used for human consumption, Canadian canola is the EU ban forbidding
such as soybean oil in the U.S. and Brazil, the import of genetically modified crops.
rapeseed and sun ower oil in Europe, palm oil This is currently under review by the EU
in Asia and canola oil in Canada. One result due to its urgent need.
of the food vs. fuel debate is that the increased
Palm Oil: According
demand for edible feedstocks tends to in ate
to the March 2006
their price compared to non-edible feedstocks.
Foreign Agricultural
Feedstocks account for 80 percent of biodiesel
Service (FAS) crop
production costs and are the main reason that
assessment, Indonesia
biodiesel is more expensive than conventional
and Malaysia together
diesel fuel. According to the USDA, it takes
accounted for over 85
about 7.3 pounds of soybean oil, which costs
percent of global supply,
about 30-35 cents per pound, to produce a
each country producing
gallon of biodiesel. Feedstock alone, therefore,
approximately 15 million mt. Much of this
accounts for approximately $2.45 per gallon
is exported, especially to the EU. An
of soy biodiesel. While fats and greases cost
issue of serious environmental concern
less and produce less expensive biodiesel, their
is the practice of clearing tropical rain
supply is more limited and localized.
forests in order to make room for more
Some of the common international biodiesel palm oil plantations. Both countries
feedstocks are: have denied this practice and have
Vegetable Oils: announced measures to protect the rain
forests. However, recently, the European
Soybeans: The U.S. is the Parliament has called for a ban on the
world’s largest producer use of biodiesel processed from palm oil,
of soybeans, producing stating that the growing production of
almost 38 percent of palm oil, sugarcane and soy in southeast
the world’s crop in Asia and South America is destroying
2006. According to the tropical forests and other ecosystems,
USDA, in 2006 the U.S. resulting in huge carbon dioxide
produced approximately emissions. They claim that carbon dioxide
7
11. released from clearing and draining peat or rain forests. If successfully cultivated,
wetlands, and also forest fires in southeast this acreage would produce approximately
Asia are related to the growing number of seven million gallons of biodiesel per year.
plantations for biodiesel production. Jatropha is also being planted in a number
of African countries and in Guatemala
Coconut: The Philippines
and the Philippines. However, it should
is the rst nation to
be noted that past attempts by the United
domestically produce
Nations to establish Jatropha plantations
and use coconut-derived
and associated industries have not proved
biodiesel. In May
economic or successful.
2007, the Philippine
government introduced Animal Fats/Tallow:
a biofuels act mandating Only the lower grades of inedible tallow are
all oil rms to blend one candidates for the biodiesel pool since higher
per cent (B1) coconut-methyl ester in their grades are absorbed by the chemical sector.
diesel products. The Philippines’ Department Consequently, tallow is not a significant
of Agriculture and the Philippine Coconut resource for U.S. biodiesel production.
Authority (PCA) plan to develop 740,000 The lower grades have higher free fatty
acres of land to meet the demand for expanded acid levels (FFA) and contain impurities,
usage of coconut-methyl ester in diesel. making pre-processing a necessary step
Jatropha Curcas (Physic Nut): Jatropha’s prior to transesterification. A major issue
major advantage is that it can be grown in with tallow-based biodiesel is its very high
virtually any tropical terrain and does not content of saturated fats, which translates
compete with food crops for arable land, to a methyl ester with poor cold weather
thereby avoiding any issues with the food vs. qualities. The cold flow pour point of
fuel debate. However, unlike the byproducts tallow-based methyl esters can be as high
of edible crops, the spent oil cake from as 59˚ F (15˚C), which is unacceptable even
jatropha cannot be fed to animals or used in warmer climates. Tallow of sheep and
in applications where its toxicity is an issue. cattle is the primary biodiesel feedstock in
Jatropha is most popular in India, which Australia and is being considered for use in
has identi ed almost 100 million acres of New Zealand.
land that could potentially be dedicated to Yellow and Brown Greases:
jatropha without impacting edible crops
100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
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Saturated Fat Monounsaturated Fat Polyunsaturated Fat
Biodiesel Feedstock Composition Impacts Performance
8
12. Other biodiesel feedstocks include the animal used. The differing levels of saturation determine
fats and vegetable oils used for cooking. Used the properties of nished biodiesel. Biodiesel
cooking oil is sometimes called “yellow” grease, made from feedstocks that contain highly
and although there is no strict de nition, trap saturated fatty acids, (such as palm and coconut
grease and sewage greases are referred to as oils, beef tallow and yellow grease), has a high
“brown grease.” The de nitions of yellow and cetane number and superior oxidative stability. It
brown grease are blurred and are often based on also helps reduce NOx emissions. One downside
the degree of oxidation, color and FAA content. is that this biodiesel has poor cold weather
Due to resource limitations, recycled cooking oil properties; it exhibits high cloud and pour points,
alone is not a viable solution for the energy crisis. which means it tends to start forming crystals
However, it is sometimes the feedstock of choice much too soon for use in colder climates. On the
for small biodiesel plants. The biggest drawback other hand, biodiesel made from oils with high
of these greases is their variable nature— they polyunsaturated content, (such as soy, canola and
often contain deposits that must be ltered out, sun ower oils), has lower cloud and pour points,
and have high FFA levels. They must undergo which make for better cold weather properties.
a series of pre-treatment processes in order to However, it has a lower cetane number and poor
meet the minimum quality requirements for oxidative stability, and also tends to produce
transesteri cation. higher NOx emissions. It is possible to impact
Feedstocks In uence Biodiesel Properties the varying properties of different biodiesel fuels
by the use of additives.
Biodiesel’s properties depend heavily on the
speci c feedstock used, which is a challenge for Challenges of Biodiesel
the industry since it is critical to ensure consistent High Cost – Biodiesel generally costs more to
quality among the various blendstocks. Each manufacture than petroleum diesel, resulting
animal fat or vegetable oil molecule used to in a wholesale price that is typically higher
produce biodiesel via transesteri cation is by $1-$2 per gallon, according to the DOE.
composed of a glycerine backbone of three Traditionally, B20 has been priced about 20
carbons, to each of which is attached a long chain cents more than diesel fuel while B2 has been
fatty acid. These long chain fatty acids react with only a few cents more. The price difference
methanol to make the methyl ester or biodiesel, is primarily due to high feedstock costs,
and may be saturated, monounsaturated or and renders biodiesel uncompetitive with
polyunsaturated, depending on the feedstock petroleum diesel. Currently the biodiesel
Not all Engines Appreciate Biodiesel: Catastrophic Failure Caused by Biodiesel Use without Adjusting Maintenance
Intervals and Using Compatible Lubricants
9
13. industry is reliant on a plethora of federal High Solvency Effect – Biodiesel has a
and state programs, subsidies, production tendency to dissolve accumulated sediments in
incentives and tax credits. For instance, diesel storage and engine fuel tanks, due to the
federal blend tax credits of $1 and $0.50 per superior solvency properties of methyl esters.
gallon exist in the U.S. for biodiesel produced These dissolved sediments can then plug fuel
from agricultural and non-agricultural lters. Sometimes the lters burst, propelling
feedstocks respectively. Similar tax credit sediment through the fuel injector system to
schemes are used in other countries. Critics cause injector deposits and potential failure.
argue that in order for biodiesel to be The solvency effect is much greater with high
enduringly successful as a viable industry, it blends of biodiesel compared to B20 and lower
must be economically self-supporting. blends. Therefore, before B100 is used for the
rst time in tanks or lines previously used for
Lower Energy Content – According to the
petroleum diesel, it is important to clean the
DOE, biodiesel (B100) contains approximately
tanks and fuel systems thoroughly to remove
8.5 percent less energy per gallon than typical
old sludge and deposits. It is also advisable to
No.2 petroleum diesel fuel. This is due to
check fuel lters frequently and change them
the oxygen content in the ester molecules as necessary.
of biodiesel, which essentially means that
the molecule is already partially reacted Materials Compatibility – Pure biodiesel
(combustion is the reaction between carbon degrades, softens or seeps through some hoses,
and hydrogen with oxygen). Therefore, one gaskets, elastomers, seals, glues and plastics
can think of biodiesel as partially burnt by with prolonged exposure, which can create
about 12 percent. The difference in density fuel system leaks. Nitrile rubber compounds,
between FAME and mineral diesel then results polypropylene, polyvinyl and Tygon materials
in the per gallon difference in energy content are especially susceptible. Using biodiesel
of approximately 8.5 percent as stated above. blends higher than B20 can damage fuel
One gallon of No. 2 diesel contains 129,050 systems components such as hoses and pump
BTUs, while one gallon of biodiesel contains seals, which contain elastomers incompatible
118,170 BTUs. While this difference in energy with biodiesel. In this situation, users should
content is often imperceptible with respect to consider replacement with compatible
power, torque and fuel economy in engines elastomers. However, this is primarily an issue
using blends up to B20, it can de nitely be with older engines manufactured before 1993,
noticeable with B100. Since fuel accounts for according to the DOE. The recent switch to
up to 50 percent of a truck eet’s cost, small ULSD has meant most OEMs have converted
differences in cost and energy content (fuel to components that are also suitable for use
economy) can result in a signi cant impact on with biodiesel. B5 and lower blends have not
truck eet pro tability. exhibited elastomer deterioration and may not
require modi cations.
Poor Cold Weather Performance – Biodiesel
freezes or gels up in cold weather sooner than B20 and higher biodiesel blends will degrade
petroleum diesel, due to its relatively high and create sediments after prolonged contact
pour point temperature. As the fuel gels, it with bronze, brass, tin, copper, zinc and lead.
becomes increasingly viscous, clogging fuel Copper pipes and ttings, brass regulators,
lters and hindering the passage of fuel zinc linings and lead solders should also be
from the tank to the engine. Cold weather avoided. Biodiesel is hydroscopic, meaning it
properties are the major reason that many attracts moisture. Once it comes in contact
people use biodiesel blends as opposed to neat with moisture, it can hydrolyze and form
biodiesel, B100. The NBB recommends that a variety of organic acids which are partly
the same cold weather performance solutions, responsible for its compatibility problems
(kerosene and cold ow additives), that are with various seal, elastomers, and metals.
utilized with No.2 diesel fuel, should also Low Oxidative Stability – Biodiesel has lower
be used with B20. While B20 usually raises oxidative (long-term storage) stability than
fuel cold weather properties such as cloud petroleum diesel. Factors affecting biodiesel’s
point, pour point and lter plugging point by oxidative stability include the degree of
2-10˚F, B5 and B2 have virtually no impact saturation of the feedstock, the level of natural
on cold ow. Biodiesel’s cold ow properties antioxidant content, carbon chain length and
are heavily dependant on feedstock selection, the presence of glycerides. In biodiesel, fuel
as described earlier in this article. aging and oxidation can create high viscosity,
10
14. high acid numbers and the formation of lter- product quality. Therefore, the spotlight is
clogging varnish and sediments. The NBB shifting to what is called second generation
recommends a six-month maximum storage life and third generation, or renewable diesel,
for B100. If the fuel is kept longer, antioxidants which has the potential to cover a greater
should be added and periodic tests should be portion of world energy demand. Unlike
performed to ensure the fuel continues to meet biodiesel, second generation renewable diesel
the ASTM D 6751 speci cation. Suitable storage is manufactured in oil re neries using a
tank materials are steel, aluminum, uorinated chemical process similar to the conversion of
polyethylene, uorinated propylene and crude oil into motor fuel. Third generation
Te on. Some suppliers use nitrogen blanketed renewable diesel can be obtained from ligno-
storage vessels to reduce the tendency of stored cellulosic sources such as straw, timber,
biodiesel to oxidize and to help keep moisture woodchips, plant waste or manure. Since
and condensation out of the tank. the technology allows renewable diesel to
be produced from any plant material, this
Increased NOx Emissions – Biodiesel causes would eliminate the competition between
a slight increase in emissions of ozone- food and fuel as well as the nished product
forming nitrogen oxides (NOx), according quality concerns that are intrinsic to rst
to the DOE. The precise composition of generation biodiesel production. The main
biodiesel in uences NOx emissions. There source of raw materials for energy would
is around 15 percent NOx variability among shift from arable land to forests, peat bogs,
the various biodiesels meeting ASTM D 6751, and crop and municipal residue. The process
with soybean oil-derived biodiesel creating is called biomass-to-liquid (BTL), in which
the highest increase in NOx due possibly the previously pelletized biomass is directly
to reactions with its high polyunsaturated gasi ed at low pressure. The resulting
fatty acid content. Although biodiesel itself synthetic gas is puri ed and then converted
contains very little bound nitrogen, NOx is into a liquid diesel fuel using a catalytic
created in the engine as nitrogen and oxygen conversion process like the Fischer Tropsch
in the intake air react at the high in-cylinder synthesis reaction. Unlike rst generation
combustion temperatures. Some effort is biodiesel, the properties of the nished
being made to solve this problem with the use second or third generation renewable diesel
of exhaust after-treatment systems in newer product are independent of the feedstock.
engines, but the possible increase in the NOx
levels when biodiesel is used in older engines While rst and second generation biodiesel
is a concern. There are research efforts is mainly produced from grain kernels only,
underway by the California Air Resources third generation biodiesel is manufactured
Board (CARB) and by the EPA to de ne the from the entire plant, offering the prospect
problem of NOx increase more precisely. of much higher yields. Plus, a signi cant
Some past work has indicated the increased environmental advantage of third generation
NOx is related to differences in injection biodiesel is its lower greenhouse gas emissions.
rates into the combustion chamber caused It has a smaller carbon footprint since the
by biodiesel’s higher viscosity and bulk amount of energy-intensive fertilizers and
modulus, which makes it less compressible fungicides remains unchanged for a far
than petroleum diesel. The higher bulk greater output of useable material.
modulus and higher speed of sound of There are two sizeable obstacles that need to
biodiesel means the pressure rises in the be overcome before third generation biodiesel
fuel lines and develops an advance of nearly arrives at the pumps—technology and
two degrees in injection timing. This in turn cost. The BTL production process is much
generates a faster pressure and temperature more complicated than transesteri cation.
rise in the combustion cylinder, leading to an Relatively high manufacturing expenditure
increase in NOx. means that third-generation biodiesel cannot
yet be produced economically on a large scale.
Second Generation Biodiesel and Biomass-
However, ultimately it offers higher potential
to-Liquid (BTL) or “Renewable Diesel”
for production and cost reductions, because
Today’s FAMEs are considered rst it can be sourced from biowaste with fewer
generation biodiesel. In spite of enormous competing end-uses. Consequently more
investment efforts, this biodiesel alone is not research projects are being launched worldwide
suf cient to ful ll growing global energy for the purpose of developing biomass-based
demand and there are concerns regarding processes to commercial maturity.
11
15. Two second-generation renewable diesel ConocoPhillips and Tyson Foods Unite to
projects are highlighted below: Produce Second Generation Biodiesel
Neste Oil’s NExBTL ® Technology In April 2007, meat producer Tyson Foods
and oil company ConocoPhillips announced
Finland’s Neste Oil has developed NExBTL , ®
plans to work together to produce second
which stands for NExt generation Biomass To
generation renewable diesel fuel from pork
Liquids diesel technology, and incorporates
and poultry fat. Using a proprietary thermal
a unique approach of combining natural
depolymerization production technology,
renewable raw materials with traditional oil
the animal fats will be processed and then
re ning processes. It is similar to “H-Bio,”
fed along with hydrocarbon feedstocks to a
the second generation biodiesel developed
hydrotreater unit, to produce a high-quality
by Italy’s ENI and Brazil’s Petrobras. The
diesel fuel that meets all federal standards
process consists of hydrogenating fatty acids
for ultra-low-sulfur diesel. The nal product
across a nickel-molybdenum catalyst under
has a high cetane value, and the processing
high pressure. It can use multiple plant oil
step improves storage stability and handling
feedstocks and animal fats to create a superior characteristics compared to biodiesel created
product with characteristics similar to ultra- by transesteri cation. The bene t of treating
clean synthetic biodiesel. The advantage of the animal fats this way is that the nished
NExBTL® and the similar H-Bio technology product could be passed through multi-
is that it can be fully integrated in existing product pipelines just as ultra-low-sulfur
oil re neries, and the nished fuel properties diesel is today.
are largely independent of the feedstock.
Such re neries already have hydrogenation The two companies estimate that the
facilities, therefore renewable diesel units operation could result in 175 million gallons
can be more easily incorporated into existing of renewable diesel a year. As previously
plants. The rst NExBTL® plant started mentioned, animal fats and cooking greases
production this year in Porvoo, Finland, with alone cannot solve the energy crisis. To put
a capacity of 170,000 tons a year. things in perspective, the U.S. consumed
approximately 62 billion gallons of diesel
NExBTL® is sulfur-, oxygen-, nitrogen-, and in 2006, according to the DOE. Thus,
aromatic-free and has a very high cetane ConocoPhillips and Tyson’s contribution
number. It can have acceptable cold weather would constitute less than one percent of the
properties, good storage stability, low water overall diesel consumption.
solubility and also reduces exhaust emissions.
However, the distillation curve is different The companies are expecting to be able
from that of mineral diesel and the lack of to take advantage of the $1 per gallon tax
light ends has some Original Equipment credit that will make the fuel cost effective.
Manufacturers (OEMs) concerned about cold Although the tax credit is set to expire in
start problems if B100 were to be used in cold 2008, it is likely to be extended given the
climates. NExBTL® biodiesel is compatible government’s commitment to ensuring that
with the existing diesel eet as well as with biodiesel stays competitive with regular fossil
diesel logistics systems, and is technically fuel diesel.
easy to blend in conventional diesels in all National Biodiesel Accreditation Program:
ratios. The EU has approved NExBTL® as a BQ-9000
certi ed EU diesel fuel.
Biodiesel fuel quality is of paramount concern
Neste has labeled NExBTL® as “renewable” and importance to the biodiesel industry.
diesel to distinguish it from traditional For this reason, the NBB has established a
biodiesel, a distinction that may prohibit quality assurance program called BQ-9000
the fuel from enjoying some incentives and for the accreditation of biodiesel producers
mandates designated speci cally for mono and marketers. The primary objective
alkyl ester biodiesel. This issue is currently of BQ-9000 is to ensure that biodiesel is
being discussed in the U.S., where the $1 per consistently manufactured per the ASTM
gallon tax credit for biodiesel would apply D 6751 standard. BQ-9000 combines the
for NExBTL® today, based on an Internal ASTM standards with an integrated quality
Revenue Service ruling that was issued in program that includes storage, sampling,
April 2007. The NBB, amongst others, is testing, blending, shipping, distribution
challenging the ruling. and fuel management practices. To receive
12
16. accreditation, companies must pass a rigorous B100) will not void their parts and
review and inspection of their quality control workmanship warranties, provided the
processes by an independent auditor. There biodiesel meets ASTM D 6751. Some
are two types of accreditation; Accredited OEMs also recommend that biodiesel be
Producer and Certi ed Marketer. purchased solely from BQ-9000 certified
A national fuel quality testing project, co- companies. Certain OEMs even fuel
funded by NBB and the NREL, discovered their new diesel vehicles with biodiesel
that 59 percent of biodiesel samples taken blends in the factory, such as John Deere
between November 2005 and July 2006 with B2 and Case IH with B5. Chrysler
were out of speci cation for incomplete also fills all its diesel-powered Jeep ®
processing, containing trace quantities of Libertys, Dodge Rams and Jeep Grand
un-reacted di- and tri- glycerides. These un- Cherokees with B5. Furthermore, the
reacted components will also combine with Energy Policy Act (EPAct) encourages
natural sterols in biodiesel, leading to large municipalities and non-combat military
molecules that will not pass through lters. vehicles to use B20 by allowing fleets
This is the same issue that caused some lter to meet part of their alternative fueled
clogging problems in Minnesota in winter, vehicle (AFV) acquisition target through
since cold weather can amplify problems purchase credits awarded for the use of
caused by out-of-speci cation fuel. The B20 or higher blends. This has compelled
NBB/NREL test results indicate that some some OEMs to warrant B20 use in these
producers are not correctly monitoring applications. For instance, Chrysler has
the quality of their biodiesel, and help to approved B20 use in its Dodge Ram
underline the importance of BQ-9000. pickup trucks for government, military
and some commercial fleet customers.
Germany and Austria have established a similar
program called the “Arbeitsgemeinschaft The NBB, together with major OEMs, has
Qualitätsmanagement Biodiesel” (AGQM) formed the B20 Fleet Evaluation Team (B20
or the “Labor Group for Biodiesel Quality FET) to develop a position on the use of
Management.” This organization includes biodiesel blends up to B20 in diesel engine
many service stations that offer biodiesel, applications in the U.S. The B20 FET
which have pledged to sell only rape methyl has identified a list of recommendations
ester (RME) since it is the sole form of biodiesel for users dated June 2005 and titled,
approved by certain original equipment “Technical Recommendations for B20
manufacturers (OEM). Fleet Use Based on Existing Data.” This
also applies to blends over B5 and below
Original Equipment Manufacturers B20, such as B11, which is popular in
(OEMs) and Biodiesel Illinois. While this list is not intended to
All engine and vehicle OEMs provide a replace warranty limitations established
material and workmanship warranty on by individual OEMs, it is a statement of
their products. These warranties do not confidence that B20 can be used trouble
cover problems caused by external factors free if appropriate precautions are taken.
out of their control, such as fuel variations. Simultaneously, the NBB is also actively
Therefore, the most important points working with the ASTM to develop a
regarding engine warranties and biodiesel separate standard for B20. This will be
are whether an OEM will void its warranty critical in enabling OEMs to increase
when biodiesel is used, and whether the fuel their recommended biodiesel blend level
supplier will stand behind its fuels in case to B20. As previously mentioned in the
of trouble. Existing and potential users of section on standards, the EMA has issued
biodiesel should consult with their OEM a B20 “Test Specification for Biodiesel
representatives to determine what the terms Fuel,” and work is also ongoing to create
and conditions of their warranty coverage distinct specifications for blends up to
might be. Local laws and regulations vary B5, and between B6 and B20.
in this respect. Position of International OEMs
Position of U.S. OEMs In Europe, since the EN 590 standard permits
All major OEMs have stated formally diesel fuel to contain up to B5 without being
that the use of biodiesel blends up to labeled, in practice, the user has no idea
B5 (and in some cases B20 and even which blend is actually lled at the pump.
13
17. As a result, most major heavy-duty and OEM Concerns with Biodiesel
passenger car European OEMs have been OEMs are worried about biodiesel’s impact
compelled to accept B5. They will honor on three key engine components - fuel system,
their warranties with the use of biodiesel lubricant performance and emissions system.
blends up to B5, provided the biodiesel meets
EN 14214. Currently, the EU is investigating While B5 is generally considered safe, users of
the possibility of allowing up to B10 in the higher concentrations of biodiesel have reported
EN 590 standard in 2008. fuel system problems such as corrosion and
deposits in injection systems and compatibility
The Japanese heavy-duty OEMs allow the use issues with rubber seals in fuel systems. While
of up to B5 in their engines, provided the neat biodiesel’s effect on engine lubrication is not
biodiesel meets JASO M360, the Japanese completely understood, one de nite fact is that
speci cation introduced in April 2007. It is its higher density, surface tension, and viscosity
similar to EN 14214, but incorporates more relative to mineral diesel creates fuel dilution
severe oxidation requirements. in the crankcase and engine corrosion issues
Below is a table that lists some of the OEMs’ plus sludge and piston deposits. Most OEMs
current positions on warranties with the use will honor their warranties in the case of these
of biodiesel blends. Since these often change, higher blends more or less on a case-by-case
the end user is strongly advised to consult basis, and only if their recommendations are
the speci c OEM before utilizing any level of implemented. However, major diesel injection
biodiesel blend. manufacturers Denso, Delphi, Siemens VDO
Manufacturer Warranty Position
Case IH All engines approved for up to B5 and most for up to B20.
Must meet ASTM D 6751 or EN 14214
Caterpillar Many engines approved for B30 and B100, others limited to
B5. Must meet ASTM D 6751 or EN 14214
Cummins Most post-2002 engines approved for up to B20, must meet
ASTM D 6751
Daimler/Chrysler All engines approved for up to B5 and some for up to B20.
Must meet ASTM D 6751
Detroit Diesel Approve up to B5, must meet ASTM D 6751
Ford Up to B5, must meet ASTM D 6751 or EN 14214
General Motors All engines approved for up to B5 and some up to B20. Must
meet ASTM D 6751
International Approve up to B20, must meet ASTM D 6751
John Deere All engines approved for up to B5, must meet ASTM D 6751
or EN 14214
Mack Up to B5, must meet ASTM D 6751
Mercedes-Benz Up to B5, must meet ASTM D 6751 plus have the necessary
oxidation stability (min. 6h, proved with EN14112 method) to
prevent damage from deposits and/or corrosion
New Holland Up to B20, must meet ASTM D 6751
Scania Up to B5 and also B100 with reduced drain intervals. Must
meet EN 14214
UD Trucks/Nissan Diesel Up to B5, must meet EN 14214 or ASTM D 6751
Volkswagon Up to B5, must meet EN 14214 or ASTM D 6751
Volvo Up to B5, must meet EN 14214 or ASTM D 6751
Fuel Injection Equipment
Manufacturer
Bosch Up to B5, must meet EN 14214
Delphi Up to B5, must meet ASTM D 6751
Siemens VDO Up to B5, must meet EN 14214 or ASTM D 6751
Stanadyne Up to B20, must meet ASTM D 6751
Denso Up to B5, must meet EN14214, ASTM D 6751, or JASO
M360 depending on region
14
18. and Bosch will not honor their warranties with In order to address some of these issues, most
the use of biodiesel blends above B5. Stanadyne, European OEMs prescribe a 50-70 percent
on the other hand, will warrant up to B20. reduction in oil drain intervals with the use of
biodiesel blends above B5. For instance, in the
The increasingly strict emissions regulations
case of Mercedes Benz trucks, this means service
oblige the OEMs to use extremely precise
intervals decrease from 100,000 km to 30,000
equipment, as well as guarantee in-use
km, a 70 percent reduction. Unfortunately,
emissions compliance for an extended
for large eets, these reduced service intervals
duration (for example, 10 years or 485,000
are scally unattractive, and act as a deterrent
miles for heavy-duty trucks in the U.S.)
to the use of biodiesel blends above B5. This,
Biodiesel poses an unknown factor in this
along with biodiesel becoming more expensive
equation – it has not been the subject of any
as subsidies expire, has led to a drop in usage
certi cation work, and its impact on emissions
of biodiesel in some countries. For instance,
and emissions system durability is not yet
the German government is reducing some of its
fully known. Moreover, various biodiesel
many subsidies and tax incentives for biodiesel,
blends may potentially impact emissions
effectively eliminating the nancial advantage.
in different ways. Many believe the OEMs
should not be responsible for differences in Pure Plant Oils
emissions levels due to biodiesel use. Some German eet operators have replaced
While the use of B5 is generally trouble-free B100 with pure plant oils, which do not meet
in the case of older diesel passenger cars and EN 14214. These oils have created numerous
heavy-duty trucks without diesel particulate issues for OEMs and operators, including
lters (DPFs), increasing problems have cold-start dif culties, corrosion and elastomer
been detected in newer engines with DPFs. degradation. A similar situation also arose in
In some applications, OEMs are using a late Brazil, where some eets were motivated by
“post” injection to help regenerate DPFs. price to mix vegetable oil directly with diesel,
This late injection may create higher levels resulting in engine failures. It is for this reason
of fuel dilution. Biodiesel is more persistent that biodiesel is strictly de ned as a mono alkyl
once it enters the crankcase and thermally methyl ester (same as a fatty acid methyl ester).
decomposes forming insolubles and deposits. Pure plant oils generally have high viscosities
OEMs have noted situations where fuel and contain substances that will form gums
dilution rates ran up to 15 percent in vehicles and deposits in fuel systems, and as such are not
operated with DPF and post injection. acceptable for use in modern diesel engines.
Fuel System Emissions Systems
Injector deposits Impact on after-
Fuel filter plugging treatment devices
and sensors
Injection pump durability
Impact on NOx
Materials incompatibility emissions
Fuel Instability
Lower BTU
Low temperature handling content/fuel economy
May reduce detergency
and anti-foam properties
of fuel additive Lubricant Performance
packages Fuel dilution
Corrosion
Viscosity increase
Oxidation
Piston Deposits
Sludge Deposits
Wear
OEM Biodiesel Concerns and Unknowns
15
19. Diesel – normal droplet size
Larger fuel spray droplet size
Late or post injection leads to
higher levels of fuel dilution
Crankcase Fuel Dilution with Biodiesel-Properties of Biodiesel Lead to Higher Fuel Dilution Levels than Mineral Diesel
Part I-Summary of the concerns and issues being faced by
the industry. In Part II, we will focus on
In this rst part of a two-issue series, the
diesel engine oil lubrication performance
reader has gained a basic understanding of
when biodiesel is used. Bench tests as well as
the nature of biodiesel, current and future
laboratory engine test data will be presented.
biodiesel production techniques, and some
Higher and Narrower boiling range of biodiesel makes it
more persistent once it enters the crankcase
400
Narrow Boiling Range of
350
Biodiesel
Temperature, °C
300
250
R M E B io d ie s e l
200
M in e r a l
150
100
50
0
10% 50% 90%
Percent of Fuel Evaporated
Crankcase Fuel Dilution with Biodiesel-Higher and Narrower Biodiesel Boiling Range Makes it More Persistent Once
Inside the Crankcase
16