Prog. Energy Combust. Sci. Vol. 24, pp.

125-164, 1998
Pergamon © 1998 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0360-1285/98 $19.00
PI!:S0360-1285(97)00034-8

COMBUSTION OF FAT A N D VEGETABLE OIL DERIVED FUELS IN

DIESEL ENGINES

Michael S. Graboski* and Robert L. McCormick

Colorado Institute for Fuels and High Altitude Engine Research and Department of Chemical Engineering and
Petroleum Refining, Colorado School of Mines, Golden, CO 80401-1887, U.S.A.

Abstract--In this article, the status of fat and oil derived diesel fuels with respect to fuel properties, engine
performance, and emissions is reviewed. The fuels considered are primarily the methyl esters of fatty acids
derived from a variety of vegetable oils and animal fats, and referred to as biodiesel. The major obstacle to
widespread use of biodiesel is the high cost relative to petroleum. Economics of biodiesel production are
discussed, and it is concluded that the price of the feedstock fat or oil is the major factor determining biodiesel
price. Biodiesel is completely miscible with petroleum diesel fuel, and is generally tested as a blend. The use of
biodiesel in neat or blended form has no effect on the energy based engine fuel economy. The iubricity of these
fuels is superior to conventional diesel, and this property is imparted to blends at levels above 20 vol%. Emissions
of PM can be reduced dramatically through use of biodiesel in engines that are not high lube oil emitters.
Emissions of NOx increase significantly for both neat and blended fuels in both two- and four-stroke engines. The
increase may be lower in newer, lower NOx emitting four-strokes, but additional data are needed to confirm this
conclusion. A discussion of available data on unregulated air toxins is presented, and it is concluded that
definitive studies have yet to be performed in this area. A detailed discussion of important biodiesel properties and
recommendations for future research is presented. Among the most important recommendations is the need for all
future studies to employ biodiesel of well-known composition and purity, and to report detailed analyses. The
purity levels necessary for achieving adequate engine endurance, compatibility with coatings and elastomers,
cold flow properties, stability, and emissions performance must be better defined. © 1998 Elsevier Science Ltd.
All rights reserved.
CONTENTS

1. Introduction 126
1.1. History of Vegetable Oil Based Fuels 126
1.2. The Transesterification Process 127
1.3. Economics of Biodiesel Manufacture 127
2. Properties of Fatty Acid Ester Fuels 129
2. I. Chemical Composition and Properties 129
2.2. Combustion Properties 13 I
2.2.1. Cetane number 131
2.2.2. Flash point 132
2.3. Distillation Temperatures 134
2.4. Specific Gravity 134
2.5. Heat of Combustion 134
2.6. Flow Properties 135
2.6.1. Low temperature flow properties 135
2.6.2. Viscosity and surface tension 137
2.7. Storage and Stability 137
2.7.1. Iodine number 138
2.7.2. Oxidative stability and gum number 138
2.7.3. Water absorption and microbial activity 139
2.8. Biodiesel Industry Fuel Standard 139
3. Engine Performance 140
3.1. Fuel Economy 140
3.2. Torque and Acceleration 141
3.3. Engine Endurance Issues 142
3.3.1. Durability studies 142
3.3.2. Elastomer compatibility 143
3.3.3. Biodiesel lubricity 143
3.3.4. Summary 146
4. Emissions 146
4.1. Regulatory Barriers 146
4.2. Regulated Emissions: Engine Stand and Chassis Studies 146
4.2.1. Engine dynamometer studies using two-stroke engines 147
4.2.2. Engine dynamometer studies using four-stroke engines 152
4.3. Discussion of Increased NO~ Emission for Biodiesel 156
4.4. Smoke Opacity 159
4.5. Unregulated Emission and Air Toxics 160

*Corresponding author.

125
126 M.S. Graboski and R. L. McCormick
4.5.1. Soluble organic fraction
4.5.2. Poly-aromatic hydrocarbons
4.5.3. Aldehydes
4.5.4. Summary
5. Conclusions and Summary of Research Needs
6. Acknowledgement
7. References
l. INTRODUCTION
Agricultural fats and oils, in raw or chemically
modified forms, have the potential to supplant a fraction
of petroleum distillates and petroleum based petro-
chemicals early in the next century. Diesel boiling range
material is of particular interest because it has been
shown to significantly reduce particulate emissions
relative to petroleum diesel. Biodiesel is a name applied
to fuels manufactured by the esterification of renewable
oils, fats, and fatty acids. By renewable it is meant that
supplies of these raw materials can be replenished by the
growth of plants or production of livestock. The ultimate
source of the energy content of these fuels is the sun. The
terms methylsoyate, soyate, soyester (for methylesters of
soybean oil), tallowate (for esters of tallow), and many
similar terms are used to describe these fuels. The
technology to produce methylesters from agricultural
fats and oils is well known. The fatty acids may be
derived from whole vegetable oils such as soybean or
rapeseed (also called canola), rendered tallows, or waste
materials such as cooking and trap greases.
The major obstacle to widespread use of fats and oils
as fuels and chemicals is the high cost of the finished
products relative to petroleum. The cost of biodiesel
produced from food-grade oils such as soybean oil is on
the order of $2-3 per gallon compared to $0.50-0.60
for petroleum diesel on a pretax basis. Soybean oil
carbon is worth approximately 30 cents per pound, while
petroleum based carbon is valued at about 7 cents per
pound. Tallow carbon is somewhat cheaper than that
from soybean oil but is still not competitive with petro-
diesel. Waste vegetable oil carbon may be competitive
with petroleum carbon but may also be limited in
volume.
Biodiesel is completely miscible with petroleum
diesel fuel (referred to as D-I for Number I and D-2
for Number 2 diesel oils) and is usually tested as a blend.
These blends are referred to by the volume percentage
biodiesel in the blend. For example, B-20 refers to a 20-
vol% biodiesel blend. B-20 is approximately 2 wt%
oxygen and the majority of studies have been conducted
at this blend level. Testing to date has revealed several
technical problems, although none seem insurmountable.
For example, biodiesel tends to increase nitrogen oxide
emissions compared to Number 2 diesel in heavy duty
engines. This represents a serious problem for biodiesel
use in ozone or PM-10 non-attainment areas. However,
biodiesel or biodiesel blends result in dramatically lower
emissions of particulate matter relative to petroleum
derived diesel fuel. This is because of the high oxygen
content of these fuels which increases the oxygen present
in fuel rich regions of the combusting fuel spray,
160
160
161
161
161
162
162
reducing the amount of soot formed. In some cases,
biodiesels do not meet wintertime cold flow property
requirements. Problems caused by incompatibility with
elastomers have also been identified for some specific
biodiesel formulations. Oxidative and biological stability
is also an issue for these biodegradable materials.
Finally, because of the greater degree of unsaturation
compared to petroleum diesels, some biodiesels can lead
to formation of engine deposits. In this article, the
current status of fat and oil derived diesel fuels with
respect to fuel properties, engine performance,
emissions, and the problem areas noted above is
reviewed.
1.1. History of Vegetable Oil Based Fuels
Early in this century, work directed at renewable
diesel fuels had been initiated. It was immediately
recognized that the use of whole vegetable oils was not
acceptable in diesel engines. Walton I in 1938 reported
on pioneering work with vegetable oils and suggested an
early concept for biodiesel. Three oils were examined in
a diesel engine which utilized 0.416 Ib/bhp-hr of fuel,
similar to a modern engine in efficiency. Steady-state
testing showed that soybean oil, palm oil, and cottonseed
oil all gave fuel economies of 90-91% compared to
petroleum diesel at wide open throttle and various
speeds. Whole oils were reported to form carbon
deposits and exhibit pour point problems; palm oil
corroded copper and brass significantly. Because of the
difficulties experienced, Walton suggested splitting of
the triglycerides and using the resulting fatty acids as
fuel.
The idea suggested by Walton evolved slowly and
considerable effort was devoted to investigating vege-
table oils. Martinez de Vedia 2 in 1944 reported on tests
with 20 and 40% linseed oil/diesel blends. With these
blends, lube oil properties including acidity, ash,
asphaltene precipitates, and Conradsen carbon increased
during use, and increased more rapidly than for diesel
alone. The author found that decanting the fuel off of the
precipitate before use could minimize fouling of
injectors and clogging of fuel filters. Carbon deposits
on engine combustion chamber parts were significantly
greater with the blends than with diesel alone. The author
stated that linseed oil blends would be troublesome if
used in commercial equipment for extended operating
periods. Huguenard 3 investigated fuel economy and
indicator card traces for cottonseed oil/diesel blends at
various injection timings in two laboratory scale IDI
diesel engines. Cottonseed oil and blends with diesel
could be run with greater timing advance than diesel
fuel. After a modest period of operation, the first engine
 Fat and vegetable oil derived fuels
failed to make rated load. The engine was dissembled
and found to be heavily carbonized and to have ring
damage. Bruwer and coworkers 4 in 1980 reported that
sunflower seed oil is inferior to diesel in terms of fuel
economy and power. Furthermore, as the injectors
coked, unburned fuel began to dilute the crankcase oil
causing ring sticking and general engine failure. The
investigations described here are supported by many
other studies that point to engine endurance issues
associated with the use of whole vegetable oils or
vegetable oils blended with diesel. 5-9
Bruwer and coworkers, 4 in one of the first reported
studies on fatty acid esters, found that using an ester of
sunflower oil seemed to resolve the problems associated
with the whole oil and in fact produced less carbon
deposits in a test engine than petroleum derived diesel.
Smoke opacity was also lower with the ester than with
diesel. Bacon and coworkers ~° report that coking and
polymerization of vegetable oils can be minimized by
transesterification. It was also noted that hydrogenation
to minimize storage stability and coking in whole oils
and esters can result in undesirable low temperature fluid
properties. Fort and Blumberg 7 performed engine testing
studies of cottonseed oil, methylester. They observed
performance comparable to diesel with no change in
power output over a 200-hr endurance test. Engler and
coworkers tt examined blends of sunflower oil and
sunflower oil ethylester prepared by converting 38, 68
and 98% of the initial oil. Unacceptable combustion
chamber deposits were observed for the 38 and 68%
conversion fuels. For the nearly pure ethylester these
deposits were not significant. These positive initial
findings with regard to engine performance, engine
deposits, and emissions have prompted considerable
recent research into fat and vegetable oil ester based
diesel fuels.
1.2. The Transesterification Process
Biodiesel may be manufactured in batch or continuous
systems by transesterification. ~2 In transesterification,
one ester is converted to another. The reaction is
catalyzed by reaction with either acid or base and
involves reaction with an alcohol, typically methanol if a
biodiesel fuel is the desired product. A simple molecular
representation of the reaction is shown in Fig. I. As
typically practiced, a basic catalyst such as sodium
hydroxide is used to convert the glycerol based triesters
(or triacyl glycerides) which make up fats and oils to
methanol based monoesters (or methylesters) yielding
free glycerol as a byproduct. A stoichiometric material
balance yields the following simplified equation:
Fat or Oil + 3 Methanol ~ 3 Methylester + Glycerol
1000 kg 107.5 kg 1004.5 kg 103 kg.
The mass flows shown are for the case of complete con-
version of stearic acid triglyceride. The process is very
simple. At slightly above room temperature this reaction
127
O H
II I
+ 3 H3C-OH
R3~C'o'~'H
H
Fat or Oil
Methanol
NaOH
or
Acid
O
II
IC CH3 HO-~H 2
RI o ' O ~
II
R2.,.C.,o,CH3 + HO-~H
R3/C'o'CH3 HO-CH2
Methyl Esters Glycerol
Fig. 1. Simple representation of the transesterification reaction.
proceeds to a conversion of 90-97%, in an excess of
methanol, within approximately 1 hr. The remaining
3-10% is glycerol, mono/di/triglycerides, and free
fatty acids. Much of the free fatty acid is converted to
soap (sodium salt of the fatty acid) and water.
Up to 0.5 wt% catalyst is required to promote the
transesterification. In most processing flow sheets the
caustic catalyst is not recovered and recycled. Thus,
fresh caustic must be continuously added. Washing to
remove the spent caustic is often accomplished with
water yielding a significant amount of wastewater from
the process. Development of a heterogeneous catalyst for
this process would significantly reduce processing and
environmental costs. The byproduct glycerol is nearly
insoluble in biodiesel and in the feed stock oil and thus
forms a separate liquid phase. The biodiesel may require
distillation to remove traces of glycerides. The glycerol
may be purified by vacuum distillation.
Ethanol or other alcohols may be used in the
transesterification process. These are generally less cost
effective to use, and are not as easily reacted with the fat
or oil as is methanol. Biodiesel can be made from waste
oils as well. Reed et al. 13 describe one method for
producing esters from waste cooking oils containing
significant quantities of free fatty acids liberated during
the cooking process. The significant difference com-
pared to conventional transesterification is that addi-
tional caustic must be added to neutralize the free fatty
acids by converting them to soap prior to transesterifica-
tion. These soaps separate from the biodiesel in final
washing.
1.3. Economics of Biodiesel Manufacture
For a typical biodiesel plant, the capital cost of the
installed facility including the cost of project develop-
ment, contingency, and other items may be on the order
128 M. S. Graboski and R. L. McCormick

Table I. Economics of biodiesel manufacture. Basis: 10 MM gal/year plant

Cost item Annual amount Unit price Annual total
Capital cost 10 years $2 per annual gallon $20 000 000
Labor and burden $20/hr 12 total $499 200
Overhead 50% $249 600
Methanol 1.167 MM gal $0.75/gal $875 250
Caustic 35.8 tons $400/ton $14 320
Power 100 kW $0.07/KWh $56 000
Steam 0.25 MM Btu/hr 5$/MM $10000
Water 1 gal/gal 5$/Mgal $50 000
Local taxes and insurance 2% Capital $400 000
Maintanence 3.5% Capital $700 000
Operating expense ($2 854 370)
Gross income needed $6 262 239
Income tax 35% ($1 491 784)
Depreciation 10 years $2 000 000
Required cash flow 20% DCF $4 770455
Glycerine revenue 738 278 gal $7.50 $5 537 084
Feedstock oil cost 71700 000 Ib $0.25 ($17 925 500)
Biodiesel 10 MM gal $2.15

3.0
Clpital Colr,t Glycerine Price Soybean
S/Annual Gallon Oil
2.5 2.00 5.00
...... 2.00 7.50 Tallow and
-- 1.50 7.50 White I
~-. 1.50 10.00
2.0

,.-°°

1.5 Wwl~eYellow
| Grease / .....'" 1 . / - . . I

.~ 1.0

• • ,-I//"'/
..
0.5

0.0 = . . . . I = . . . .

0.05 0.10 0.15 0.20 0.25 0.30

Feedstock Oil Cost, $/Ib

Fig. 2. Sensitivity of biodiesel cost per gallon to feed stock cost.

of $1.00-2.00 per annual gallon. The manufacturing
costs of biodiesel are dominated by the cost of the oil
feed stock. This is readily shown by the following
engineering economic estimate.
In this calculation, the 10 million gallon per year plant
is assumed to cost $2 per annual gallon, a 20% DCF
(discounted cash flow) return on investment is required,
and 100% equity financing is assumed. The capital
includes the basic installed plant, interest during
construction, soft development costs such as permitting,
feed stock and product sales and purchase contracts,
working capital, and project contingency. A 10-year
project and depreciation life is assumed. With a 35%
combined Federal and State income tax rate, the plant
annual gross income must be $6.26 million to satisfy the
return requirement. Operating costs are based upon
chemical industry experience (see for example, Ref. 14).
Total operating costs are on the order of $2.8 million.
Withers and Noordam 15 report a cost of $0.9 million for
a canola to biodiesel conversion facility with a capacity
of 2.7 million gallons per year, in line with the operating
costs estimated here. Table 1 shows that the largest line
item expense is the cost of feed stock oil at $17.9 million
when priced at a market level of $0.25 per pound for
soybean oil.
The plant design is assumed to produce a high quality
glycerol. The glycerol byproduct, valued at $7.50 per
gallon ($0.75 per pound), produces revenue which is
approximately equal to the sum of the required return
and operating costs. Thus, the cost of the feed stock oil
must be recovered completely from biodiesel sales. The
selling price of biodiesel is thus near the purchase price
of the feed stock oil.
Different capital costs, financing assumptions and
 Fat and vegetable oil derived fuels 129

operating scenarios will lead to somewhat different
results but will not alter the general conclusion. For
example, it might be argued that burdened and over-
headed labor costs are too high. Since the labor cost is a
small part of the overall production cost, assuming no
increase in labor needs for considerably larger scale
plants has an inconsequential effect on biodiesel selling
price.
Figure 2 shows a sensitivity plot with cases for lower
capital and varying glycerol values as a function of feed
stock oil price. Three separate feed stock cases are shown
on the sensitivity plot. These are use of soybean oil or
other vegetable oil, use of tallow and commodity white
grease (CWG), and the use of waste yellow grease.
Choice white grease is a commodity traded with a
standard specification developed by the soap industry.
Yellow grease is primarily restaurant grease and off-
specification white grease. The prices for soybean oil,
tallow and C W G are typical late 1995 cash prices
reported in the Wall Street Journal. The yellow grease
price is based upon conversations with collectors work-
ing for rendering operations producing animal feed.
Figure 2 suggests that waste yellow grease is the feed
stock of choice. It is the only feed stock capable of
producing biodiesel that can compete with Number 2
diesel. The spot price of Number 2 oil has averaged
about 5 0 c e n t s per gallon during 1995. Since the
rendering industry consumes the lions' share of the
waste yellow grease today, its use for biodiesel
manufacture could drive up the yellow grease price.
Table 2. Typical elemental composition of soybean oil methyl
esters and conventional Number 2 diesel fuel
Number 2 diesel Methyl soyester ~
wt% C 87 77.2
wt% H 13 11.9
wt% O 0 10.8
wt% S < 0.05 --
~'Average of data from Refs 19-23.
Very little information on the properties and use of waste
yellow grease derived biodiesel is available.
The predominant ester studied is the methylester of
soybean oil, or methylsoyate. Soybean oil is the major
vegetable oil produced in the United States. European
biodiesel is based upon rapeseed oil methylester and this
is the second most widely tested form of biodiesel.
Significant studies have also been conducted on tallow
esters and limited data is available on a wide range of
other materials. This predominance of soy and rape
esters is reflected in this review.
2. PROPERTIES OF FATTY ACID ESTER FUELS
Engine and vehicle studies of fat and oil derived
diesels have produced highly variable results. In most
cases this can be traced to the quality and purity of the
fuel. However, in many cases experimental error or
variability is large (or not reported at all) and the results
are meaningful only in a very qualitative sense. This
section reviews fuel properties relevant to engine
performance and to understanding the technology of
production and use of these fuels.
2.1. Chemical Composition and Properties
The chemical composition of fat and oil esters is
dependent upon the length and degree of unsaturation of
the fatty acid alkyl chains. Table 2 presents elemental
analysis data for methylesters of soybean oil and
conventional diesel fuel. The carbon/hydrogen ratio of
biodiesels from other sources will be slightly different,
depending upon the degree of unsaturation. The most
important compositional difference between D-2 and
biodiesels is oxygen content. Biodiesel contains 10-
12 wt% oxygen, which lowers energy density and, and as
will be shown, lowers the particulate emission. In the
United States, on road commercial Number 2 diesel can
contain up to 5 0 0 p p m sulfur by ASTM D-2622.
Biodiesel is essentially sulfur free. Sulfur is converted

Table 3. Structural formula, melting, and boiling points for fatty acids and methyl esters in the diesel boiling range
Fatty acids Methyl esters
Acid No. of Structure Melting Boiling Melting Boiling
chain carbons point point point point
(°C) (°C) (°C) (°C)
Caprylic 8 CH3(CH2)rCOOH 16.5 239 -40 193
Capric 10 CH3(CH2)aCOOH 31.3 269 -18 224
Lauric 12 CH 3(CH2) 10COOH 43.6 304 5.2 262
Myristic 14 CH ffCH2) 12COOH 58.0 332 19 295
Palmitic 16 CH3(CH2) ~4COOH 62.9 349 30 338
Palmitoleic 16 CH 3(CH2)5CH=CH(CH 2)7COOH 33 -- 0 --
Stearic 18 CH3(CH2) ~rCOOH 69.9 371 39.1 352
Oleic 18 CH 3(CH2)7CH=CH(CH 2)7COOH 16.3 -- -19.9 349
Linoleic 18 CH 3(CH 2)4CH=CHCH2CH=CH(CH 2)7COOH -5 -- -35 366
Linolenic 18 CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)TCOOH -I I -- -- --
Arachidic 20 CH3(CH2) laCOOH 75.2 -- 50 --
Eicosenoic 20 CH 3(CH2)7CH=CH(CH 2)9COOH 23 -- -15 --
Behenic 22 CH 3(CH2)20COOH 80 -- 54 --
Erucic 22 CH3(CH 2)7CIq=CH(CH2) IICOOH 34 -- -- --
130 M. S. Graboski and R. L. McCormick

Table 4. Weight percent of fatty acids in various fat and oils feedstocks
Carbon Saturated acids Mono unsaturated acids Di Tri
number
8 10 12 14 16 18 > 18 < 16 16 18 > 18
Beef tallow -- -- 0.2 2-3 25-30 21-26 0.4-1 0.5 2-3 39-42 0.3 2
Butter I-2 2-3 1-4 8-13 25-32 8-13 0.4-2 1-2 2-5 22-29 0.2-1.5 3
Coconut 5-9 4-10 44-51 13-18 7-10 1-4 -- -- -- 5-8 I-3
Cod liver -- -- -- 2-6 7-14 0-1 0-2 10-20 25-31 35-52
Corn -- -- -- 0-2 8-10 1-4 1-2 30-50 0-2 34-56
Cottonseed -- -- -- 0-3 17-23 1-3 23-41 2-3 34-55
Lard -- -- -- I 25-30 12-16 0.2 2-5 41-51 2-3 4-22
Linseed -- -- -- 0.2 5-9 0-1 -- -- -- 9-29 8-29 45-67
Palm -- -- -- 1-6 32-47 1-6 -- -- -- 40-52 2- I 1
Palm kernal 2-4 3-7 45-52 14-19 6-9 1-3 1-2 0-1 10-18 1-2
Peanut -- -- -- 0.5 6-11 3-6 5-10 I-2 39-66 17-38
Rapeseed . . . . 2-5 1-2 0.9 0.2 I 0-15 50-60 i 0-20 5-10
Safflower . . . . 5.2 2.2 76.3 16.2
Soybean -- -- -- 0.3 7-11 3-6 5- I 0 0-1 22-34 50-60 2-10
Sunflower 6.0 4.2 1.4 18.7 69.3 0.3
Tung . . . . . . . . . 4-13 8-15 bulk

to sulfur oxide in the tailpipe and a fraction of the sulfur Table 4 summarizes typical fatty acid composition
oxide is converted to sulfuric acid, which is counted as data for various triglycerides. For most fats and oils of
particulate, a regulated pollutant. Sulfur oxides are also interest the majority of the fatty acids have 16 and 18
regarded as air pollutants although they are not regulated carbon length chains. Animal tallow is composed of
as such from diesel engines. Petroleum derived diesel about 60% saturated, paimitic and stearic acids. The
also contains from 20 to 40 vol% aromatic compounds. remainder is singly unsaturated oleic acid. Soybean
Aromatics are known to increase emissions of particulate oil, corn oil, peanut oil etc. contain predominantly
and NOx. Biodiesel is essentially non-aromatic. unsaturated acids, the majority containing oleic and
Petroleum diesel contains essentially no olefinic bonds. linoleic acids (doubly unsaturated). Rapeseed oil from
Biodiesels can contain a significant number ~f these
reactive, unsaturated sites.
Table 5. Cetane number of various biodiesels
All naturally occurring fats and oils are esters of the
tri-alcohol, glycerol. These are known as glycerides, Reference Fuel Cetane
number
triglycerides, or triacylglycerides. With few exceptions,
the carboxylic acids (fatty acids) from which the fats and Number 2 diesel 40 (min)-52
oils are derived are all straight-chain compounds ranging 16 Soybean oil methylester 51.4
in size from three to 18 carbons. Table 3 shows the 17 Soybean oil methylester 45.8
18 Soybean oil methylester 48.0
chemical structure of the fatty acid chains found in the 19 Soybean oil methylester 56.4
most common biodiesel source materials. Except for C3 20 Soybean oil methylester 53.1
and C5 compounds, only acids with an even number of 21 Soybean oil methylester 54.7
carbons occur naturally. Acids may be saturated (contain 23 Soybean oil methylester 46.2
24 Soybean oil methylester 56.9
only single bonds) or unsaturated (contain one or more 25 Soybean oil methylester 50.3
double bonds). A saturated fat is one that cannot 31 Soybean oil methylester 5 I. I
chemically add hydrogen. An unsaturated fat can be 31 Soybean oil methylester 45.7
hydrogenated; for each degree of unsaturation, that is Average Soybean oil methylester 50.9
each double bond, one hydrogen molecule can be added
26 Rapeseed oil methylester 54.4
per fatty acid. Table 3 also shows the melting and boiling 27 Rapeseed oil methylester 48.0
points of the various fatty acids. The saturated acids 28 Rapeseed oil methylester 51.6
exhibit higher freezing points than the unsaturated acids. 29 Rapeseed oil methylester 51.5
Stearic acid, for example, is solid to 70°C, while oleic 30 Rapeseed oil methylester 50.0
32 Rapeseed oil methylester 61.8
acid melts at ! 6°C. The only difference is the presence of Average Rapeseed oil methylester 52.9
a single double bond in the structure of oleic acid. For
freezing point, chemical structure is very important. The 23 Soybean oil ethylester 48.2
boiling points of the acids, on the other hand, are 23 Soybean oil butylester 51.7
dependent on the length of the carbon chain but nearly 25 Tallow methylester 58.8
32 Rapeseed oil ethylester 64.9
independent of the degree of unsaturation of the fatty 33 Sunflower oil methylester 49.0
acid. These observations regarding the effect of chemical 33 Cottonseed oil methylester 51.2
structure on melting and boiling points also apply to 34 Palm oil methylester 50.0
esters of the fatty acids, although the boiling and melting 34 Palm stearin methylester 52.0
35 Frying oil ethylester 61.0
points are significantly lower, as noted in Table 3.
 Fat and vegetable oil derived fuels 131

64

62 ~ Soy/No. 2 Ref. 24 rZ=0.89

--O-- Tallow/No. 2 Ref. 24 r==0.98 .~
60 ~ Soy/No. 2 Ref. 18 ?=0.92
SoylNo.2 Ref. 19 rZ=0.90
58
56 vv~

i
• v
54 0

52 • •
50
48

4446 ~~_~.~4~ ~e •

42 . . . . , • . • . , ....
i , .... , .....
. . . . i . . . . ,
. . . . i . . . .

0 20 40 60 80 100 120
Weight Percent Biodiesel
Fig. 3. Cetane number for blends of soy and tallow methylesters with Number 2 diesel.

some sources contains a high percentage of the relevant to biodiesel, which contains no aromatic
monounsaturated, C22 erucic acid. compounds.
The cetane number of biodiesels depends on the parent
2.2. Combustion Properties oil source but in general is at the high end of the range
typical of Number 2 diesel, as noted in Table 5. Reported
2.2.1. Cetane number cetane numbers range from 45.8 to 56.9 for soy and from
48 to 61.8 for rapeseed methylesters. This broad range of
The cetane number of the fuel, specified by ASTM values is probably caused by differences in the fractional
D-613, is a measure of its ignition delay with higher conversion of triglycerides to esters and by the presence
cetane numbers indicating shorter time between the of residual methanol and glycerol in the fuel. Exami-
initiation of fuel injection and ignition, a desirable nation of flash point and distillation data presented below
property in diesel engine fuel. The cetane index is confirms this conclusion for the references giving cetane
defined by ASTM D-976. The cetane index is a numbers below about 50. The average of the available
calculated property that correlates well with cetane data presented in Table 5 is 50.9 for soy and 52.9 for
number for natural petroleum stocks. Cetane index is rapeseed esters. For the other esters listed, only one data
also a measure of fuel aromaticity and is therefore not point is available but they have cetane numbers in the
4 8 - 6 0 range. Highly saturated esters such as those
Table 6. Cetane number for pure fatty acid esters
prepared from tallow and used frying oil have the highest
Reference Fuel Cetane cetane numbers. The effect of blending biodiesel on
number cetane number is near linear for mixtures of esters with
36 Caprylic acid methylester 18.0 either Number 1 or Number 2 fuels, t9'25 This is shown in
37 Caprylic acid methylester 33.6 Fig. 3 where the high correlation coefficients support a
36 Capric acid methylester 47.9 linear relationship between cetane numbers of the neat
37 Capric acid methylester 47.2 fuels and blends, in spite of the apparent curvature of the
37 Capric acid ethylester 51.2
36 Lauric acid metbylester 60.8 trend for soybean oil methylesters. The data in Fig. 3, as
37 Lauric acid metbylester 61.4 well as a great deal of additional published data (see
36 Myristic acid methylester 73.5 Ref. 20, for example), implies that the neat cetane
37 Myristic acid methylester 66.2 number of ester fuels can be used as the blending cetane
37 Myristic acid ethylester 66.9
36 Palmitic acid methylester 74.3 number. Furthermore, this statement is true over the
37 Palmitic acid methylester 74.5 entire composition range of mixtures of esters and diesel.
36 Stearic acid methylester 75.6 Cetane number data for pure esters are compiled in
37 Stearic acid methylester 86.9 Table 6. Cetane number increases with chain length,
38 Stearic acid etbylester 76.8
decreases with number of double bonds, and decreases as
38 Oleic acid methylester 55.0
38 Oleic acid ethylester 53.9 double bonds and carbonyl groups move toward the
38 Linoleic acid methylester 42.2 center of the chain. For pure esters of stearic acid, cetane
38 Linoleic acid ethylester 37.1 number was approximately 75, but for esters of linolenic
38 Linolenic acid methylester 22.7 acid with three double bonds, cetane number had dropped
38 Linolenic acid ethylester 26.7
to the mid-twenties. Cetane number increased from 47.9
132 M.S. Graboski and R. L. McCormick

Table 7. Flash points for various biodiesels to 75.6 for saturated C l0 through C ~sesters. At and above
C t2, the cetane numbers were above 60. Preparation of
Reference Fuel Flash point
(°C) esters with longer chain alcohols, such as ethanol or
butanol, had little effect on octane number. Emission
Number 2 diesel 60-72 testing has shown that above 55-60, increased cetane
16 Soybean oil methylester > 110
has little or no impact on further emissions reductions.39
17 Soybean oil methylester 179
20 Soybean oil methylester 143 Increasing cetane number has been shown to reduce
21 Soybean oil methylester 174 nitrogen oxide (NO~) emissions.4° Cetane number can be
23 Soybean oil methylester 141 enhanced using ignition improvers which suggests a
24 Soybean oil methylester > 66
strategy for eliminating the increased NO, emission
25 Soybean oil methylester 117
31 Soybean oil methylester > 110 usually observed with biodiesels and blends. Clark et
43 Soybean oil methylester 127 al. 23 showed that neat biodiesel does not respond to
Average Soybean oil methylester ! 31 treatment with ethylhexylnitrate which is widely used as
a cetane improver for low quality diesel fuels. Sharp 41'42
26 Rapeseed oil methylester 84
28 Rapeseed oil methylester 152 showed the same for a 20% blend of biodiesel in diesel
30 Rapeseed oil methylester 188 fuel (B-20). However, Sharp found that B-20 did respond
31 Rapeseed oil methylester 250 to a different cetane improver, di-t-butyi peroxide, and
32 Rapeseed oil methylester 175 NOx was decreased.
Average Rapeseed oil methylester 170

25 Tallow methylester 138 2.2.2. Flash point

43 Tallow methylester 96
44 Tallow methylester 23 a Flash point (ASTM D-93) is a measure of the
Average Tallow methylester I 17 temperature to which a fuel must be heated such that
the mixture of vapor and air above the fuel can be
23 Soybean oil ethylester i 60
23 Soybean oil butylester 158 ignited. All Number 2 diesel fuels have relatively high
32 Rapeseed oil ethylester 185 flash points (54°(2 minimum, 71°(2 typical). The flash
33 Sunflower oil methylester 183 point of neat biodieseis is even higher, typically greater
33 Cottonseed oil methylester 110 than 90°C, as noted in Table 7. Low flash points
34 Palm oil methylester 174
34 Palm stearin methylester 165 measured in some studies (i.e., Ref. 44) may be caused
35 Frying oil ethyl ester 124 by residual methanol in the ester. This may also be the
cause of the large range of flash points reported for a
aNot included in average.
given ester in Table 7. Because purity is uncertain, it is

Table 8. Distillation data for various biodiesels

Reference Fuel IBP (°C) T10 (°C) T50 (°C) T90 (°C) EP (°C)
Number 2 diesel 185 210 260 315 345
17 Soybean oil methylester 320 331 337 343 351
20 Soybean oil methylester 302 328 334 351 356
23 Soybean oil methylester -- -- 336 342 --
24 Soybean oil methylester -- 321 (7%) -- -- --
25 Soybean oil methylester 310 330 336 324 338
43 Soybean oil methylester 265 329 335 337
Average Soybean oil methylester 299 328 336 340 346

27 Rapeseed oil methylester 332 352 351 355 409

28 Rapeseed oil methylester 316 333 336 346 350
29 Rapeseed oil methylester 330 -- -- -- 340
30 Rapeseed oil methylester -- 335 -- 342 --
Average Rapeseed oil methylester 326 340 344 348 366

25 Tallow methylester 304 326 331 337 337

43 Tallow methylester 21 g 323 332 353 354
44 Tallow methylester 104 (?) -- 327 338 --
47 Tallow methylester 211 -- 323 -- 327
Average Tallow methylester 209 324 328 342 339

23 Soybean oil ethylester -- -- 336 344 --

23 Soybean oil butylester -- -- 352 364 --
34 Palm oil methylester 324 330 334 343 363
34 Palm stearin methylester 320 331 335 343 349
44 Tallow ethylester 99 -- 335 349 --
44 Tallow butylester I 13 -- 346 353 --
 Fat and vegetable oil derived fuels 133

38o

36O

340

320

300

280

260
E
240

220

200
seed Ester
180 Methyl Tallow Ester

160
IBP TIO TSO TgO EP
Fig. 4. Distillation curves for Number 2 diesel and various esters; data are averages from Table 8.

Table 9. Specific gravity of various biodiesels Table 10. Heat of combustion data for various biodiesel samples

Reference Fuel Specific Reference Fuel HHV LHV

gravity (Btu/Ib) (Btu/lb)

Number 2 diesel 0.85 Number 2 diesel 19300 18640

16 Soybean oil methylester 0.8855 16 Soybean oil methylester 17176 16000
18 Soybean oil methylester 0.8831 17 Soybean oil methylester 17650 --
19 Soybean oil methylester 0.8844 18 Soybean oil methylester 17996 --
20 Soybean oil methylester 0.8855 20 Soybean oil methylester 17156 --
22 Soybean oil methylester 0.8810 21 Soybean oil methylester -- 15965
23 Soybean oil methylester 0.8840 22 Soybean oil methylester -- 15700
24 Soybean oil methylester 0.8880 23 Soybean oil methylester 17127 --
43 Soybean oil methylester 0.8870 24 Soybean oil methylester 17087 --
48 Soybean oil methylester 0.889 25 Soybean oil methylester 17650 --
Average Soybean oil methylester 0.8853 43 Soybean oil methylester 17248 --
47 Soybean oil methylester 17106 16034
26 Rapeseed oil methylester 0.8738 Average Soybean oil methylester 17355 15925
27 Rapeseed oil methylester 0.885
28 Rapeseed oil methylester 0.882 26 Rapeseed oil methylester 17506 --
29 Rapeseed oil methylester 0.883 28 Rapeseed oil methylester -- 16224
30 Rapeseed oil metbylester 0.8825 29 Rapeseed oil methylester -- 15985
31 Rapeseed oil methylester 0.8855 30 Rapeseed oil methylester -- 15940
32 Rapeseed oil methylester 0.8802 31 Rapeseed oil methylester 17136 --
Average Rapeseed oil methylester 0.8820 32 Rapeseed oil methylester 17446 --
Average Rapeseed oil methylester 17363 16050
25 Tallow methylester 0.8755
43 Tallow methylester 0.8772 25 Tallow methylester 17382 --
44 Tallow methylester 0.8750 43 Tallow methylester 17186 --
47 Tallow methylester 0.8745 44 Tallow methylester 17380 --
Average Tallow methylester 0.8756 Average Tallow methylester 17283 --

23 Soybean oil ethylester 0.8810 23 Soybean oil ethylester 17208 --

32 Rapeseed oil ethylester 0.876 32 Rapeseed oil ethylester 17433 --
34 Sunflower oil methylester 0.8800 33 Sunflower oil methylester -- 16580
33 Cottonseed oil methylester 0.8800 33 Cottonseed oil methylester -- 16735
34 Palm oil methylester 0.8700 34 Palm oil methylester 17271 --
34 Palm stearin methylester 0.8713 34 Palm stearin methylester 17138 --
35 Frying oil ethylester 0.8716 35 Frying oil ethylester 17428 16004
44 Tallow ethylester 0.8710 44 Tallow ethylester 17940 --
44 Tallow butylester 0.8680 44 Tallow butylester 17733 --
134 M.S. Graboski and R. L. McCormick

difficult to compare flash points of esters from various
sources. A material with about 90°(2 or greater flash point
is considered as non-hazardous from a storage and
fire-hazard point of view under U.S. Department of
Transportation regulations. Neat biodiesel is thus much
safer than diesel in this regard. In blends, the diesel flash
point will prevail up to the 50% blend level and then the
flash point will begin to rise. 2° The Engine Manufacturers
Association (EMA) 45 has expressed concem that because
of the oxidative instability of soy and tallow ester, flash
point (as well as other properties discussed below) may
change during storage. This possibility does not appear to
have been investigated in quantitative studies.
2.3. Distillation Temperatures
As mixtures of a few relatively similar compounds, fat
and oil ester fuels have a narrow boiling range relative to
Number 2 diesel and exhibit average boiling points
ranging between ~- 325 and 350°C. As noted in Table 8
and Fig. 4, this temperature range is near the high end of
the range reported for diesel. In B-20 blends, fuels
meeting the ASTM T-90 distillation specification (as
measured by ASTM D-86) can be produced. However,
EMA 4~ and others have reported that intake valve
deposit formation is a problem with soy based B-20 at
light load and this may be related to the large percentage
of olefinic, high boiling molecules in soyesters. Note that
several of the fuel samples reported in Table 8 have
suspiciously low initial boiling points, suggesting the
presence of methanol or glycerol which was not removed
after ester synthesis. These fuels might also be expected
to have low octane numbers and flash points, as was
noted by Sims 44 in his study of tallow methylesters.
2.4. Specific Gravity
Number 2 diesel exhibits a specific gravity of 0.85
(ASTM D-287). Biodiesel specific gravity is reported to
vary between 0.86 and 0.90 (see Table 9) and is typically
0.88. Therefore volumetric metering of biodiesel (as in
the unit injectors used in modern diesel engines) results
in the delivery of a slightly greater mass of fuel. As
discussed in the following section, biodieseis have a
lower energy content on both a volumetric and a mass
basis. Therefore, although a unit injector might deliver a
larger mass of fuel, the actual energy delivered is less
than for Number 2 diesel.
2.5. Heat ofCombusfion
It is generally accepted that fuel consumption is
proportional to the volumetric energy density of the fuel

Table 11. Low temperature flow properties of biodiesels

Reference Fuel Cloud point (°C) Pour point (°C) CFPP (°C)
50 Number 2 diesel - 15 to 5 - 3 5 to - 15 - 10 to - 2 0
16 Soybean oil methylester -2 -- --
17 Soybean oil methylester - 1 -7 -4
20 Soybean oil methylester -3 -7 -4
21 Soybean oil methylester 0 -- --
22 Soybean oil methylester -2 -4 --
23 Soybean oil methylester 2 -1 --
24 Soybean oil methylester -I -- --
25 Soybean oil methylester -- -1 --
43 Soybean oil methylester 3 19 --
50 Soybean oil methylester 3 -4 1
Average Soybean oil methylester -0.5 -3.8 -4.4

26 Rapeseed oil methylester -1 -9 --

27 Rapeseed oil methylester -4 -- --
29 Rapeseed oil methylester -4 - 12 - 13
30 Rapeseed oil methylester -11 -- 20
31 Rapeseed oil methylester -- -7 --
32 Rapeseed oil methylester 0 - 15 --
Average Rapeseed oil methylester -4.0 - 10.8 3.6

25 Tallow methylester -- 13 --
43 Tallow methylester 12 9
44 Tallow methylester -- 6 --
50 Tallow methylester 16 I0 I1
Average Tallow methylester 13.9 9 II

23 Soybean oil ethylester - I -4 --

32 Rapeseed oil ethylester -2 - 15 --
34 Sunflower oil methylester -- -7 --
33 Cottonseed oil methylester -- 3 --
34 Palm oil methylester -- 16
34 Palm stearin methylester -- 17
35 Frying oil ethylester 9 8
44 Tallow ethylester -- 6
44 Tallow butylester -- 6 --
 Fat and vegetable oil derived fuels 135

based upon the lower or net heating value (LHV).
Table 10 reports heating values for diesel and various
esters. Number 2 diesel contains typically 131 295 Btu/
gal (18 642 Btu/Ib) while biodiesels contain approxi-
mately 10% less (1 Btu/Ib = 2.236 MJ/kg). The ratio is
0.892 for soy diesel. Thus volumetric fuel economy will
be lower on biodiesel and biodiesel blends. As will be
shown below, fuel energy content based fuel economy is
unaffected. Freedman and Bagby 36 and Klopfenstein and
Walker46 report heats of combustion for pure fatty acid
methylesters.
2.6. Flow Properties
2.6.1. Low temperature flow properties
The key flow properties for winter fuel specification
are cloud and pour point. Cloud point, ASTM D-2500, is
the temperature at which wax formation might begin to
plug the fuel filter. It is measured as the temperature of
first formation of wax as the fuel is cooled. Pour point
(ASTM D-97) is a measure of the fuel gelling point. This
temperature is a measure of the temperature at which the
fuel is no longer pumpable. The pour point is always
lower than the cloud point. The cloud point is not
generally affected by additives called flow improvers.
However, flow improver additives can decrease the size,
or inhibit the formation, of the wax crystallites formed
upon cooling the fuel and thus lower the temperature at
which wax plugging becomes a problem. Pour point
additives can lower the temperature of fuel gelling
significantly. The cold filter plugging point, CFPP
(International Petroleum Standard IP 309 or ASTM D
4539) temperature is determined by dynamic testing and

20
•--e-- Soy/No. 1 Diesel
--O-- Soy/No. 2 Diesel
10 Tallow/No. 1 Diesel
--V-- Tallow/No. 2 Diesel

"6 -10
I1.
"0

o -20

-30

-40

i i l l !

0 I0 20 30 40 50

Volume Percent Biodiesel

10
Soy/No. 1 Diesel
--O-- Soy/No. 2 Diesel
Tallow/No. I Diesel
Tallow/No. 2 Diesel

oO -10

O
n
,.. -20
0
o.

-30

-40

! ~ i i i

0 10 20 30 40 50

Volume Percent Biodiesel

Fig. 5. Effect of blending soy and tallow methylesters on fuel cold flow properties; data from Ref. 50.

J~EC$ 24:2 ~C
136 M.S. Graboski and R. L. McCormick

measures severity of wax precipitation. This test esters were inferior to the soy esters, consistent with their
measures the temperature at which fuel filters are chemical structure.
expected to plug due to waxy precipitates. IP 309 is Cold flow or flow improver additives can be used to
simpler to conduct than ASTM D 4539. However, improve the cold flow properties of diesel fuels. These
ASTM D 4539 has been found to correlate better with additives do not prevent wax formation (that is, do not
North American vehicle performance 49 because of minor change the cloud point) but keep the small wax crystals
differences in fuel system design. from growing and combining. They thus affect pour
In winter time, Number 2 diesel fuels are often diluted point and cold filter plugging point. Flow improver
with Number 1 or kerosene to meet wintertime flow additives will be required for commercial biodiesel fuels
specifications throughout North America and fuel cloud and blends, especially for winter use. The Midwest
and pour points are varied by refiners to meet local Biofuels 5° study of the effect of pour point depressants
climatic conditions. Increasingly, D-2 fuels are being showed that gelling could be eliminated with appropriate
treated with additives to minimize the problem. Midwest commercial additives. The pour point of neat soy
Biofuels5j report data for diesel fuels without flow diesel was reduced to - 4 0 ° C with a commercial
improver additives. The D-I fuel studied exhibited cloud additive although 1000 ppm of additive was required.
and pour points of below - 40°C. The D-2 fuel exhibited However, the results of this study did not clearly show a
cloud and pour points of - 14 and - 21°C. Wintertime reduction in CFPP even with high additive concen-
cold flow properties of fuels are highly variable between trations. Development of new flow improver additives
suppliers and there is a wide difference reported for fuels specifically for fatty acid esters may be a fruitful area.
in round robin testing studies. Harrington 52 showed that the small palmitic and
A compilation of biodiesel cloud, pour, and cold filter stearic acid contents of sunflower and linseed oils greatly
plugging points is reported in Table 11. All biodiesel increase the cloud point compared to oleic acid esters
fuels exhibit poor cold flow properties with cloud and alone. Modification or purification of these materials
pour points 20-25°C higher than those of Number 2 might therefore have a disproportional effect on cold
diesel. These values are relatively high when compared flow properties. A more recent study 53 examined
to winter ambient temperatures. Freezing points of so-called winterization where the oil for ester is
organic molecules are very sensitive to chemical refrigerated to induce crystallization of the high freezing
structure. The structural properties of biodiesel that
affect freezing point are degree of unsaturation, chain
length, and degree of branching. Highly saturated tallow Table 12. Viscosity of biodiesels
esters are poorer in this respect than soy and rape esters. Reference Fuel Viscosity
Methyl soy and rape esters exhibit average cloud points (cs @40°C)
of about 0 and - 5 ° C and pour points of about - 4 and Number 2 diesel 2.6
-10°C, respectively. Methyl tallowate exhibits an 16 Soybean oil methylester 3.97
average cloud point of 14°C and a pour point of 10°C. 18 Soybean oil methylester 3.77
The effect of chain length, degree of saturation, and 20 Soybean oil methylester 4.3
21 Soybean oil methylester 3.9
branching has not been considered in biodiesel manu- 23 Soybean oil methylester 4.08
facturing. It has been suggested that isopropyl esters will 24 Soybean oil methylester 4.23
have better cold flow properties than methyl, ethyl, 25 Soybean oil methylester 4.06
or butylesters, 5~ although no data to support this 31 Soybean oil methylester 4.32
proposition were presented. Reducing chain length and/ 43 Soybean oil methylester 4.06
48 Soybean oil methylester 4.1
or increasing chain branching would improve the cold Average Soybean oil methylester 4.08
flow properties of the fuel. Chain length and degree of
branching might be altered through both plant breeding 26 Rapeseed oil methylester 6.1
or genetic engineering approaches, as well as through 27 Rapeseed oil methylester 4.48
28 Rapeseed oil methylester 4.57
chemical processing of the biodiesel to cleave certain 29 Rapeseed oil methylester 4.5
double bonds or to form branched isomers. Very little 30 Rapeseed oil methylester 4.5
practical research has been done in the chemical 32 Rapeseed oil methylester 5.65
processing area. The cold flow properties of biodiesel Average Rapeseed oil methylester 4.83
fuels are clearly an area in need of considerable research.
25 Tallow methylester 4.47
Midwest Biofuels 50 also reported data on soy ester and 43 Tallow methylester 4.11
tallow ester blended with Number i and Number 2 diesel 44 Tallow methylester 5.83
fuels. The diesel fuels used for blending had cloud and Average Tallow methylester 4.80
pour points at the low end of the range typical of diesels.
23 Soybean oil ethylester 4.41
Blends of soyate and tallowate with D-I and D-2 fuels 32 Rapeseed oil ethylester 6.17
showed that cloud and pour points increased as the 34 Palm oil methylester 4.5
amount of ester blended increased. The effect with D-I 34 Palm stearin methylester 4.6
was significantly larger than with D-2 as shown in Fig. 5 35 Frying oil ethylester 5.78
where the increase in temperature is much steeper for 44 Tallow ethylester 5.93
44 Tallow butylester 6.17
Number I than Number 2 oils. In both cases, the tallow
 Fat and vegetable oil defivedfuels 137

--t-- Soy M~/Imaor ~IO°C, Ref. 21

--0--SoyMolhylutor
~20eC,R~•32
7 R~ M~lhylutar~

i i i i i i

0 20 40 60 80 100
Weight Percent Biodiesel
Fig. 6. Effect of blending soybean and rapeseed esters on diesel fuel viscosity.

point components. The lower freezing liquid phase is figure suggest blend viscosity is lower than would be
then decanted• Yields of soyester, having a cloud point of predicted from a linear combination model, probably
-20°C, were only 30% by weight using this method• If because dissolution of biodiesel in D-2 minimizes
commerical cold flow improver additives were blended intramolecular interactions responsible for this property.
prior to winterization, yield increased to 80% for a cloud Based on the curves in Fig. 6, the viscosity of blends
point of - 11°C. containing up to 30 wt% of soy or rape methylesters wi!l
Van Gerpen 54 has presented data on the impact of most likely meet standards for Number 2 diesel.
contaminants and impurities on the cold flow properties Surface tension is another fuel property that affects
of methyl soyester. Unsaponifiable matter (sterols, spray atomization, droplet size, and other important
tocopherols, and other hydrocarbons) is present in properties of the diesel spray• Only very limited data on
crude soybean oil at about 1.5 wt%. This leads to the surface tension of neat biodiesels and blends is
levels of less than ! % in methylesters. Unsaponifiable available. A typical value for Number 2 diesel is
matter had no effect on cold flow properties up to the 22.5 dyne/cm at 100°C. Stotler 24 reports a value of
2% level. The impact of unconverted mono- and 34.9 dyne/cm at 60°C for neat soy methylester and
diglycerides, having saturated fatty acid chains, on Reece and Peterson 26 report 25.4 dyne/cm at 100°C for
cold flow properties was also examined. These materials rapeseed oil methylester.
had little effect on pour point up to the ! wt% level but
exhibited a significant effect on cloud point, even at 2.7. Storage and Stability
0.05 wt%. Unsaturated monoglycerides had no impact
on cold flow properties. Stability encompasses thermal stability under both
hot and cold conditions, resistance to oxidation,
2.6.2. Viscosity and surface tension
Table 13. Stability in terms of iodine number for biodiesels
The ASTM D-445 specification of maximum 4.1 cSt
Reference Fuel lodine
viscosity at 40°C is barely met by soybean oil number
methylesters, as shown in Table 12. Viscosity values
for esters of rapeseed oil and tallow exceed this value Number 2 diesel 8.6
17 Soybean oil methylester
significantly. In any case, the viscosity of neat biodiesels 20 Soybean oil methylester 133.9
is higher than for typical Number 2 diesel. High viscosity 23 Soybean oil methylester ! 35. I
leads to poorer atomization of the fuel spray and less 24 Soybean oil methylester 130.5
accurate operation of the fuel injectors• Additionally, the Average Soybean oil methylester 133.2
viscosity of biodiesel and biodiesel blends increases
23 Soybean oil ethylester 123
more rapidly as temperature is decreased than that of 32 Rapeseed oil methylester 97.4
Number 2 diesel. 45 Monoglyceride impurities have also 32 Rapeseed oil ethylester 99.7
been shown to significantly increase the viscosity of 34 Sunflower oil methylester 125.5
methyl soyesters. 54 The effect of biodiesel content on the 34 Cottonseed oil methylester 105.7
35 Frying oil methylester 63.5
viscosity of blends is shown in Fig. 6. The curves in this
138 M.S. Graboski and R. L. McCormick

polymerization, and microbial activity during storage,
and absorption of water. The main source of instability in
biodiesel fuels is unsaturation in the fatty acid chain. If
two or more double bonds are present, they have a
mutually activating effect. The metals and elastomers in
contact with biodiesel during storage can also impact
stability. Oxidation leads to the formation of hydro-
peroxides, which can attack elastomers or polymerize to
form insoluble gums.
2.7.1. Iodine number
Iodine number (DIN 53241/IP 84/81) is a measure of
the degree of unsaturation of the fuel. Unsaturation can
lead to deposit formation and storage stability problems
with fuels, as noted above. Soy and rapeseed methylester
have iodine values of approximately 133 and 97, as noted
in Table 13. Data do not appear to be available for tallow
esters but a lower value is expected based on the greater
degree of saturation of this material. Mercedes Benz
experience 55 suggests that fuel with iodine number
greater than 115 is not acceptable because of excessive
carbon deposits. Many biodiesels have iodine number
greater than this value, specifically methylesters of
soybean oil (see Table 13). Ryan et al. 56 addressed
soybean, sunflower, and cottonseed oil use in engines
and suggest that the maximum iodine number should be
limited to 135. Many biodiesel fuels are produced from
feed stocks that are naturally highly unsaturated.
Removal of the unsaturation by, for example,
hydrogenation leads to a worsening of cold flow
properties. Research must be directed at additives that
can act to stabilize the unsaturated bonds in biodiesel
fuels to obtain an acceptable stability.
2.7.2. Oxidative stability and gum number
Oxidative stability is measured by ASTM D2274.
EMA 45 reported that compared to Number 2 diesel,
methylesters of tallow and soy were far more prone to
oxidation in this test. Number 2 diesel consumed 5% of
the available oxygen, tallow methylesters consumed
60%, and soybean oil methylesters consumed 90%. Van
Gerpen 54 has noted that certain minor components of
biodiesel, such as tocopherol, are natural antioxidants
and that these are removed if the biodiesel is purified by
distillation. In comparative oxidation tests, the peroxide
value (a measure of the amount of hydroperoxides
present) increased roughly four times faster for a distilled
soy methylester than for undistilled. Interestingly,
formation of hydroperoxides resulted in a significant
increase in cetane number over the course of these
relatively short-term tests (up to 24 days). Clearly an
understanding of the maximum acceptable hydro-
peroxide level in biodiesel is needed. This information
must include the impact of hydroperoxides on elastomers

Table 14. Proposed fuel property standard for biodiese145

Property Units Test method Diesel Soybean oil Rapeseed oil
(USA) (ASTM D975) methylester methylester
(NBB standard) (DIN V 51606)
Density at 15°C g/cc ASTM D 1298 -- 0.86-0.90 0.875-0.900
Viscosity at 40°C mm2/s (cSt) ASTM D445 1.3-4.1 1.9-6.0 3.5-5.0
Flash point °C ASTM D93 52 min 100 min 100 min
Cold filter plugging
Summer °C ASTM D4359 * By customer 0 max.
Winter °C - 2 0 max.
Pour point
Summer °C ASTM D97 * By customer --
Winter °C
Sulfur content wt% ASTM D2622 0.05 max. 0.01 max. 0.01 max.
Distillation
5% Evaporation °C ASTM D 1160 None To be determined
95% Evaporation °C 282-338 None To be determined
Carbon residue wt% ASTM D189 0.35 max. 0.5 max. 0.3 max.
Coradson
Centane number ASTM D613-86 40 min 40 rain 49 min
Ash content wt% ASTM D482 0.01 max. 0.02 max. 0.01 max.
Water content ASTM D1796 0.05 vol% max. Visual 300 mg/kg max.
Particulate matter g/m 3 DIN 51419 -- Visual 20 max
Copper corrosion ASTM D130-88 3 max. 3 max. I max.
(3 hr at 50°C)
Oxidation stability g/m 3 ASTM D2274 To be determined --
Acid value mg KOH/g ASTM D664 To be determined 0.5 max.
Methanol content wt% To be determined None 0.3 max.
Monoglycerides wt% To be determined None 0.8 max.
Diglycerides wt% To be determined None 0.1 max.
Triglycerides wt% To be determined None 0.1 max.
Bound glycerin wt% To be determined -- --
Free glycerin wt% To be determined To be determined 0.02 max.
Total glycerin wt% To be determined To be determined 0.25 max.
Iodine number DIN 5324 IflP 84/81 -- None 115 max.
Phosphorous content mg/kg DGF C-VI4 To be determined 10 max.
 Fat and vegetable oil derived fuels 139

Table 15. Fuel economy for biodiesel (soybean oil methylesters)
and biodiesel/Number 2 diesel blends over the EPA transient
test, 1991 DDC Series 60 engine 19
Biodiesel CO2 Fuel
(%) (BtuPahp-hr) (Btu/bhp-hr)
0 7176 7326
20 7040 7192
35 7080 7130
65 7006 7133
100 7038 7038
Avg/std dev 7068/66 7 t 64/106
and metals, fuel combustion properties, microbial
activity, and gum formation.
Oxidation products formed in biodiesel will affect fuel
storage life and contribute to deposit formation in tanks,
fuel systems and filters. Gum number is a measure of
deposit formation. Fuels with high iodine numbers may
possess high gum numbers. Clark et al. 23 determined
gum numbers for methyl- and ethylesters of soybean oil
and found 16400 and 19 200, respectively. A compar-
able value for Number 2 diesel is 6-7. Bessee and Fey 57
examined the compatibility of pure soy methylesters, as
well as blends with D-2 and JP-8, with six metals
commonly found in fuel systems. The test continued for
6 months with periodic visual inspection and measure-
ment of Total Acid Number (TAN), a measure of the
extent of fuel oxidation as well as corrosive tendency. At
the end of the 6-month test, TAN had not increased for
the base fuels containing no biodiesel. All biodiesel fuels
exhibited either a dramatic increase in TAN or the
formation of gum deposits. Gum deposits were most
significant for metals containing copper while acid
numbers were highest for samples in contact with steel
and aluminum. Clearly soy based biodiesel fuels exhibit
poor stability relative to conventional diesel. This is also
true for rapeseed based biodiesel, as demonstrated during
a 2-year storage stability study where peroxide and acid
values increased by more than one order of magnitude. 32
This is a particularly important area for future research if
these fuels are to become commercially acceptable.
2.7.3. Water absorption and microbial activity
Water present in fuel can cause the formation of rust
and, in the presence of acids and hydroperoxides formed
by fuel oxidation, lead to corrosion. Water is also a
necessary ingredient for microbial growth, which can
occur at the interface between the fuel and any free water
phase. ASTM standard D-975 allows up to 500 ppm
water in D-2. As the solubility of water in D-2 is only
about 60 ppm (at 25°C), 58 any water above this level will
be present as a separate phase either at the bottom of the
tank or suspended as an emulsion. Water solubility data
are available for methyl soyester and for a 20% blend
with D-2. 54 The solubility of water in pure methyl
soyester was found to be ~- 1500ppm while only
40 ppm (a value thought to be statistically the same as
the 60 ppm reported in Ref. 58) dissolved in the B-20.
Pure esters subjected to conventional fuel handling
practices will most likely be saturated with water. Thus,
upon blending of this water-saturated material with D-2,
a separate water phase will form providing a site for
microbial growth.
Biodiesels produced from soybean and rapeseed are
readily biodegradable and furthermore, the presence of
biodiesel (i.e., in B-20) enhances the biodegradability of
petroleum derived diesel in the presence of water. 32
However, there appear to be no data from controlled tests
available on the impact of microbial activity on biodiesel
fuels during storage or on the use of additives to prevent
microbial growth. Growth,of algae in fuel storage tanks
was noted in a biodiesel transit bus demonstration
program. ~06
2.8. Biodiesel Industry Fuel Standard
Data on fuel properties discussed above, and the data
on engine performance and emissions which follows,
exhibit a high degree of variability for a given biodiesel
source. One possible cause of this is the fact that no
attempt was made to insure that the biodiesel fuels all
met the same quality standard. The National Biodiesel
Board (NBB) has been developing a fuel standard for soy
diesel, which is shown in Table 14 along with a DIN
(German) standard for rapeseed oil methylester. The
EMA has stated that development of such a standard is
necessary if any manufacturer is to extend warranty
coverage to biodiesel fueled engines. The EMA 45 cites a
number of areas of concern being addressed by NBB's
fuel specification including viscosity, flow properties,
oxidative stability, corrosion, free methanol and
esterification byproducts, and biological growth.
Several of the standards are currently undefined such
as oxidative stability and acid value. Results presented in
previous sections indicate that standards for these
properties are critical for commercial development of

Table 16. Fuel economy data for a series of engines operating with catalysts and timing changes (btu/bhp-hr)
Fuel Set-up DDEC MUI DDEC MUI MECH-L- 10 MUI-6V-
6V-92-TA 6V-71N 6V-92TA 6V-92 1987 92TA 1987
1991 1977 1988 -1981/1989
Reference 59 60 41 61 24 24
DF-2 Stock 8593 8374 8426 8735 7252 8911
B-20 Stock 8529 8439 8258 8759 7192 8837
B-20 Timing 8599 8375 8475 8874 7066 8873
B-20 Timing + cat 8580 8835 8421 8835 7138 8819
Timing deg 3 4 1 2 ?
140 M.S. Graboskiand R. L. McCormick

biodiesel fuels and research must be directed at their
definition. Efforts by researchers to insure that the
biodiesels they use meet the standards in Table 14 should
lead to results that are more consistent than those
reported in the past.
3. ENGINE PERFORMANCE
3.1. Fuel E c o n o m y
In most reported studies, fuel consumption is calcu-
lated from the carbon dioxide emissions and an analysis
of the fuel carbon content. A more accurate approach is to
combine CO2 emission measurements with a gravimetric
measurement of fuel consumption. The uncertainty in
fuel economy values from CO2 emissions alone is
necessarily larger since the researchers do not close the
fuel/emissions carbon balance. The carbon balance
approach was taken by Graboski et al. 19 for soy
methylesters and blends with Number 2 diesel tested in
a four-stroke engine using the EPA heavy duty transient
test. Table 15 presents fuel economy data in Btu/bhp-hr
(1 Btu/bhp-hr = 0.0141 MJ/kW-hr) from this study. In
these tests, carbon input to and carbon output from the
engine differed by less than 2%. The standard deviation
in fuel economy by each method is ~ 1.5%. The data
clearly show that within experimental error, the energy
efficiency is independent of fuel composition.
Table 16 presents fuel economy data for a series of
engines operating on biodiesel and evaluated with and
without catalysts and timing changes. Timing changes
are investigated for biodiesels to eliminate the increased
NOx emissions observed for these fuels, as described in
Section 4 of this review. In general, these data show that
adding biodiesel to D-2 has no effect on energy fuel
economy. Within the accuracy of the data, employing a
catalyst and retarding timing for NOx control also does
not significantly impact fuel economy.
In addition to transient testing, energy fuel economy
data are available for steady-state and multi-mode
steady-state testing. For example, Clark et al. 23 studied
diesel, methylsoyate and ethyl soyate in a John Deere
4239TF direct injected turbocharged diesel engine
attached to an eddy current dynamometer. Fuel
economy, torque and horsepower at wide-open throttle
were all directly related to volumetric heating value of
the fuels.
Much of this data is summarized in Fig. 7 which
presents energy economy data for biodiesel and biodiesel
blends compared to Number 2 diesel for steady-state and
transient testing and covering a broad range of engine
models and vintages. Biodiesel blends vary from 10% to
neat, and include methyl, ethyl- and butylesters of
soybean oil and tallow. As the figure shows, the energy
fuel economy is independent of the fuel mixture fed to
the engine. Thus, the crude oil replacement benefits of
biodiesel depend on the total quantity used but not the
blend concentration.
Several road tests support the conclusions from engine
testing. Battelle 63 reported on a soy methylester B-20 bus
study carried out at Bi-State Development Agency in St

11000

10000
r.-
&
r--

--z
9000

E
0
e-

8 8000
uJ
Slope=1.004
"I r2=0.979
LI..
7000
._m

rn
6000

5000 I I I I I

5000 6000 7000 8000 9000 10000 11000

NO. 2 Diesel Economy, Btu/bhp-h
Fig. 7. Fuel economyfor neat biodiesel and blends.Data includea wide range of engines with soy and tallow based methylesters,
from Refs 16, 18, 22, 24, 4 I, 42, 44 and 59-62.
 Fat and vegetable oil derived fuels 141

Louis where five buses each were run on B-20 and five Table 17. Chassis dynamometer based fuel economy data
on control Number 2 diesel. Approximately (mile/gal) 67'6s
200000 miles were accumulated with each fleet. The Cycle Biodiesel 1988 DDC 1981 DDC
diesel buses were run 7 days per week while the 6V-92TA 8V-71
biodiesel buses were operated 5days per week. (%) (mpg) (mpg)
The measured fuel economy was 3.76 mpg for B-20 CBD Stock 0 3.69 3.59
and 4.01 mpg for control diesel, a 6% reduction. A 1-3% CBD Stock 20 3.68 3.63
loss was expected based upon the lower heating value of CBD Timing 20 3.54 3.59
biodiesel and no explanation was provided for the CBD Cat 20 3.35 3.18
discrepancy. The fuels were not interchanged for a given CBD Timing + cat 20 3.26 3.30
Arterial Stock 0 4.67 3.92
bus; the fleet size was so small that hardware differences Arterial Stock 20 4.72 3.91
may have a significant effect on mileage. Data on Arterial Timing 20 4.89 3.93
passenger loading, driver assignment and routes were not Arterial Cat 20 4.64 3.40
provided. Within the limitations of the design of this Arterial Timing + cat 20 4.56 3.84
Composite Stock 0 3.70 3.66
study, energy content based fuel economy was Composite Stock 20 3.63 3.52
unaffected by blending biodiesel with diesel. Composite Timing 20 3.50 3.63
ATE Management and Service Company 64 reported Composite Cat 20 3.34 3.21
on a study conducted by Cincinnati Metro. Six buses Composite Timing + cat 20 3.33 3.43
were tested with soy methylester B-30 fuel. Four were
equipped with 1987 MUI and two with 1989 Electronic
DDC 6V-92 two-stroke power plants. Prior to the test all
engines were tuned up and received new injectors. Each Table 18. Effect of biodiesel content on engine peak torque. A
bus was power baselined on a chassis dynamometer with 1991 Detroit diesel series 60 engine 19
D-2. The buses were not assigned to fixed routes and
% Biodiesel/test no. Peak torque, ft-lb
experienced a variety of driving situations. Fuel mileage
(1200 rpm)
data were given for each bus and mileage was on average
5% lower with B-30. The expected loss in mileage based 0/1056 1283
upon fuel heating value was 3.2%. The agreement is thus 0/1071 1279
0/1085 1278
excellent within the accuracy of this type of study. 0/1111 1286
Daniel 65 reported on the Link Transit Biodiesel 20/1064 1275
Demonstration Project in the state of Washington. This 35/1105 1270
study was a 1-month 104 000-mile demonstration of 20% 65/1117 1256
100/1091 1210
soybean oil methylester biodiesel. The base diesel was
not defined. They saw no significant change in fuel
economy for 1991 and 1993 6V-92TA DDEC II engines This is probably because of the effect of back pressure on
in Orion 1 Coaches. The expected change would have vehicle performance regardless of the fuel, although
been a 2.2% loss in mileage. back pressure measurements were not reported.
Yost 66 reported on a 6-month field test by Spokane Based upon the data described above, neat biodiesel
Transit on D-I with 30 and 20% soy methylester. and biodiesel blends exhibit a fuel economy proportional
Eighteen coaches were used (6 each with 6V-71,6V-92, to their lower heating value. No improvement or
6 L-71 engines of 1974-92 vintage). The fuel mileage degradation in energy efficiency is expected.
was 1/2 mpg better than with D-1. The lower heating
value of D-I is approximately the same as for methyl 3.2. Torque and Acceleration
soyester. However, it is not known how fuel economy
differences were actually computed and whether there The torque developed is related to the energy density
was any control of properties on the D-i employed. of the fuel. Studies have documented reductions in
Howes and Rideout 67"68 investigated emissions and torque for biodiesel blends and neat biodiesel. Graboski
fuel economy for two urban buses using three bus chassis et al. 19 found that the peak torque decreased with
cycles for diesel, soy methylester B-20, as well as B-20 biodiesel blend content, using a common Number 2
with timing changes and catalyst. Table 17 shows the diesel base stock, as shown in Table 18. Four separate
fuel economy in mpg based on CO2 emissions. No data determinations of petro°diesel peak torque bracket the
on fuel composition were reported and it was not stated biodiesel blend runs and are shown to demonstrate that
whether the B-20 was produced by mixing with the the torque does not change with time (chronologically
diesel reference fuel used. Table 17 shows that there was shown by run number). The relative torque between neat
no significant effect of biodiesel addition on mileage, biodiesel and 100% Number 2 is 94.6% which is in good
both with and without a 1.5° timing change. The agreement with that expected from the energy density
confidence limits on the data encompass the expected ratio of the fuels. Peak torque is not significantly affected
2.2% loss in mileage based upon fuel energy content. up to 35% biodiesel. Ortech International 18 presented
Addition of a catalyst caused a 6.2 and 8.3% loss in torque data for a DDC 6V-92 TA engine and reported no
mileage for the 6V-92 and 8V-71 engines, respectively. significant loss in torque at up to 40% biodiesel in
142 M.S. Graboski and R. L. McCormick
blends, in agreement with the Series 60 observations
given above. A more recent Ortech study 69 utilized a
Cummins NI4 engine and observed peak torque to
decline by the same percentage as fuel energy density for
biodiesel blends.
The U.S. Army conducted acceleration and pull bar
tests at the U.S. Army Proving Grounds, Yuma Arizona
on five different military vehicles. 7° The Army has
recently used JP-8 as a battlefield fuel in place of
Number 2 diesel. Biodiesel has a higher energy density
than JP-8 and can also reduce smoke. A 20% biodiesel
blend with JP-8 provided 6.8 and 5.6% faster accelera-
tion times for a cargo carrier and a tactical truck
compared to JP-8 alone. Three other vehicles showed no
difference between the blend and the JP-8. Acceleration
times worsened for all five vehicles by 11-14.5% when
the JP-8/biodiesel blend was compared to D-2. The
drawbar pull test measures delivered torque. Except for
one vehicle, all showed equal or increased drawpull
value operating on JP-8/biodiesel compared to neat JP-8
and 6.2 to 19.2 lower drawpull value than D-2.
The test results show that acceleration and torque are
in general related to the energy density of the fuel used.
Torque generation at intermediate throttle positions will
be lower but the requirement for torque can be met by
increasing the throttle position slightly. Thus, the only
power related drivability problems that might be
experienced with biodiesel are slightly lower accelera-
tion at wide-open throttle and slightly reduced horse-
power at wide open throttle. Intermediate cruise
conditions are not affected.
3.3. Engine Endurance Issues
At this time, most engine manufacturers have not
extended warranty coverage to biodiesel. 55'71-74 There-
fore, an important barrier to biodiesel use is sufficient
endurance testing to allow manufacturers to warranty
engines operating on these fuels. A test stand durability
study is typically required because in on-road demon-
stration testing vehicles do not operate long enough on
the fuel. EMA 45 has summarized many of the key
endurance issues and the important fuel properties which
might affect endurance. Unreacted mono-, di-, and
triglycerides, free fatty acids, methanol and glycerol
need to be removed. Triglycerides are unconverted
vegetable oil or fat and form injector deposits, as noted in
early studies using raw oils on fuels. Monoglycerides,
glycerol, and fatty acids 'dry' corrode bearing metals.
Because of the high boiling point of biodiesel, lube oil
dilution and valve/port deposits are an issue. Valve
deposits occur at light load when low volatility fuel is
deposited on valve surfaces and undergoes coke-forming
reactions. High boiling fuel that becomes mixed with the
lube oil will not evaporate as the engine oil heats up.
Lube oil dilution by biodiesels leads to different in-use
lube oil properties (such as lube oil acidity) than
petroleum diesel and needs to be carefully examined.
Solvent properties relative to engine elastomers are also
important as unsaturated methylesters, or oxidation
products such as hydroperoxides and carboxylic acids,
can act as plasticizers. Water absorption into the
biodiesel might lead to corrosion of fuel system parts.
Many of these problems can be addressed through proper
purification of the raw methylester fuel to eliminate
glycerine and unconverted mono- and diglycerides.
3.3.1. Durability studies
To address these issues a number of long term
durability tests have been performed. Several of these
studies were funded by NBB and two of the most
significant are reviewed here. National Biodiesel Board
(NBB) 75 funded a 1000-hr durability test using a DDC
6V-92TA, electronic controlled engine and a 20%
methyl soyester blend. Approximately 10000 gallons
of the B-20 blend were consumed during the test. The
conditioning cycle included idle, wide-open throttle, and
intermediate power conditions. At about 700 hr, the
following conditions were observed: low fuel return
pressure, low horsepower, low fuel consumption, and
high crankcase blowby. It was observed that fuel
retuming to the day tank was black and significant
deposits o n air box covers, piston components, and
injectors was observed. The fuel lines, fuel filters, and
fuel transfer pump were replaced during a brief shut-
down at 700 hr. After a longer shutdown at 750 hr, it was
found that engine parameters had returned to normal.
During the final 250 hr, performance deteriorated in a
pattern similar to the first 750 hr. After engine tear down,
substantial deposits were found on many engine
components. The source of these deposits appeared to
be the lube oil. Cavitation erosion of the injector needle
valves had caused injectors to deteriorate to the point that
almost no fuel atomization was occurring. Deteriorating
fuel pump seals were proposed to have introduced
microscopic air bubbles into the fuel causing the
cavitation erosion. Elevated soot and wear metals were
observed in the lubricant. Broken fire and compression
rings were also found on several cylinders. Softening of
fuel system seals was observed.
A second NBB-funded durability study was performed
using a 1987 Cummins NI4 engine and B-20 (soy
methylester). 76 The test was intended to be of 1000-hr
duration but was terminated at 650 hr due to failure of
the engine PT pump, a part of the fuel system. Failure
was caused by build up in the pump of a residue
composed of fatty acid esters, free fatty acids, and acid
salts. This same residue had plugged a fuel filter and the
PT pump earlier in the durability test. Fuel injectors were
in good condition at the end of the test. Oil analysis
revealed no significant degradation. It was proposed that
the operational problems experienced during this test
were caused by instability toward oxidation of the B-20
fuel. Notably, both the neat soy diesel and No. 2 diesel
used to make the B-20 used in this study were found to be
stable.
The University of Idaho 32 has conducted 200-hr
durability tests with 4-stroke, direct injected, naturally
aspirated engines. The fuels used were D-2, neat
 Fat and vegetable oil derived fuels
rapeseed methyl- and ethylesters, neat hydrogenated
soybean oil ethylester (frying oil ethylester), as well as 80
and 20% blends of the hydrogenated soy ester with D-2.
No significant problems were encountered in these
relatively short tests. At the conclusion of the tests,
lube oil iron content was significantly higher for the
rapeseed oil based fuels compared to D-2 suggesting
abnormal wear. This was not the case for the hydro-
genated soybean oil fuels. The unsaturation of the
rapeseed ester fatty acid chains probably lead to
oxidation and acid formation causing corrosion.
Goya174 reported a study using the ISO 8178-4 off
road test with rapeseed methylester. A Deere 4239T
engine was run for 1450 hr. Power loss was 6-8%. After
1000 hr of rated operation, carbon build-up in ports and
piston rings was observed. After 300 hr of light load
testing, lacquer and varnish deposits were observed on
combustion chamber parts. Some gaskets were
distressed, suggesting incompatibility with methylesters.
Additional studies provide some confirmation of the
problems noted above. Lucas 7° reported similar fuel
filter and pump problems to those described above in his
study of soy methylester B-20 formulated with JP-8 (jet
fuel). Fleet studies with rapeseed oil methylesters 29'3°
have found that fuel tank coatings can be dissolved by
these fuels. The impact of these contaminants on the
engine fuel system was not assessed.
Low duty cycle engines may be especially subject to
lube oil dilution. Blackburn 77 reported 50% oil viscosity
loss in 50 hr using ethyl soyate. Macchi 7s reported a
higher dilution for rapeseed methylester. Schloeg179
reported serious dilution with viscosity dropping 50%
and total base number dropping 30% in 200 hr. The low
duty cycle engines used showed valve and port deposits.
3.3.2. Elastomer compatibility
Many of the problems encountered during the
durability studies described above can be traced to
incompatibility of biodiesel with certain elastomers. The
solvent properties of biodiesel can dissolve elastomers as
well as fuel tank deposits and lead to fuel filter and
Table 19. Results of biodiesel lubricity tests for soybean oil methylester and ethyl- and methylesters of rapeseed oil
Fuel BOCLE result
(g)
Conventional low sulfur diesel 8° 4200
Conventional low sulfur diesel 9~ 4250
Methyl soyester s° 6100
Methyl rapeseed ester 9~ 7000
Ethyl rapeseed ester 9~ > 7000
B-2 (Soy methylester) 8° 4400
B-5 (Soy methylester) s° 4500
B- 10 (Soy methylester) 8° 5200
B-20 (Soy methylester) s° 5200
B-30 (Soy methylester) 8° --
B-20 (Rape methylester) 91 4600
B-50 (Rape methylester) 9t 5550
B-20 (Rape ethylester) 91 4700
B-50 (Rape ethylester) 9] 5700
143
injector plugging. 7j-74 Most of the elastomers used with
conventional diesel swell by absorption of aromatic
compounds. This swelling is normal and is accounted for
in fuel system design. Biodiesel fuels may leach
aromatics from the elastomer as well as additives
designed to prevent hardening and cracking.
Methylesters have been shown to swell trilobutyl-
dilene and nitrile rubber, common automotive seal and
gasket materials. 55 Fluorine containing elastomers did
not exhibit significant swelling. Hawkins et al. sj
reported acceptable performance with Viton A. Bessee
and Fey 57 examined the effect of exposure to methyl
soyester and D-2 blends on the tensile strength,
elongation, hardness, and swelling of several common
elastomers. Nitrile rubber, Nylon 6/6, and high-density
polypropylene all exhibited changes in physical
properties. Teflon ®, Viton ® 401-C, and Viton ® GFLT
were unaffected. There is general agreement that
fluorinated elastomers must be used for biodiesel
service. 29"55'73 Most engine manufacturers appear to be
using this type of elastomer in their newer model
engines.
The effect of fatty acid structure (e.g., degree of
saturation) on elastomer compatibility does not appear to
have been examined. Perhaps most importantly, the
impact of biodiesel purity does not appear to have been
addressed in quantitative studies. Highly unstable free
fatty acids as well as unreacted mono-, di-, and
triglycerides, glycerol, and methanol may have a great
impact on elastomers. These aspects of compatibility
with elastomers are a topic for future research.
3.3.3. Biodiesel lubricily
Fuel lubricity is important because in many fuel-
pumps the moving parts are actually lubricated by the
diesel fuel itself. Lubricity is measured by the Ball On
Cylinder Lubricity Evaluator or BOCLE test, and the
High Frequency Reciprocating Rig or HFRR test.
Results are shown in Table 19. The BOCLE test is
accurate to _+ 200 g and fuels with good lubricity give
BOCLE results in the 4500-5000 g range. For the HFRR
HFRR
Scar (mm) friction
0.492 0.24
0.405 --
-- --
0.140 --
0.085 --
0.193 0.13
0.206 0.13
0.190 --
0.180 --
0.165 --
0.165 --
144 M, S. Graboski and R. L. McCormick

I I ~ I II

I~ I ~ =IIII~ ~°~ t ~ t ~ t ~ to ~ l

~o ~ I ~ I I~
O0 0 0 0

o
~
•
0
~ ~
0 0 0 0 0
II

II

E
o ~ ~ ~ ~ ooo ~

"?,

i
 Fat a n d v e g e t a b l e oil d e r i v e d fuels 145

N 2 d 2 ~ ~ 2¢d ~ N d N ~ 4 d ~ d d ~ N

~ . m. . ~. m ~ ~. ~. --. ~. ~. ~ ~. ~ ~ ~. ~. ~. ~ ~. ~. ~.

/ I I t I I I I "~ I I I I

II
¢ ¢ ¢ ¢ d ~ ~ ¢ ¢ ¢ d d e d d d d d d dd

~=~=~ ~ =~. ~ .= =~ ~ .N ~ ¢. -~ =. ~ ~ ~ ~ - - ~ =~..

~. H. ~ .- . . . . . ~ ~. N. ~ ~. ~ ~ ~ ~ ~ ~ ~ ~

. . . . . . . . . . . . . . ~ = ~ ~ ~ ~

-- ~ ~,,+ ~ ++~ ~,t.+ ~'~

r..)

, i.-

E-
146 M.S. Graboskiand R. L. McCormick
test, scar values over 0.400 mm are considered failing.
These results show that biodiesel, or at least soybean and
rapeseed oil methylesters, have superior iubricity when
compared to conventional low sulfur diesels. Blending
biodiesel at concentrations of 20 vol% or higher results
in an improvement in lubricity over that of the D-2.
3.3.4. Summary
These durability results suggest that the use of
biodiesel blends can result in a loss of oxidative stability
of the lube oil and degradation of fuel system elastomers
and coatings, which may have ultimately damaged fuel
pumps and injectors. Oxidative stability of the biodiesel
itself can impact elastomer compatibility although no
studies of this effect appear to have been done.
Hydroperoxides formed upon oxidation, as well as
impurities such as unconverted mono- and diglycerides
and glycerine can lead to engine deposit formation.
Biodiesels have superior lubricity to conventional diesel
so this will not be an engine endurance issue.
4. EMISSIONS
4.1. Regulatory Barriers
In the United States, diesel engines are currently
regulated for smoke opacity, total nitrogen oxides (NOx),
total particulate matter less than 10/xm (PM-10 or PM),
carbon monoxide (CO), and total hydrocarbon (THC)
according to test procedures defined by EPA in the Code
of Federal Regulations. s2 Since the magnitude of diesel
emissions are fuel composition dependent, emission
certification testing is conducted with 'certification
diesel fuel' which represents the U.S. annual average
diesel. Depending on the type of diesel engine and its
use, EPA has defined a useful life. For many on road
engines, the defined useful life is 290000 miles. Diesel
engines must meet emission standards throughout
their useful life without deterioration. This is demon-
strated to EPA through deterioration testing. There are
other emissions from diesel engines such as aldehydes
and poly-aromatic hydrocarbons (PAH) which are
currently unregulated but which may be regulated in
the future in an attempt to control ambient levels of air
toxins.
EPA is presently considering a regulatory action to
define 'substantially similar' diesel fuels. Substantially
similar fuels must demonstrate similar emissions, engine
performance and durability. Petroleum distillates contain
no chemically bound oxygen and EPA's current defi-
nition of diesel fuel limits oxygen content to less than
1 wt%. 83 Current in-use diesel fuels Ray contain very
small amounts of oxygen (i.e., 0.1%) present in additives
such as cetane enhancers. A blend of conventional diesel
with oxygenates, or the neat oxygenates, may not be
considered substantially similar to conventional diesel
fuel. These fuels would then be subject to the require-
ments of Section 21 l(b) of the Clean Air Act, which
requires health effect testing. Non-substantially similar
fuels might also obtain a fuel formulation use waiver
based upon extensive emissions and durability testing
which demonstrates equivalency.
Under the Clean Air Act Amendments of 1990,84
diesel fuel and fuel additives must undergo health effects
testing to determine the potential impact of emissions on
the public. EPA has defined a three-step program which
involves a literature study of the mutagenicity and
detailed speciation of diesel exhaust emissions, a live
animal exposure test protocol, and an optional extended
exposure study based upon the findings of the first two
steps. To control costs, EPA has allowed the refining
industry to form a consortium to test diesel fuel. Exhaust
toxic materials from biodiesel blends are likely to be
different than diesel (as discussed below in the section on
Emissions of Unregulated Air Toxins) and thus require
separate testing not funded through the consortium.
Since the type of oxygenate could significantly impact
the type and quantity of irritants and mutagenic
compounds in the exhaust, very extensive testing may
be required for biodiesel fuels. Engine family, blend
level, and the type of oxygenate (soy ester, tallow ester,
etc.) are variables which could result in very costly
testing matrices producing a significant barrier to
widespread use of biodiesel blends.
4.2. Regulated Emissions: Engine Stand and
Chassis Studies
Biodiesel and biodiesel blends can alter all regulated
emissions from diesel engines relative to petroleum
derived diesel. Quantitative values of regulated
emissions are dependent on the engine technology
employed and the type of emission test used.
An important property of oxygenates in diesel fuel in
general is their ability to reduce total particulate
emissions from an engine. For regulatory purposes, the
level of PM emission in g/bhp-hr (0.7457 g/bhp-hr =
1 g/kW-hr) is determined by an engine dynamometer test
known as the EPA heavy duty transient test. 82 Particulate
emissions are defined by EPA as condensed or solid
material collected on an appropriate filter at a temper-
ature of 52°C or lower. Particulate matter thus includes
soot carbon, fuel and lube oil derivatives, and sulfuric
acid aerosols. Particulate matter is often fractionated in
terms of sulfate, soluble organic fraction (SOF) or
volatile organic fraction (VOF), and carbon. 85 Extraction
of particulate samples (SOF method) using an ethanol-
toluene solvent yields similar results to volatilization
under vacuum at high temperatures (VOF method). In
the following discussion, SOF is used to refer to the
fraction measured by either the SOF or VOF methods.
Soot is produced by pyrolysis reactions in the flame
front in the combustion chamber. Fuel based SOF
emissions are principally generated during the engine
start. Lubricating oil is emitted from the engine by the
action of scavenging air and exhaust gases, which
vaporize and shear oil droplets from cylinder surfaces.
Biodiesel, and diesel fuel oxygenates in general, can
 Fat and vegetable oil derived fuels 147

impact soot and fuel based SOF but not lubricating oil
based SOF as it is not involved in the combustion
process.
Regulated emissions (NOx as NO2, CO, THC, PM) as
well as the SOF fraction of total PM, reported on a gram
per brake horsepower hour basis, are logically separated
into data for older two-stroke engines and for modern
four-stroke engines. Diesel engines are significant
contributors of NOx and PM to ambient air pollutant
inventories. The quantity of CO and THC derived from
diesel engines is generally small in comparison to
emissions from light duty vehicles. For this reason,
biodiesel fuels are being considered for use on the basis
of their impact on PM and NOx, and the following review
is primarily directed toward these emissions. It is
important to note, however, that diesel oxygenates such
as biodiesel produce large reductions in emissions of CO
and THC which might be important in some air sheds.
4.2.1. Engine dynamometer studies using two-stroke
engines
The two main types of diesel engines are classified as
two-stroke and four-stroke. Two-stroke engines produce
power for every piston stroke, rather than for every two
as in the case of four-stroke engines. Before the stringent
emission controls on diesel engines began to be imposed
in the 1990s, two-stroke diesel engines were favored for
their low weight to power ratio. However, lubricating oil
losses to the exhaust are much higher for two-stroke
engines resulting in excessive particulate emissions.
Also, a substantial portion of the air supplied to the
engine by the turbocharger is not used to control
emissions in the combustion process but instead is used
to improve the volumetric efficiency through cylinder
scavenging during valve overlap. That is, some of the air
is blown through the cylinder with both intake and
exhaust valves open to purge the cylinder of exhaust
gases. Oil droplets may be blown out during this
scavenging portion of the two-stroke cycle. This results
in a lower exhaust temperature (345°C maximum
compared to about 540°C for four stroke engines on
the EPA heavy-duty transient test) which affects the
performance of the turbocharger and exhaust catalysts.
Soy-diesel emissions. This collection of investigations
was primarily directed by the National Biodiesel Board
(NBB) for the EPA Urban Bus Rebuild/Retrofit
Program. Two-stroke Detroit Diesel engines represent
a substantial portion of the power plants used in older bus
fleets in the united states. For the general marketplace,
EPA is in the process of regulating fuels through a
substantially similar rule that requires that new fuels and
additives not increase any regulated emission in the
diesel fleet. In certain captured fleet operations, EPA
allows combined hardware and fuel changes which
provide certain emissions benefits. In the case of urban
buses, older engines are subject to rebuild rules that
require a defined reduction of particulate emissions (at
least 20%). Other emissions must be maintained at or
below the emission standards for the engine model in
question when compared to emissions from D-2
certification fuel when the engine is in the OEM
(original equipment manufacturer) configuration.
Because biodiesel fuels are known to increase emissions
of NO~, these investigations centered on strategies for
obtaining a PM reduction with no net NOx increase. The

"~ 30
U)
.e_ • PM
GI 0 NOx
4)
20
tl
rn
o
o 7
J
.oq
.~ 10

D.
3
x -10
0
Z
.N
=) -20
o)
=..
t~
t-
O -30

o
Q. -40 . . . . i , , , , I . . . . I . . . . I . . . . I . . . .

0 2 4 6 8 10 12

Weight Percent O x y g e n in Biodiesel Blend

Fig. 8. Change in PM and NO, emissions as a function of oxygen content for soybean oil methylesters in a stock, two-stroke engine
(DDC 6V-92TA-etectronic); data selected from Table 20.
148 M.S. Graboski and R. L. McCormick

Table 21. The effect of the addition of 20% soybean oil methylester biodiesel to diesel on PM emissions from two-stroke engines
Reference Engine SOP % for base diesel Change in PM (%) Change in NO.~ (%)
16 6V-71 N-77 MUI 88 -2.4 2.4
17 6V-92TA-91 DDECI1 40 -11.2 5.4
24 6V-92TA-87 MUI NA -5.1 3. I
31 1987 6V-92TA MUI 52 +5. I 6.1
41 1988 6V-92TA DDECII 58 0 4.8
59 1991 6V-92TA DDECII 25 -22.5 2.5
60 1977 6V-71N-MUI 75 + 14.5 1.4
61 1981/89 6V-92TA-MUI 54 - 3.0 4.4
87 1989 6V-92TA DDECIIa NA - 15.4 2.3
~Measurements for B- 10 blend.

20

0
O4
10

c 0
@
c
0 -10
ID

~ -20
o.

-30 i i i i i i i

20 3O 40 50 60 70 80 90 100
Percent SOF in Total PM for No. 2 Diesel
Fig. 9. Percentage PM reduction using B-20 for two-stroke engines as a function of SOF level when burning Number 2 diesel. Data
for both mechanical and electronic engines in Table 20.

NBB strategy was to investigate how NO~ and PM are
affected by timing, tuning, rebuilding, and SOF oxida-
tion catalysts to determine how much PM reduction was
achievable with no net NOx change.
Table 20 presents a summary of emissions from these
older engines investigated using the EPA heavy-duty
engine dynamometer transient test protocol. Most of
these were in-use engines that had a significant number
of operating hours logged before biodiesel testing. All
tests with biodiesel, designated as B-XX where XX is the
volume percentage of biodiesel in the blend, utilized the
reference diesel denoted as D-I or D-2 as the blend
stock. The percentage changes in NO~ and PM columns
indicate the change in these emissions relative to stock
engine set-up with the base diesel fuel.
For stock, two-stroke engines without timing changes
or exhaust catalyst, the following general emissions
trends result relative to the base diesel fuel when soyester
biodiesel is blended with Number 1 or 2 diesel fuel:
• NOx increases;
• PM, CO and THC decrease;
• the soot (solid carbon fraction of PM) mass emission
decreases.
Figure 8 is representative of how NOx and PM
emissions vary with the oxygen content of blends of base
diesel and soybean oil methylester fuels for two-stroke
engines. This plot includes only data for electronically
controlled Detroit Diesel 1991 DDEC II 6V-92TA
engines. Table 21 presents data for PM and NOx changes
and SOF levels for principally B-20 blends in a
collection of mechanical and electronic two-stroke
engines. With 20% biodiesel (2% oxygen), the NO,.
increase varied from 1.4 to 6.1%, PM changed by
- 2 2 . 5 % to +14.5%, and SOF (on the base diesel fuel)
ranged from 25 to 75%. Low SOF percentages are
obtained from newer model engines and engines with
low miles or hours of operation. Since the SOF portion of
PM from older engines is 50-75% of the total PM, the
full value of the oxygenate for PM reduction is not
realized and PM emissions may actually appear to
increase. This is clearly shown in Fig. 9 where the
percentage reduction in total PM emissions is shown as a
function of the base diesel SOF mass emission for two-
and four-stroke engines. As SOF emissions decrease, the
impact of biodiesel on particulate becomes noticeable.
The data suggest that the PM increase or decrease is

• PM
o NOx
20
v ¥
l
o -10
| •
"~ -20
•
J~
•,.-, -30
e,.
a. -40 u . . .
2 4
Weight Percent Oxygen in Biodiesel Blend
Fig. 10. Change in PM and NOt emissions as a function of oxygen content in several stock, two-stroke engines; data for soy, tallow,
and rape methylesters from Table 20.
independent of engine vintage or type of fuel injection
system. The impact on PM emissions does depend on
engine wear as it impacts oil consumption. Worn engines
slip oil past the rings to the air intake ports. During
scavenging when the intake port and exhaust valve are
open, air transports oil from the intake ports to the
exhaust resulting in oil based PM. For high SOF
engines ( > 50% of PM as oil), little PM benefit is
obtained with biodiesel. There is little reason to
believe that PM actually increases at very high SOF
emissions. The apparent increase at high SOF
emission levels is probably due to the lack of
repeatability inherent in emissions measurements from
engines that are significant oil users.
Tables 20 and 21 suggest that the NOx increase is
independent of engine vintage, injector technology, and
wear to a good approximation. Figure t0 is similar to
Fig. 8 except that it contains all data from Table 20,
including data on rapeseed and tallow esters and all
engines listed. The PM reduction correlates poorly with
fuel oxygen content and aside from the two data points at
10% oxygen (neat biodiesel) there may be no correlation.
For this data set biodiesel may have had no effect on PM
on average. However, the NOx increase correlates
reasonably well and is thus independent of engine and
SOF level. A discussion of possible causes of the
increased NOx emissions is provided in a later section of
this review.
A series of studies showed that by retarding the
injection timing of older engines from 1-4 °,
the emissions of NOx for B-20 can be decreased to a
level equal to or below the D-2 base emissions with no
timing change. Retarding the timing also increases the
particulate emission since changes that reduce NO~
Fat and vegetable oil derived fuels 149
• •
.
. i . . . . u . . . . i . . . . i . . . .
6 8 10 12
cause a decrease in cylinder peak temperature resulting
in an increase of PM and a corresponding increase in fuel
consumption. For the various two-stroke engines
studied, the NOx decreased by 1.9% to 7.3% per
degree of timing change with a 4 ° maximum change
investigated. Simultaneously, PM increased by 0.5% to
8.5% relative to B-20 with no timing change. Changes of
several degrees can negatively impact drivability.
Rebuilding and retuning also impacted NOx. Importantly
for a given engine, the percentage changes in NOx and
PM were independent of the fuel. Thus, at any given
engine set-up (timing, rebuild, tuning), NO~ was always
greater for B-20 fuels while PM was always lower.
In order to obtain NOx neutrality while maintaining
the desired PM reduction, NBB proposed to combine a
timing change with an oxidation catalyst. It was found
that for two-stroke engines with a catalyst and timing
change, there was little advantage compared to the stock
engine with catalyst and D-2. The reason for this result is
that oxidation catalysts can convert the SOF portion of
the PM only. Oxidation catalysts are flow through
monoliths. Engine emissions of liquid oil droplets and
soot are generally less than one micron in size and are not
readily captured by impaction due to changes in flow
direction. Thus, these materials pass through the catalyst
monolith. Only combustible species that are able to
diffuse rapidly to the catalyst surface can be oxidized.
Lube oil and fuel species are vapor when the engine is
under sufficient load to produce a sufficiently high
exhaust temperature. Thus, the efficiency of oxidation
catalysts to convert PM is generally much less than
100% and is dependent on the severity of the drive cycle.
Non-soy biodiesel studies. The Adept Group 31
investigated a 1983 6V92TA MUI engine rebuilt to
150 M.S. Graboski and R. L. McCormick

Table 22. Chassis dynamometer based emissions results for B-20 fuel, older two-stroke engine, NY bus composite cycle66'68
NO~ PM SOF Aldehydes
(g/mile) (g/mile) (%) (g/mile)
1981DDC 8V-71
D-2 35.2 0.91 51.8 0.40
B-20 30.7 1.48 72.2 0.42
B-20 + catalyst 32.2 0.89 48.3 0.25
B-20 + timing change 26.3 1.55 67. I 0.48
B-20 + catalyst + timing change 34.3 1.12 49.4 0.30

1988 DDC 6V-92TA

D-2 27.3 1.30 65.6 0.31
B-20 27.1 1.46 68.0 0.31
B-20 + catalyst 23.7 1.02 5 !.0 0.28
B-20 + timing change 26.9 1.79 52.0 0.39
B-20 + catalyst + timing change -- 1.21 36.5 0.34

1987 EPA D-bus low emission standards using blends of
soy and rape (canola) methylesters with CARB and U.S.
low sulfur diesel fuels (EPA diesel). Transient test
emissions were reported for CARB and EPA diesel and
are listed in Table 20. The average SOF emission from
the engine was 51% of total PM for the two diesel
baseline fuels. NOx increased for both rapeseed and soy
esters in proportion to the oxygen content of the fuel, and
this data is included in Fig. 10.
Emission measurements reported are not replicated
except for the CARB baseline data that show significant
variation. At 20% rapeseed methylester NOx increased
by 4.5 and 3.8% respectively for EPA and CARB diesel
blends, while NOx increased 5.7% for the soy methy-
lester-CARB blend. PM was reduced by 10.2 and 4.8%
respectively using 20% blends of rape methylester with
EPA and CARB diesel base stocks. PM increased 5.1%
for a 20% blend of soy methylester with CARB diesel.
However, the CARB diesel baseline PM decreased by
4.8% for the soyester series compared to the rape-ester
series. If this is taken as a measure of experimental
uncertainty, then it can be concluded that the effect of
rape and soy methylesters in 20% blends for NOx and
PM emissions is the same.
Table 20 also presents data collected using a 6V-92TA
DDECII engine comparing soy and tallow methylester/
D-2 blends. 59 The NOx emission for 20% soy and tallow
blends were 4.51 and 4.71 g/bhp-hr respectively while
the PM emissions were 0.214 and 0.219 g/bhp-hr. Within
the precision of the data for this engine, there is no
significant difference between NOx and PM emissions
for soy and tallow based fuels.
Bennethum and Winsor 88 examined the oxygenated
compound diglyme (diethylene glycol dimethylether) in
a 1991 6V-92TA DDECII engine. Heavy-duty transient
test results with the treated fuel showed a 6% PM
reduction at 0.2% oxygen as diglyme. At 2% oxygen as
diglyme, a 20% PM reduction was observed while NOx
remained essentially unchanged. McCormick et al. 87
investigated 1% oxygen blends in a 1989 6V-92TA
DDECII engine using n-octanol, decanoic acid, and
methyl soyester. All oxygenates tested produced a
significant PM reduction in the range of 12-17%.
Methyl soyester produced a more than 2% increase in
NOx emissions, significant at the 95% confidence level.
The lower molecular weight oxygenates (decanoic acid
and octanol) did not significantly change NOx. These
studies suggest that the effect of oxygenates in general is
to reduce PM based upon the quantity of oxygen added to
the fuel. Furthermore, the data suggest that NOx
emissions may depend upon the oxygenate used
although given the very small data set this conclusion
must be regarded as tentative.
Chassis studies with two-stroke engines. Howes and
Rideout 67"68 of Environment Canada tested two in-use
buses for NBB using three cycles, the CBD, the Arterial,
and the NY Bus Composite on a small roll water brake
chassis dynamometer. Low sulfur diesel and a B-20
blend (undefined triglyceride source but most likely
soybean oil) were investigated. Regulated emissions as
well as sof and aldehydes were measured. Additionally
the effect of catalyst and injection timing was studied.
Table 22 presents a summary of results for the NY
composite cycle. For the 1981 8V-71 powered bus, B-20
apparently raised the particulate emission by 50%.
Employing a catalyst and altering engine timing never
reduced emissions to the low sulfur diesel case. The
catalyst did effectively reduce a portion of the aldehydes
that are responsible for the odor from the vehicle. With
the 1988 6V-92TA powered bus, timing change and
catalyst resulted in a minor (7%) particulate reduction,
no NOx change, and an aldehyde increase. In both cases,
the SOF emission from the engine was high indicating a
large lubricating oil emission. The increase in B-20 PM
emissions with either a reduction or no change in NOx is
Table 23. Emission comparison of low sulfur D-2 and neat
soyester, CBD cycle, 6V-92 two-stroke (average of several
runs) 89
Emissions Low 100% Change
(g/mile) sulfur Methyl (%)
diesel soyester
THC 2.58 1.04 -59.8
NOx 44.53 48.68 9.3
CO 56.87 36.23 -36.3
PM 5. I 0 2.71 -46.8
 Fat and vegetable oil derived fuels 151

I I I I
~. r-:

I I II I t

I ~ - ~~ ~ - ~
II II ~, I, ~7, , ~ ,S?
&
i~lll~llll ~o ~~1_ _ _ o o
II
<

2
r-
II

. - . . . .~ . . . . . ~.~. . . . .- . . _ . . ~. ~.~.~.~.~.~.~,--~ . . . . -.

o
~ _ _ ~ ~ ~ ~_ ~ ~ ~ ~ ~ ~ ~o ~ o oo~o ~
c-

,o
E

E
E ~ z ~ ~ ~ ~ ~ ~ z z ~ ~

~+

o~
b-

~2 E
.r- ._ ,r" .- E
E ~ E
152 M.S. Graboski and R. L. McCormick

not in agreement with the reported engine studies and
may reflect the much greater degree of difficulty of
performing high quality chassis measurements.
Graboski 88 obtained results for a Denver RTD bus
fueled on low sulfur diesel and neat soy methylester
biodiesel. These previously unpublished data are
presented in Table 23. The bus was powered with a
high mileage DDEC-II 6V-92 TA power plant and was
ready for rebuild. The bus had exceptionally high
particulate emissions because of a turbocharger mal-
function but was not an oil user. Thus the SOF
percentage of the total PM was probably low, although
it was not measured. For this bus, biodiesel increased
NOx by 9% and lowered PM by 46.8%. The Adept
Group 3] reported CBD cycle data for the 1983 6V92TA
MUI engine described previously. For 20% soy methyl-
ester in CARB diesel, THC, CO and PM decreased 16.7,
20.2 and 6.1%, respectively, while NOx increased 4.5%.
Battelle 63 presented CBD chassis cycle data for buses
fueled with control diesel and B-20 (soy methylester)
which were collected using the West Virginia University
mobile chassis dynamometer. The emission results were
highly variable across fleets and changed dramatically
from the first tests conducted at 8000 miles to the second
set collected at 40 000 miles. NOx increased by 20% for
both fuels from the first to the second test that suggests
that the bus inertia was characterized differently, the
cycle was driven differently, or emissions measurements
were inconsistent between tests. The diesel buses
consumed 4quarts of oil per 1000miles while the
biodiesel buses used 1.7 quarts suggesting that a direct
comparison of PM emission data to estimate a biodiesel
impact could be confounded by differing SOF emissions.
Two diesel engines were repaired during the fleet test
and consequently oil consumption fell. Since PM is
dominated by lube oil emissions for these 1988 buses,
little or no PM benefit might be expected for biodiesel.
For all tests the biodiesel fleet emissions for NOx, CO,
and THC were 3.2% lower, 11.3% lower, and 9.1%
lower, respectively, than for the diesel fleet. The PM
emission was 9.2% higher. The percentage changes
might be meaningless because the buses fueled with
diesel and those fueled with biodiesel were different. The
problem with this data set is that control and candidate
fleets are too small to determine statistically significant
emissions differences due to fuel changes. Although
apparent percentage differences were reported by
Battelle, NOx and PM emissions for the two fuels
were statistically the same at the 95% confidence level
due to the large variation in measurements across the two
fleets.
These results show that more in-use data are required
to quantify the benefits of biodiesel fuels. However, the
general conclusion that biodiesel increases NOx and
decreases hydrocarbon and CO holds whether testing is
done in an engine dynamometer or chassis dynamometer
format. Particulate emissions will either remain constant
for high oil use engines or decrease for engines that do
not emit a large percentage of PM as oil (measured as
SOF).
4.2.2.Engine dynamometer studies using four-stroke
engines
Four stroke engines produce one power stroke for
every two-piston strokes. The additional stroke is for
purging the cylinder of combustion gases. The most
modern four-stroke engines are turbocharged and
intercooled to increase the power output per unit
weight and to control NOx emissions. In addition, these

CB
.o_ 20
G)
¢/)
10 ____._9

_o
0-
A

-I0
ne
-20
n

-30
O
Z
.c_ -40

r- -50 O NOx DDC Engines

t~
t-
• PM Cummins Engines
O
-6o L~ NOx Cummins Engines
c-

O
-70 . . . . i . . . . D . . . . i . . . . i . . . . J . . . .
o.
0 2 4 6 8 10 12

Weight Percent Oxygen in Biodiesel or Blend

Fig. I I. Change in PM and NOx emissions for soy methylester as well as rapeseed methyl- and ethylester blends in stock, four-stroke
engines; data from Table 24.

engines have sophisticated electronic controls, which
are capable of varying the fuel injection timing and other
engine parameters to minimize emissions. Four-stroke
engines are more efficiently lubricated and thus the
SOF portion due to fugitive oil emissions is much
lower than for two-stroke engines, being typically 30%
or less.
Available results for four-stroke engines are summar-
ized in Table 24. Data are reported for methylesters of
soybean oil as well as methyl- and ethylesters of
rapeseed oil. Figure 11 shows how biodiesel emissions
change with blend level in four-stroke engines from
two manufactures and model years from 1987 to 1995.
The results include four independent studies using
different DDC Series 60 engines. 19"42'87"9° Data for
Cummins L-10, N-14, and B5.9 engines24'69'9] are also
included• Differences between engines from the two
manufacturers are probably related to the different
approaches taken toward optimization of the NOJPM
trade-off. It is important to note that, when operating on
D-2, engines from both manufacturers meet emissions
standards for the given model year. Figure 11, compared
to Figs 8 and 10 for two-strokes, shows that the NOx
increase in the newer four-stroke engines may be less
than for older two-stroke engines as a function of fuel
oxygen. For example, at 2 wt% oxygen the NOx increase
is roughly 3%, compared to about 5% for two-strokes,
and the PM reduction is roughly 15%, compared to
perhaps 10% for two-strokes. The larger change in PM
emissions might be expected because of the much lower
SOF fraction in four strokes. For the three Cummins
engines, the average NO~ increase was only 0.4% and the
slope of the regression line was less than 0.02. Therefore,
within the uncertainty of these data, NOx emissions did
not increase for the Cummins engines as a group.
_ 2O
10
Jo
~ -10
0
Ilg
r-
c
m
I~. -70 • , i . . . . i
0 2
W e i g h t P e r c e n t O x y g e n in Biodiesel or Blend
Fig. 12. Comparison of change in PM emissions for four-stroke engines, with and without diesel oxidation catalyst, at various
biodiesel levels;data from Refs 24, 69 and 91 for soybeanoil methylester,rapeseed oil methyl-and ethylesters.
Fat and vegetableoil derived fuels 153
Inspection of the data in Table 24, however, indicates
that the two 1987 model year engines did produce a NOr
increase. The 1995 B5.9 engine actually exhibited a
decrease in NOx emissions when operating on soybean or
rapeseed ester fuels. However, the PM reduction
obtainable with the Cummins engines was markedly
less than obtained with the DDC engines. It must be
noted that these conclusions are based on only two
engines for oxygen content above 2%.
Figure 11 suggests that the regulated emissions
change nearly linearly with oxygen content for a given
manufacturer's calibration or engine design approach. If
linearity is assumed, then the air-shed wide emissions
effects of biodiesel in four-stroke engines are inde-
pendent of its concentration in Number 2 fuel and
depend only on engine manufacturer or calibration.
Clearly, a larger body of data on four-stroke engine
emissions is needed. These data must include a wider
range of blending levels, triglyceride sources other than
soy, and a wider range of engine technologies.
For biodiesel content above 20%, the data in Table 24
consistently indicates a small increase in emissions of
SOF, for studies that measured SOF. This suggests that
the combination of biodiesel or a biodiesel blend and a
diesel oxidation catalyst might yield enhanced PM
reduction benefits. Several of the studies reported in
Table 24 examined the effect of oxidation catalysts and
the results are summarized in Fig. 12. Data are available
only for Cummins engines and suggest that a large
enhancement in PM reduction can be obtained by
combining these two approaches. Only one study
tested the oxidation catalyst without biodiesel. Based
on the single data point a definitive conclusion cannot be
drawn, however the data suggest that for four-stroke
engines the use of an oxidation catalyst is far more
• 1967 Cummins I.-10
0 1967 Cummins N-14
• 19e5 Cummins B5.9
- - -- W ~ Catalyst
VV'~llout Catalyst
. . . . t . . . . i . . . . i . . . . i . . . .
4 6 8 10 12
154 M.S. Graboski and R. L. McCormick
effective for PM reduction than biodiesel at any blend
level. When the oxidation catalyst and biodiesel are
combined, PM reductions in excess of 50% can
apparently be obtained at the higher oxygen contents.
One approach to reducing biodiesel NOx emissions to
a level equal to that from D-2 has involved either
increasing cetane number or decreasing aromatics. The
effect of these properties on diesel emissions in general
is revealed in several studies (see Ref. 40, for example).
Generally, biodiesel blends do not respond to ethyl-
hexylnitrate cetane additive treatments. 23'41"42 Sharp 42
found that B-20 did respond to di-t-butyl peroxide in a
DDC Series 60 engine, as noted in Table 24. He was able
to lower NO~ by 6.2% while preserving a 9.1% benefit
in particulate emissions from biodiesel. This is an
important result that needs to be replicated in other
engines and with other diesel base stocks. Note,
however, that B-20 produced no noticeable increase in
NOx for this engine. The same additive had no effect on
NOx in a two-stroke 6V-92. 41
Graboski et al. 19 proposed that NO~ neutral blends
with biodiesel could be produced by altering either the
base fuel aromatic content or natural cetane number.
This thesis was recently tested by Daniels et al. 92 with a
1995 DDC Series 50 engine. A low aromatic fuel
(23.9%) was treated with biodiesel (to make B-20) and a
small amount of cetane (n-hexadecane) to raise the
cetane number of the test blend to the same value as
Number 2 certification fuel. The lower aromatic content
of the fuel compared to certification fuel was enough to
offset the NOx increase produced by the biodiesel. At the
same time, the particulate matter was reduced relative to
the certification fuel by 24%. It could be argued that the
particulate benefit was due to the properties of the base
stock and not the biodiesel since reducing the aromatic
content also reduces particulate matter. However, the
particulate emission for the biodiesei/low aromatic blend
was 14% below that from the low aromatic base stock
alone. This suggests that fuel reformulation with oxygen
and aromatic control is a route to producing NOx neutral
but PM reducing fuels.
Timing changes have been investigated in Cummins
L-1024 and Cummins N-1469 engines and results are
summarized in Table 24. As noted for two-stroke
engines, retarding injection timing can reduce NOx
with a loss of some effectiveness for PM reduction and
a loss of fuel economy. For example, in the Ortech N-14
study, 69 changing the timing actually increased PM
emissions on B-20 to 4.1% above the base diesel level.
The same timing with an oxidation catalyst produced a
23% reduction in PM and a simultaneous 3.5% reduction
in NOx. Similar results were observed in the L-10 study.
Additional data are needed to confirm and quantify these
results, however, the requirement that engines have a
special calibration for operation on biodiesel is not
without costs. The engines will have to be certified for
emissions compliance with the new timing and somehow
restricted to operate only on the specific biodiesel blend
used for certification.
Other diesel oxygenates. Spreen et al. 93-95 studied a
fuel set with cetane number from 45 to 60, aromatics
from 10 to 30%, and 0, 2 and 4% oxygen by weight.
Tests were conducted using a DDC Series 60 and a
Navistar DTA-466, each tested with both 1994 and 1998
calibrations. Oxygen was added as monoglyme (ethylene
glycol dimethylether) and diglyme (diethylene glycol
dimethylether). For the Series 60, the change from 1994
to 1998 calibration involved completely different ECM
programs. For the Navistar engine, timing was simply
retarded 3 °. Fuels with monoglyme were more respon-
sive to ethylhexylnitrate cetane enhancer than diglyme.
The data were regressed and summarized as a model.
Because of the limited number of oxygen combinations,
the models are statistically weak for the effect of fuel
oxygen. For the Series 60, at 5 g NOx calibration, 1%
oxygen increased NOx 0.8% and particulate was reduced
8%. For the 4 g calibration, NOx was increased 0.5% but
the increase was not statistically significant. PM was
reduced 7%. For the DTA-466, only diglyme signifi-
cantly affected NOx at the 5-g calibration. Fuel oxygen
had a significant effect for PM reduction with the 5- and
4-g calibrations. It is not clear how these results
relate quantitatively to biodiesel. They are included
here because they suggest that the effect of oxygen on
NOx emissions might be further diminished in 1998
calibration engines.
Chassis studies with four-stroke engines. Peterson and
Reece 96 investigated 1994 and 1995 Cummins B 5.91
engines in two Dodge pickup trucks on a chassis
dynamometer using the double arterial cycle and the
chassis version of the Heavy-Duty Transient test.
Rapeseed methyl- and ethylester fuels were used in
testing. The arterial cycle gave lower emissions on a
g/mile basis compared to the heavy-duty chassis cycle
but the relative effect of fuel oxygen on emissions was
essentially the same. NOx decreased by 13% and PM
increased by 43% compared to diesel for the ethylester.
NOx for the methylester was 3.4% higher than for the
ethylester with the 1994 truck, while PM was 6% higher.
It is not clear why the chassis based emissions do not
follow the trends observed by Sharp 91 using the engine
dynamometer test procedure. The rapeseed ethylester
used by both Sharp 91 and Peterson and Reece 96 was
94.75% esterified and contained significant amounts of
glycerol and mono-, di- and triglycerides. While this
low purity level might prove problematic in engine
endurance tests, it is not known how purity influences
emissions performance.
Other emissions studies. FEV Engine Technology 18
investigated injection timing and injection pressure for
Table 25. Thirteen-mode steady-state emissions for the Navistar
HEUI engine; % change relative to base diesel t8
Biodiesel 10 20 30 50 100
(%)
NO~ 3.5 5.3 6.9 15.8 28.2
PM -33.9 -24.1 -37.5 -26.8 -33.9
HC -28 -32 -53 -50.7 -75.5
CO -10.6 -8.1 -18.8 -6.9 -13.8
BSFC 1.9 2.2 3.2 8.5 12.4
 Fat and vegetableoil derived fuels
various soy blends with diesel, in comparison to diesel,
using a 13-mode steady-state test with the Navistar 7.3 1
HEUI engine. It is important to note that NO, emissions
are primarily related to engine load and speed and less
dependent on whether the operation is transient or steady
state but particulate and other emissions are significantly
affected by transient operation. Table 25 presents the
emissions from the stock engine. Data are presented
which provide several strategies for optimizing the fuel
management function with respect to emissions. FEV
found that NOx increased with biodiesel under all
conditions of speed and load. However, the rate of
generation of particulate and its form varied with
conditions. Biodiesel blends reduced particulate at high
speed and all loads. At lower speeds, particulate was
reduced at light and heavy loads but particulate was
increased at intermediate loads. SOF was always higher
for biodiesel.
The FEV steady-state study also found that relatively
low blending levels of 10-30% methyl soyester are more
responsive to parameter changes over the engine map
than high blends (50 and 100%). For the low oxygen
blends, it was possible to lower NOx at fixed PM but not
to simultaneously reduce PM and NO~ using engine
timing and pressure changes. Any change made to
pressure or timing for biodiesel blends worked equally
well for Number 2 diesel. Thus, NO, emissions increased
and PM, CO and THC emissions fell relative to diesel at
any fixed configuration. An exhaust gas recirculation
(EGR) strategy was examined and it was claimed that a
proposed strategy (not necessarily optimal) could reduce
NO, by 10% without PM or fuel economy penalty.
Again, all fuels might gain from this benefit.
Police e t al. 28 investigated a direct injected 90 bhp
diesel engine using a 13-mode steady-state test with
Number 2 diesel and 100% rapeseed oil methylester.
Both fuels had the same cetane number (51.5-51.6). The
diesel had a high boiling with a T-90 of 346°C. At low
speed (2200 rpm), as torque increased the ratio of NO~
lbr the ester fuel compared to diesel increased from 1.2
to 1.4, while at rated speed (3800 rpm), the NOx ratio
was constant at about 1.2. These data indicate that NOx
emissions increase at all points in the engine map but
even more so under lugging conditions.
Marshall 22 conducted multi-mode steady-state testing
using a Cummins L-10 engine which showed that NO~
increased from 6.4 to 7.4 g/bhp-hr when comparing D-2
and 100% methyl soyester. He examined ethanol, ETBE
(ethyl t-butylether), and alkylate as NOx reduction
additives. Addition of 20% heavy alkylate made a NOx
neutral fuel compared to the base diesel. This agrees
with the results of Daniels et al. 92 who employed
n-hexadecane (similar to alkylate) and reduction of
aromatic content to reduce NOx emissions. These
studies demonstrate how diesel can be reformulated to
include oxygenates but with a lower aromatic content to
simultaneously control emissions of NO~ and PM.
McDonald et al. 97 examined unique mining transient
cycles. Testing was conducted without and with a diesel
oxidation catalyst on D-2 and B-100. The catalyst
155
produced sulfate under some heavy load test conditions
resulting in increased particulate. In the cycles driven,
soy ester reduced NOx and particulate. NO, fell by 5 to
10%. Particulate matter without catalyst fell 25 to 33%.
With catalyst, the PM fell 50% relative to D-2. Peak
power decreased 9% and fuel consumption increased
13.7% on soybean oil methylester. The fact that NOx and
PM both decreased may be a result of the specific cycles
used or may be related to the calibration of the
Caterpillar engine employed.
Schumacher et al. 88 examined five tractors using the
ISO 8178 CI, 8-mode steady-state test. Peak power
generally fell in proportion to the soy diesel content.
Smoke was reduced with most soy diesel blends. With
neat ester, smoke was reduced 50 to 70% and
simultaneously NOx increased by 3 to 35%. GoyalTM
used the ISO 8178-4 off-road test with neat methyl
soyester. A Deere 4045T engine run on soyester showed
a 4-6% power loss. Emissions showed a 10% NOt
increase and a 4% PM decrease. By adjusting the fuel
pump for equal engine output power, the NOx emission
fell to a 2% increase but PM increased by 12%. PM was
much higher in SOF for the soyester (28% for diesel
versus 70% with soyester). With a 4 ° timing retard, NOt
fell more than 20% and soy diesel NOx was nearly equal
to diesel NOx at both power settings. PM was 25% lower
than base diesel.
Rantanen et al. 27 presented the results of a study
which utilized four European heavy duty engines
ranging from 200 to 280 bhp with the ECE R49 multi-
mode steady-state test. Rapeseed oil methylester
emissions were compared to a typical Finnish diesel
fuel which has an analysis essentially the same as U.S.
average Number 2 diesel except for a higher sulfur
content. Neat rape methylester used in three different
engines produced a 4-10% increase in NO~ and a 2 -
33% reduction in PM. Krahl et al. 99 reviewed European
data on regulated emissions from rape methylester. Most
data are for light duty diesels using various European
multi-mode steady-state engine tests and U.S. light duty
FTP driving cycle. Emissions are highly dependent on
the driving cycle. NOn increased for all cycles and
engines discussed. The typical increase was 20%.
Particulate generally decreased and the PM reduction
was cycle dependent, with the FTP giving the smallest
decrease (0-20%), and the 13-mode steady-state test
giving a 0-60% decrease.
Staat and Gateau 29 reported the results of a 3-year test
program using rape methylester. Chassis and engine
testing using Renault bus engines for 0 and 100% ester
were presented. Using the 13-mode engine test, NO~
emissions increased by 9.5%. Using the AQA chassis
cycle NOx decreased by 6.4%. PM decreased by 37.5%
in the engine test and by 8.3% in the chassis test.
Montagne3° presented data for naturally aspirated and
turbocharged Renault truck engines fueled with 5 and
20% rape methylester blends using a European chassis
truck driving cycle. NOx increased by up to ~ 5% with
increasing ester level for two naturally aspirated and two
turbocharged engines tested in vehicles. Particulate was
156 M.S. Graboski and R. L. McCormick

20~ Biodill~ 3S% ~iolIieIiil

12oo- 1200"

-. . °° (
~ ,.,o ,. '~*
\ ~ ./-~10.,~ °:~ ,'~--;L

(_ 2. ,.,zx

eO0 800 1000 1200 14~0 ~00 1800 800 800 1000 1200 1400 1600 1800

65% Biodiesel 100% Biodiesel

• 1.0 I o ) "~, 1~ 1.0 I

o. ,,,~,
''~:--~.0) ,o
~ ~
4~0::~
~., :~2'- , o ~ , 7 ~ . . ~ ~ '(~,~.~
~ ..~Y~,~-:~-'~-~'?/~ ~ '~ ° ~ ° ~
~00 800 10~0 1200 1400 1(100 lifO0 ~0 800 10~0 1200 1400 1600 1800

q.,*d, ~ Speed, q . .

Fig. 13. Contour plots showing ratio of NOx emission with biodiesel to NOx for Number 2 diesel as a function of speed and torque in
the heavy-duty transient test. DDC series 60 engine; data from Ref. 19.

nearly unchanged for three engines but doubled for the
fourth engine with B-20. For that vehicle, no PM change
was seen for B-5.
While the steady-state emission studies described in
this section are not relevant from an emissions
compliance point of view, they confirm that an
increase in NOx emissions is typically observed using
biodiesel. However, NOx and PM are highly dependent
upon the engine or chassis cycle employed and
under some conditions PM increased and NOx went
down. It is not clear from these studies whether the NOx
increase occurs at all speeds and loads or only in specific
regions of the engine map. The very different test
procedures and blending Number 2 diesel stocks used
in these studies make it difficult to draw general
conclusions.
4.3. Discussion of Increased NOx Emission for
Biodiesel
Data from the soydiesel study of Graboski e t al. 19
have been reanalyzed to gain a greater understanding of
the increase in NOx emissions. Modal or real time NOt
emissions data for biodiesel or biodiesel blends, as ppm
NOx in the diluted exhaust, have been normalized by
dividing by the real time NOx emissions for Number 2
diesel. This NOx ratio is then plotted as contours over the
engines speed-torque map. This approach was used to
generate the plots in Figs 13 and 15.
Figure 13 shows contour plots for neat soydiesel and
soydiesel at several blend levels. The NOx emission is
clearly dependent upon speed and load. The figure shows
that NOx is elevated at low speed and high torque
 Fat and vegetable oil derived fuels
1200
0.00 0.23
1000
0.00 0.00
800
0.25 1.29
¢: 6oo
0.95 0.74
400
0.45 0.50
200
0.73 0.58
0
600 800 1000
Fig. 14. Percentage of total work generated over different regions of the heavy-dutytransient cycle; shaded regions represent nearly
75% of work generated.
(roughly 1000 rpm and 600-1000 ft-lb) for the Series
60 engine. NOx levels are also elevated in the
1200-1600 rpm range and at torque below 400 ft-lb. At
the highest speeds and loads, NO~ emissions are
essentially unchanged with biodiesel. The NO~ increase
becomes more significant as the oxygen content of the
fuel increases. In Fig. 14, the work done in various
regions of the transient cycle is shown as a percentage of
total work. The shaded areas represent ~ 75% of the
work performed and so increased NOx concentration in
the exhaust in these regions will have the biggest impact
on the NOx mass emission. Clearly the most important
region of the DDC Series 60 map for NOx emissions
increase is the 1400-1600 rpm and 200-600 ft-lb range.
The increase in exhaust NOx concentration observed in
this region most likely accounts for all of the increase in
NO~ mass emissions observed for this engine when
operating on biodiesel fuels.
McCormick e t al. 87 reported on the relative NOx
emissions for 2% oxygen as octanol or as methyl
soyester, compared to a base Number 2 diesel for
transient tests conducted with the same DDC Series 60
engine. Figure 15 shows contour plots of the modal (real
time) data collected over the test cycle. The increased
NOx emissions are concentrated in the same regions as in
the previously described study. The type of oxygenate
157
2.22
2.14
1.09
0.24
0.16
0.17 0,20 0.63 0.00
1200 1400 1600 1800
Speed, rpm
has an impact on the local NOx emission. Octanol
produces a much smaller relative NOx peak under the
lugging condition and actually lowers NOx at high speed
and load. The form of the oxygenate is clearly important
in determining the NOx emission and further research
into the causes of this could help to improve the emission
characteristics of biodiesel and other oxygenated diesel
fuels.
Fuel density is known to effect emissions of NOx
from diesel engines. For example, Signer et al. loo report
a 3-4% increase in NOx for a 3.5% increase in fuel
density using the EEC 13-mode test cycle. The NO~
increase occurred because the fuel injectors inject a
constant volume or larger mass for the more dense fuel,
at a given speed and load. Because a larger mass of fuel
is burned, more NO~ is produced. As noted in Table 9,
the density change for neat biodiesel relative to base
diesel fuel is ~ 3.5%. Note, however, that biodiesels and
biodiesel blends have a reduced heating value relative to
the Number 2 diesel. For example, the heating value of
the 2 wt% oxygen soyester blend is more than 2% lower
than for the base diesel but density would be expected to
be well below 1% different. This lower heating value
effect competes with, and should be larger than the effect
of fuel density on the heat and NOx generated per
injection.
158 M.S. Graboski and R. L. McCormick

NO=(mye=ler)/NO,(diuel)
1200

1000

80O

.Q

600
e"
Er
40O

200

60O 800 1000 1200 1400 1600 1800

Speed, rpm
NO=(octanol)/NO=(diesel)
1200

d= 6o0
$

600 800 1000 1200 1400 1600 1800

Speed, rpm
Fig. 15. Contour plots showing ratio of NOx emission with oxygenate to NO~ emission without oxygenate as a function of speed and
torque in the heavy-duty transient test. DDC series 60 engine, 2 wt% fuel oxygen, 17 vol% oxygenate, s7

Parker I°l has recently discussed possible causes for
the increased NOx during biodiesel and diesel oxygenate
combustion:
1. An increase in the flame temperature in either the
premixed or diffusional burn regimes. While
oxygenated fuels have a lower adiabatic flame tem-
perature, carbonaceous PM or soot particles are
very effective heat radiators. Therefore, the net
result of the PM reduction caused by supplying
oxygen to the fuel pyrolysis zone may be to
increase flame temperature because of this loss of
radiant heat transfer.
2. Spray properties may be altered due to differences
in viscosity, surface tension, and fuel boiling point
for the oxygenated fuels. Spray properties affected
may include droplet size, droplet momentum and
hence degree of mixing and penetration, evapora-
tion rate, and radiant heat transfer rate. A change in
 Fat and vegetable oil derived fuels
any of these properties might lead to different rela-
tive duration of the premixed versus diffusional
burn regimes. Since it is possible that different
fuel fractions are consumed in premixed and diffu-
sional burn, and since the two burning processes
may have different pollutant formation character-
istics, this difference in ignition delay could be the
cause of the increased NOx emission. Changes in
spray properties may also change characteristics of
the diffusional burn regime that lead to increased
flame temperature and higher levels of NOr
formation.
3. Oxygenates may change ignition delay in ways not
detected by measuring cetane number. Ignition
delay within an engine can be a function of both
the fuels used and fuel spray properties. The impor-
tance of ignition delay is that longer delays provide
time for more fuel to become premixed and
therefore consumed in the premixed phase rather
than in the diffusional burn phase with possible
differences in emissions as discussed above.
4. Fuel chemistry effects in the flame region could
account for a change in nitric oxide production.
Thermal, or Zeldovich NO is unaffected by fuel
chemistry, however, prompt NO can account for
30% or more of the total nitric oxide emission. ~°2
Since prompt nitric oxide is sensitive to radical
concentrations at the flame front, an increase in
prompt NO could be attributed to fuel chemistry
effects. The various mechanisms of NOx formation
have been extensively reviewed. 1°3
5. Removal of the carbonaceous PM from the com-
bustion environment may eliminate NO-carbon
reactions. The importance of NO-carbon reactions
in diesel combustion is unknown.
Given that not all oxygenates described in the
literature increased NO~ but all gave a similar level of
PM reduction; the data reported here do not support
hypothesis (1) above. The current data are insufficient to
distinguish between the remaining hypotheses, however,
we can discuss the effect of oxygenated blending on the
fuel physical properties important in spray combustion.
Diesel spray properties, specifically the droplet size
distribution and Sauter mean diameter, are influenced by
fuel surface tension and viscosity. 39 Sauter mean
diameter has been shown to increase with increasing
surface tension and viscosity, t°4 As noted, increased
Table 26. Smoke opacity results (%) for Number 2 diesel and biodiesel blends using the CFR 40 Part 86 Subpart I procedure
Reference Engine Set-up
60 DDC 6V-71 N-77 MUI Stock
Stock
Stock + cat
Stock + cat
69 Cummins N-14-87 MUI Stock
Stock
Stock
Stock + cat
159
droplet size can reduce the fraction of fuel burned in the
premixed combustion phase and lead to increased
duration of diffusion flame combustion. We have
estimated the surface tension and viscosity of biodiesel
and other diesel oxygenate blends and found changes in
fuel properties that are easily large enough to impact
spray properties which in turn impact emissions. 87
Another factor which may be relevant to the increased
NOx emissions from biodiesels is the relatively high
boiling point of these oxygenates. Higher boiling point
fuels may require longer to be heated to boiling and to
vaporize. This effect may reduce the rate of droplet
evaporation and lead to consumption of a smaller
fraction of the fuel in premixed relative to diffusion
burn combustion. Clarification of these issues awaits
additional engine, combustion bomb, and modeling
studies.
4.4. Smoke Opaci~
Smoke emissions are regulated using a procedure
specified in the Code of Federal Regulations. Jo5 Smoke
is only loosely related to total particulate since opacity is
greater for dark smoke than for white smoke and in fact,
smoke opacity may be completely uncorrelated with
mass emissions of PM. In most instances, smoke opacity
is used as an indicator of engine malfunction in an
inspection and maintenance program. Only a limited
number of studies have examined smoke opacity using
the CFR procedure and these results are summarized in
Table 26. Fosseen 6° report data for a two-stroke engine
that show no benefit in smoke opacity for biodiesel.
Combination of an oxidation catalyst and biodiesel
provided a significant reduction in smoke opacity.
Ortech 69 reported smoke opacity measurements for
B-10 and B-20 soy blends in a four-stroke engine. The
use of biodiesel significantly reduced smoke opacity.
Biodiesel had the greatest effect on smoke in the lugging
mode where B-10 reduced smoke by 28.6% and B-20
reduced smoke by 50%. Combining an oxidation catalyst
with B-20 provided only a small additional benefit.
A number of studies report smoke opacity for engines
or vehicles at various speeds and loads using non-
standard procedures. Lucas 7° reported the results of snap
idle and long term smoke reduction benefits using
biodiesel blends with JP-8 compared to JP-8 alone. All
vehicles showed marked smoke reduction with the
Fuel Mode
Acceleration Lugging Peak
D-2 1.2 1.8 1.8
B-20 (Soy) 1.1 1.9 2.0
D-2 1.4 2.1 2.1
B-20 (Soy) 0.9 1.7 1.7
D-2 7.1 1.4 22.5
B-10 (Soy) 6.3 1.0 20.7
B-20 (Soy) 5.4 0.7 18.3
B-20 (Soy) 5.3 0.7 17.3
160 M.S. Graboski and R. L. McCormick
biodiesel blends in snap idle testing. One vehicle tested
had a initial opacity of 57% without biodiesel. After the
introduction of biodiesel blends, the initial opacity was
46% falling to 22% after 10000 miles. Biodiesel might
have exhibited detergent action in the fuel system.
Several studies have noted that the Bosch smoke number
is reduced 10-20%, especially at higher loads, when
operating on B-20.18"2s'4s Fosseen, in an NBB funded
study of biodiesel performance in a bus fleet, also noted a
20% reduction in opacity. ~°6 Based on these data it
seems likely that, for newer two-stroke and four-stroke
engines, biodiesel significantly reduces smoke opacity.
4.5. Unregulated Emissions and Air Toxins
At some future time, regulatory agencies may limit the
emission of specific compounds, classes or compounds,
or fractions of the exhaust such as SOF. Thus it is
important to have an understanding of the impact of
biodiesel on these emissions, and to understand if use of
biodiesei leads to an increase in emissions of any specific
classes of toxic compounds. Air toxic emissions from
diesel can be divided into two groups: those in the THC
portion of the gaseous emission and multi-ring PAH
found in the SOF portion of the particulate. Many
volatile compounds are known to have mutagenic or
carcinogenic activity. The most important of these are
light aldehydes (such as formaldehyde and acetaldehyde)
diolefins especially 1,3-butadiene, and light aromatics,
particularly benzene. Only limited data on these
emissions are available from testing in the U.S. on soy,
tallow and waste oil based esters. The European
Community has gathered more extensive data for rape
methylesters, using primarily the European steady-state
test, on a variety of heavy-duty diesel engines. However,
few studies have reported quantitative mass emissions of
air toxins for biodiesel fuels. Thus, at this time it is
difficult to draw general conclusions on unregulated
emissions for biodiesei and this is clearly an area in need
of more extensive research.
4.5.1. Soluble organic fraction
Particulate is conventionally speciated into three
fractions. These are soot or carbon, liquids derived
from fuel and oil (SOF), and sulfuric acid from fuel
sulfur (measured as sulfate). SOF is unregulated except
in California ARB diesel. SOF contains PAH and nitro-
PAH compounds known to be highly mutagenic. As
noted in an earlier section of this review, much of the
SOF from two-stroke engines is engine lubricant and so
it is difficult to assess the impact of biodiesel on the total
SOF emission. Based on steady-state testing, biodiesel
particulate is believed to be much higher in SOF than
Number 2 diesel fuels, although this is not particularly
clear from the transient emissions data reported in Tables
20, and 23. The fact that use of diesel oxidation catalysts,
which are designed to convert SOF, leads to even higher
PM reduction for biodiesei fuels than for Number 2
diesel also indicates that biodiesel increases SOF.
Future research must address the questions of the
effect of biodiesels on mass emissions of SOF and on
the nature of the SOF with respect to reactive, toxic, and
mutagenic properties. Some data related to these
questions are described in the section on PAH emissions
below.
4.5.2. Poly-aromatic hydrocarbons
A large number of qualitative studies seem to indicate
that use of biodiesel decreases PAH. McDonald e t al. 97
examined emissions for off-road mining applications
using a Caterpillar 3304 PCNA and the ISO 8178-C! 8
mode off-highway test as noted above. Mutagenicity
with soyester and a diesel catalyst was reduced to one-
half of that of D-2. The reduction is due to a reduction in
emissions of PAH. Krahl et al. 99 reviewed European
data on air toxins from rape methylester fuels. Most data
were based on light duty diesels using various European
multi-mode steady-state engine tests and the U.S. light
duty FFP driving cycle. Emissions are highly dependent
on the driving cycle. PAH emissions with biodiesel in
direct injection engines ranged from 80 to I 10% of those
for D-2 for the FTP, and from near zero to 80% of diesel
PAH emissions for various steady-state tests. Staat and
Gateau29 reported the results of a 3-year test program
using rape methylester blends. Chassis and engine
testing using Renault bus engines for 0, 30 and 50%
blends suggested that total PAH emissions were
unchanged. Montagne3° presented data for naturally
aspirated and turbocharged engines Renault truck
engines fueled with 5 and 20% rape methylester blends
using a European chassis truck driving cycle. For
turbocharged engines, rape methylester decreased
PAH by 40-50%. Shafer ~°7 reported the results of a
study by Mercedes Benz using palm oil esters. The
Mercedes Benz indirect injection bus engine employed
experienced a total PAH decrease.
In much more quantitative studies, Rantanen et al. 27
presented results for air toxins as well as regulated
emissions from rape methylesters. Brake specific PAH
emissions were reported at several steady-state condi-
tions. Total PAH emissions decreased by approximately
75% for B-30 and by more than 85% for B-100 relative
to Finnish D-2. Mutagenicity tests were conducted based
upon Salmonella strains that are highly sensitive to nitro-
PAH compounds. This showed mutagenic activity was
only about 10% lower for the biodiesel particulate than
for D-2, for the one set of engine data reported. Using
nitro-PAH insensitive strains, the mutagenicity of rape
methylester exhaust fell to about one-third that of diesel.
Thus, for rape methylester, the total PAH emission is
lower but the mutagenic activity of the PAH appeared to
be significantly higher than for diesel. This may be
caused by the presence of nitrated polycyclic hydro-
carbons like l-nitropyrene. Based upon EPA transient
tests in a Cummins B5.9 engine, Sharp 91 reported that
PAH emissions were also reduced with biodiesel. For
neat ethyl- and methylesters of rapeseed oil brake
specific PAH emissions declined by 37 and 54%,
 Fat and vegetable oil derived fuels
respectively. The PAH reduction was in the range of 20-
30% for B-50 blends and was insignificant for B-20.
Kado t°8 reported on PAH emissions from diesel and
neat methyl and ethyl rape esters. The GC/MS
analytical technique employed was reported to exhibit
a standard deviation of about 10%. Emissions of
phenanthrene, pyrene and benzanthracene were 2 0 -
40% less for the ester than for diesel. Benzopyrene
increased slightly. Using AMES Salmonella testing, the
esters exhibited lower activity exhaust than the diesel
base fuel.
4.5.3. A l d e h y d e s
As for PAH, a great deal of qualitative information is
available on the effect of biodiesel on emissions of
aldehydes. McDonald e t al. 97 examined emissions for
off-road mining applications using a Caterpillar 3304
PCNA and the ISO 8178-C1 8 mode off-highway test as
noted above. Formaldehyde was not significantly
increased using a blend or neat soyester. A diesel
oxidation catalyst reduced formaldehyde by 26%. Krahl
et al. 99 found that total aldehydes for direct injection
engines generally increased with biodiesel by 0-75%,
independent of test cycle. Staat and Gateau z9 reported
that for 0, 30 and 50% blends, C~ through C5 aldehyde
emissions increase with ester concentration. Acrolein
increased by 50% with 50% ester blends. The increase in
acrolein, a carcinogenic air toxin, was attributed to
glycerides in the boidiesel fuel, again reinforcing the
need fi)r high purity biodiesel. Montagne 3° presented
data for naturally aspirated and turbocharged engines,
Renault truck engines fueled with 5 and 20% rape
methylester blends using a European chassis truck
driving cycle. For turbocharged engines, rape methyl-
ester increased formaldehyde by about 60%, and
increased acrolein by 25-40%. Shafer ~°v reported the
results of a study by Mercedes Benz using palm oil
esters. Compared to diesel, all aldehydes except
acrolein decreased. The increase in acrolein was
attributed to glycerol in the fuel. Above 50% load at
rated speed all regulated and unregulated emissions
for the ester were lower, while at lighter load and rated
speed, diesel emissions are lower. In chassis studies
with buses, Howes and Rideout 67'68 reported no
increase in formaldehyde emissions for B-20 (soy)
relative to D-2.
Rantanen et al. 25 presented results lbr air toxics as
well as regulated emissions from rape methylesters.
Exhaust gases were analyzed by FTIR. Formaldehyde
was found above the detection limit in diesel and rape
methylester exhaust at the same levels. Thus, even
though rape methylester could yield formaldehyde by
lbrmation of a methyl radical from the ester, the authors
suggest that this did not occur to any significant degree.
Based upon EPA transient tests in a Cummins 5.9-1
engine, Sharp 91 reported that biodiesel (REE and RME)
does not in general increase aldehyde emissions and
oxygenates may have actually produced a reduction in
emissions of formaldehyde.
161
4.5.4. S u m m a r y
There is considerable data that emissions of SOF, or at
least the fraction of the PM that is SOF, increases for
biodiesel. There also seems to be agreement that the use
of biodiesel results in both a decrease in emissions of
PAH, and in the mutagenic activity of the diesel exhaust.
The mutagenic activity of the PAH itself, however, may
be higher than that from conventional diesel. Because of
the limited number of truly quantitative studies (such as
Refs 27, 91 and 108), it is not possible to state the
magnitude of the PAH decrease that might be expected
for a given engine technology or biodiesel source. The
most quantitative studies find no increase in aldehyde
emissions for high quality (high purity) biodiesel.
However, emissions of acrolein may increase if glycerol
or glycerides are present in the fuel.
There is some evidence that emissions of benzene
increase for rape methylester but it is unknown if this
phenomenon is generally true for all biodiesel fuels and
all drive cycles. For example Krahl et al. 99 found
benzene emissions for direct injection engines fell by
50% for the FTP but increased by 40% in steady-state
testing. Staat and Gateau 29 reported benzene emissions
increased by about 15% for 50% ester fuel. Shafer ~°7
reported benzene, xylenes, and toluene increased with
palm esters. It is important to note that definitive studies
in this area have not been performed. Therefore, any
conclusions drawn regarding unregulated emissions and
toxins must be treated as preliminary observations.
5. CONCLUSIONS AND SUMMARY OF RESEARCH NEEDS
Research and development efforts using primarily
methylesters of various fats and oils have shown that
these biodiesels can be suitable fuels for diesel engines.
The use of biodiesel in neat or blended form has no effect
on the Btu based engine fuel economy. The lubricity of
these fuels is superior to conventional diesel and this
property is imparted to blends at levels above 20 vol%.
Emissions of PM can be reduced dramatically through
the use of biodiesel in engines that are not high lube oil
emitters. Emissions of NOx increase significantly for
both neat and blended fuels in both two- and four-stroke
engines, The increase may be lower in newer, lower NOr
emitting four-strokes, but additional data are need to
confirm this conclusion. Efforts at eliminating this NO,
increase based on combinations of injection timing
changes and SOF oxidation catalysts are successful but
work equally well for petroleum derived diesel.
Biodiesels manufactured from soybean or rapeseed oils
cannot be priced low enough for market forces alone to
guarantee their use. Price is almost totally governed by
feed stock cost indicating that lower cost waste oils may
be more economically attractive. Other approaches, such
as plant breeding or modification to improve oil yield or
chemical modification of the oil to produce high value
coproducts may also have promise.
The data reviewed in this article suggest a number of
162 M.S. Graboski and R. L. McCormick
important areas for future research. Among the most
important recommendations is the need for all future
studies to employ biodiesel of well known composition
and purity and to report detailed analyses. Other areas for
additional research include:
1. Examination of lower cost feed stock materials for
manufacture of esters, including studies of the
transesterification process applied to these feeds,
purification and properties of the ester product,
and performance in engines and vehicles.
2. Development of a highly active heterogeneous
catalyst for the transesterification reaction, capable
of achieving very high glyceride conversion, is
needed. While this development will have only a
minor impact on biodiesel production cost, it will
greatly simplify the production process. This pro-
cess simplification will allow improved control of
product quality.
3. Processing schemes for producing additional
products from fats and oils, as well as biodiesel
with improved properties (higher stability and
lower boiling point, for example) should be investi-
gated. By producing a suite of valuable products,
the biodiesel sales price might be lowered
significantly.
4. The effect of biodiesel purity on properties,
stability, and performance in engines and vehicles
needs further investigation. The purity levels
necessary for achieving adequate engine
endurance, compatibility with coatings and elasto-
mers, cold flow properties, stability, and emissions
performance must be defined.
5. A detailed understanding of what constitutes an
acceptable level of oxidative and biological
stability is needed, along with knowledge of
acceptable levels of oxidative degradation pro-
ducts.
6. A detailed understanding of the effect of biodiesel
chemical structure on cold flow properties and
stability is needed. Additionally, flow improver
additives and stabilizers specific for biodiesels
and biodiesel blends need to be developed.
7. Fundamental modeling, combustion bomb, and
shock tube studies of biodiesel combustion, includ-
ing the causes of increased emissions of NOx, are
needed. These should include the impact of bio-
diesel on fuel spray properties. Basic research in
engines to more fully understand the NOffPM
tradeoff as a function of speed and torque may
allow optimization of engine calibration for biodie-
sel. These studies will apply not just to biodiesel
but to diesel oxygenates in general.
8. Substantially more in-use and engine-testing data
in four-stroke engines using all sources of biodiesel
are required. Detailed quantitative measurements
of regulated emissions and unregulated toxic
emissions are needed.
9. The effect of cetane improvers and blending diesel
reformulation on biodiesel emissions performance
should be investigated in much more detail.
10. Definitive studies of the effect of biodiesel from
various sources, and diesel oxygenates in general,
on emissions of toxic, mutagenic, and carcino-
genic compounds need to be performed.
Acknowledgement--The authors wish to thank the U.S.
Department of Agriculture, Office of Energy and New Uses
for supporting the preparation of this review.
REFERENCES
I. Walton, J., Gas & Oil Power, p. 167, July 1938.
2. Martinez de Vedia, R., Diesel Power and Diesel
Transportation, p. 1298, December 1944.
3. Huguenard, C. M., Dual fuel diesel engines using cotton-
seed oil with variable injection timing. M.S. thesis, Ohio
State University, 1951.
4. Bruwer, J. J., van D Boshoff, B., Hugo, F., du Pleiss L. M.,
Fuls, J., Hawkins, C., van der Walt, A. and Englebrecht,
A., Sunflower seed oil as an extender for diesel fuel in
agricultural tractors. Presented at the 1980 Symposium of
the South African Institute of Agricultural Engineers, 11
June 1980.
5. Varde, K. S., Vegetable oil fuels. In Proceedings of the
International Conference on Plant and Vegetable Oils as
Fuels, American Society of Agricultural Engineers,
Publication 4-82, p. 303, 1982.
6. Baranescu, R. A. and Lusco, J. J., Vegetable oil fuels. In
Proceedings of the International Conference on Plant and
Vegetable Oils as Fuels, American Society of Agricultural
Engineers, Publication 4-82, p. 312, 1982.
7. Fort, E. F. and Blumberg, P. N., Vegetable oil fuels. In
Proceedings of the International Conference on Plant and
Vegetable Oils as Fuels, American Society of Agricultural
Engineers, Publication 4-82, p. 374, 1982.
8. Johanson, O. and Mordstrom, O., Vegetable oil fuels. In
Proceedings of the International Conference on Plant and
Vegetable Oils as Fuels, American Society of Agricultural
Engineers, Publication 4-82, p. 337, 1982.
9. Peterson, C. L. and Feldman, M., EMA test cycles:
influence of fatty acid composition on engine deposits, in
The potential of vegetable oil as an alternate source of
liquid fuel for agriculture in the Pacific Northwest--V.
Final report of College of Agriculture and Engineering,
University of Idaho, pp. 132-137, 1987.
10. Bacon, D. M., Brear, F., Moncrieff, I. D. and Walker, K.
L., The use of vegetable oils in straight and modified form
as diesel engine fuels. In Beyond the Energy Crisis,
Volume 3, Third International Conference on Energy Use
Management, ed. R. Fazzolare and C. B. Smith. Pergamon
Press, New York, 1981, p. 1525.
I 1. Engler, C. R., Johnson, L. A., Jegasothy, H., Reddy, M.B.
and Yarbrough, C.M., Proceedings: Vegetable Oil as a
Diesel Fuel Seminar 111,Peoria, IL, p. 71, 1983.
12. Freedman, B., Pryde, E. H. and Mounts, T. L., J. Am. Oil
Chem. Soc., 1984, 61, 1638.
13. Reed, T. B., Graboski, M. S. and Gaur, S., Biomass and
Bioenergy, 1992, 3, 111.
14. Peters, M. S. and Timmerhans, K. D., Plant Design and
Economics for Chemical Engineers. McGraw-Hill, New
York, 1980.
15. Withers, R. V. and Noordam, M., Proceedings of the 3rd
Liquid Fuels Conference, 15-17 September, Nashville,
TN, 366pp., 1996.
16. Fosseen Manufacturing and Development, Emission
testing on biodiesel and biodiesel blends. Final Report
No. NSDB4FI5 to National Soy Diesel Development
Board, Jefferson, MO, July 1994.
17. Manicom, B., Green, C. and Goetz, W., Methyl soyate
evaluation of various diesel blends in a DDC 6V-92TA
 Fat and vegetable oil derived fuels
engine, Ortech International. Final Report No. 93-E14-21
to Fosseen Manufacturing and Development, 12 April
1993.
18. FEV Engine Technology, Inc., Emissions and perfor-
mance characteristics of the Navistar T444E DI engine
fueled with blends of biodiesel and low sulfur diesel.
Phase 1 Final Report to National Biodiesel Board, 6
December 1994.
19. Graboski, M. S., Ross, J. D. and McCormick, R. L., Soc.
Automotive Eng. Technical Paper No. 961166, 1996.
20. Schumacher, L., Chellappa, A., Wetherell, W. and
Russell, M. D., The physical and chemical characteriza-
tion of biodiesel low sulfur diesel fuel blends. Final Report
to National Biodiesel Board, Jefferson, MO, 30 December
1995.
21. McDonald, J., Purcell, D., McClure, B. and Kittelson, D.,
Soc. Automotive Eng. Technical Paper No. 950400, 1995.
22. Marshall, W., Improved control of NOX emissions with
biodiesel fuels. Final Report, DOE Contract DE-AC22-
94PC91008, March 1994.
23. Clark, S. J., Wagner, L., Schrock, M. D. and Piennaar, P.
G., J. Am. Oil Chem. Soc., 1984, 61 (10), 1632.
24. Stotler, R. and Human, D., Transient emission evaluation
of biodiesel fuel blend in a 1987 Cummins L-10 and DDC
6V-92-TA. ETS Report No. ETS-95-128 to National
Biodiesel Board, 30 November 1995.
25. Midwest Biofuels Inc., Biodiesel Cetane Number Engine
Testing Comparison to Calculated Cetane Index Number.
Midwest Biofuels Inc., Overland Park, Kansas, 1993.
26. Reece, D. and Peterson, C. L., Progress report Idaho on-
road test with vegetable oil as a diesel fuel. In
Proceedings: First Biomass Conference of the Americas,
National Renewable Laboratory, 30 August-2 September,
p. 891, 1993.
27. Rantanen, L., Mikkonen, S., Nylund, L., Kociba, P.,
Lappi, M. and Nylund, N.-O., Soc. Automotive Eng.
Technical Paper No. 932686, 1993.
28. Police, G., Prati, M. V., Auriemma, M. and Alfuso, S.,
Regulated emissions of DI diesel engines fuelled with
methyl ester of rape seed oil. In Fuels for Automotive and
Industrial Diesel Engines. Institution of Mechanical
Engineers, London, p. 139, 1993.
29. Staat, F. and Gateau, P., Soc. Automotive Eng. Technical
Paper No. 950053, 1995.
30. Montagne, X., Soc. Automotive Eng. Technical Paper No.
962065, 1996.
31. Adept Group, Emissions and engine performance of soya
and canola methyl esters with ARB#2 diesel fuels, Report
to Saskatchewan Canola Development Commission,
Saskatoon, Saskatchewan, July 1995.
32. Peterson, C. L., Reece, D. L., Thompson, J. L., Zhang, X.,
Hammond, B. L. and Beck, S., Development of rapeseed
biodiesel for use in high-speed diesel engines. Report to
U.S.D.O.E., Contract No. 93BIO9233, University of
Idaho, No. 302, September 1996.
33, Geyer, S. M.. Jacobus, M. J. and Lestz, S.S., TransASAE,
1984, 27, 375.
34, Masjuki, H., Zaki, A. M. and Sapuan, S. M. Methyl ester
of palm oil as an alternative diesel fuel. In Fuels for
Automotive and hzdustrial Diesel Engines. Institution of
Mechanical Engineers, London, p. 129, 1993.
35. Peterson, C., Reece, D., Hammond, B., Thompson, J. and
Beck, S., Making and testing a biodiesel fuel made from
ethanol and waste french fry oil. Idaho Department of
Water Resources Report, July 1995.
36. Freedman, B. and Bagby, M. 0., J. Am. Oil Chem. Sot.,
1990, 67 (9), 565.
37. Klopfenstein, W. E., Proceedings: Vegetable Oil as a
Diesel Fuel Seminar 111, Peoria, IL, p. 104, 1983.
38. Knothe, G., Bagby, M. O. and Ryan, T. W,, Soc.
Automotive Eng. Technical Paper No. 971681, 1997.
39. Heywood, J. B., Internal Combustion Engine Fundamen-
tals. McGraw-Hill, New York, 1988.
163
40. Ullman, T,, Mason, R. and Montalvo, D., Study of cetane
number and aromatic content effects on regulated
emissions from a heavy-duty engine. Southwest Research
Institute Report No. 08-2940, CRC Contract VE-1,
September 1990.
41. Sharp, C. A., Transient emissions testing of biodiesel in a
6V-92TA DDEC engine. Southwest Research Institute
Report 6602 and 6673 to National Biodiesel Board,
October 1994.
42. Sharp, C. A., Transient emissions testing of biodiesel and
other additives in a DDC Series 60 engine. Southwest
Research Institute Report for National Biodiesel Board,
December 1994.
43. Ali, Y., Hanna, M. and Cuppett, S., J. Am. Oil Chem. Soc.,
1995, 72 (12), J7654-1.
44. Sims, R., TransASAE, 1985, 29, 716.
45. Engine Manufacturers Association, Biodiesel Fuels and
Their Use in Diesel Engine Applications. Engine
Manufacturers Association, Chicago, IL, August 1995.
46. Klopfenstein, W. E. and Walker, H. S., J. Am. Oil Chem.
Soc., 1983, 60 (8), 81.
47. Ali, Y. and Hanna, M., Bioresource Technology, 1994, 47,
131.
48. Scholl, K. W. and Sorenson, S. C., Soc. Automotive Eng,
Technical. Paper No. 930934, 1993.
49. Chandler, J. E., Horneck, F. G. and Brown, G. I., Soc.
Automotive Eng. Technical Paper No. 922186, 1992.
50. Midwest Biofuels Inc., Biodiesel pour point and cold flow
study. Report to National Soydiesel Development Board,
30 September 1993.
51. Schmidt, K. and Van Gerpen, J., Soc. Automotive Eng.
Technical Paper No. 961086, 1996.
52. Harrington, K., Biomass, 1986, 9, 1.
53. Dunn, R. O., Shockley, M. W. and Bagby, M. O., Soc.
Automotive Eng. Technical Paper No. 971682, 1997.
54. Van Gerpen, J., Hammond, E. G., Yu, L. and Monyem, A.,
Soc. Automotive Eng. Technical Paper No. 971685, 1997.
55. Shafer, A., Biodiesel research--Mercedes Benz-engine
warranty policy. Presented at Commercialization of
Biodiesel: Establishment of Engine Warranties,
University of Idaho National Center for Advanced
Transportation Technology, pp. 125-141, 1994.
56. Ryan III, T., Dodge, L. G. and Callahan. T. J., J. Am. Oil
Chem, Soc., 1984, 61, 1610.
57. Bessee, G. B. and Fey, J. P., Soc. Automotive Eng.
Technical Paper No. 971690, 1997.
58. Garrett, T. K., Automotive Fuels and Fuel Systems.
Volume 2: Diesel. Society of Automotive Engineers,
Warrendale, PA, 1994.
59. Ortech International, Evaluation of methylsoyate/diesel
blend in a DDC 6V-92TA engine: optimization of NOX
emissions. Report 93-E14-36, 20 July 1993; Evaluation of
tallow/diesel blend in a DDC 6V-92TA engine. Report 93-
E14-37, 21 July 1993.
60. Fosseen manufacturing and development, optimize 20%
methylsoyate and diesel blend- 1977 DDC 6V-71N coach.
Report to National Biodiesel Board, Contract 219-2, 10
January 1995.
61. Fosseen manufacturing and development, DDC 6V-92 TA
MUI coach upgrade emission optimization on 20%/80%
soy/diesel blend. Report 260-2 and 241-1, 30 September
1994.
62. Ali, Y., Eskridge, K. M. and Hanna, M. A., Bioresource
Technology, 1995, 53, 243.
63. Batelle Institute, Interim alternative fuel transit bus
assessment results, Columbus, OH. Report to National
Renewable Energy Laboratory, August 1995.
64. ATE Management and Service Company, Inc., Cincinnati
metro soydiesel project-100000 mile field test. Final
Report, Cincinnati, OH, January 1994.
65. Daniel. T., Link Transit Biodiesel Demonstration Project.
Presented at Commercialization of Biodiesel: Establish-
ment of Engine Warranties, University of Idaho National
164 M.S. Graboski and R. L. McCormick
Center for Advanced Transportation Technology, pp. 71-
77, 1994.
66. Yost, D., Biodiesel Research--Spokane Transit Project.
Presented at Commercialization of Biodiesel: Establish-
ment of Engine Warranties, University of Idaho National
Center for Advanced Transportation Technology, p. 69, 1994.
67. Howes, P. and Rideout, G., Evaluation of biodiesel in an
urban transit bus powered with a 1988 DDEC II6V92 TA
engine. MSED Report No. 95-26743-1, Environment
Canada, 1995.
68. Howes, P. and Rideout, G., Evaluation of biodiesel in an
urban transit bus powered with a 1981 DDC 8V-71 engine
MSED Report No. 95-26743-2, Environment Canada,
1995.
69. Ortech Corporation, Operation of Cummins NI4 diesel on
biodiesel: Performance, emissions and durability. Final
Report for Phase I to National Biodiesel Board, Report
No. 95 El I-B004524, Mississauga, Ontario, 19 January
1995.
70. Lucas, W. Summary Test Report for the Bio-Diesel Fuel
Evaluation for the U.S. Army Tactical Wheeled Vehicles,
U.S. Army Yuma Proving Ground, Yuma, AZ, April 1995.
71. Baranescu, R., Biodiesel research--engine warranty
policy. Presented at Commercialization of Biodiesel:
Establishment of Engine Warranties, University of Idaho
National Center for Advanced Transportation Technology,
pp. 102-106, 1994.
72. Koontz, K., Biodiesel research--engine warranty policy-
cummins. Presented at Commercialization of Biodiesel:
Establishment of Engine Warranties, University of Idaho
National Center for Advanced Transportation Technology,
pp. 107-124, 1994.
73. Walker, L., Biodiesel research--Detroit diesel-engine
warranty policy. Presented at Commercialization of
Biodiesel: Establishment of Engine Warranties,
University of Idaho National Center for Advanced
Transportation Technology, p. 69, 1994.
74. Goyal, M., Biodiesel research--Deere power-diesel
engine durability issues using biodiesel. Presented at
Commercialization of Biodiesel: Establishment of Engine
Warranties, University of Idaho National Center for
Advanced Transportation Technology, 1994.
75. Fosseen Manufacturing and Development, 1000 Hour
durability testing DDC 6V-92TA DDEC II engine. Final
Report to National Biodiesel Board Contract No. 214-1,
27 January 1995.
76. Ortech Corporation, Operation of Cummins NI4 diesel on
biodiesel: Performance, emissions and durability. Final
Report for Phase 2 to National Biodiesel Board, Report
No. 95 El I-B004524, Mississauga, Ontario, 20 December
1995.
77. Blackburn, J., Pinchen, R., Nobre, J., Crichton, B. and
Cruse H., Soc. Automotive Eng. Technical Paper No.
831355, 1983.
78. Macchi, S., Overview on Biodiesel Utilization for S + L +
H Tractor Engines. AVE AVL Conference, "Engine and
Environment", Graz, Austria, 1991.
79. Schloegl, H. and Weisbauer, H., Motor und Umwelt.
Sommerakademie, Graz, Austria, 1989.
80. Howell, S., Lubricity of biodiesel fuel: Update No. 3.
Report to National Biodiesel Board, MARC-IV, Kansas
City, MO, 21 July 1994.
81. Hawkins, D., Fuls, J. and Hugo, F., Soc. Automotive Eng.
Technical Paper No. 831356, 1983.
82. United States Code of Federal Regulation, Vol. 40, Part
86, Subpart N.
83. Kortum, D., New fuels and fuel additives, Section 21 l(b)
Programs. Presented at Commercialization of Biodiesel:
Environmental and Health Benefits, Mammoth Hot
Springs, Yellowstone National Park, p.30, 21-22 May
1996.
84. Clean Air Act Amendments of 1990, Section 21 I.
85. Coordinating Research Council, Chemical methods for the
measurement of unregulated diesel emissions--carbonyls,
aldehydes, particulate characterization, sulfates, PAl-I/
NO2PAH. CRC Report No. 551, 1987.
86. Winsor, R. E., in Fuels for Automotive and Industrial
Diesel Engines. Institute of Mechanical Engineers:
Seminar 1993-2, London, 1993.
87. McCormick, R. L., Ross, J. D. and Graboski, M.,
Environmental Science and Technology, 1997, 31, 1144.
88. Bennethum, J. and Winsor, R., Soc. Automotive Eng.
Technical Paper No. 912325, 1991.
89. Graboski, M. S., Chassis testing of Denver RTD bus
#4882 fueled on neat soydiesel. Unpublished results,
1993.
90. Liotta, Jr, F. and Montalvo, D., Soc. Automotive Eng.
Technical Paper No. 932734, 1993.
91. Sharp, C. A., Emissions and lubricity evaluation of
rapeseed derived biodiesel fuels. Final Report from
SWRI to Montana Department of Environmental Quality,
November 1996.
92. Daniels, T. L., McCormick, R. L. and Graboski, M. S.
Unpublished results, 1996.
93. Ullman, T. L., Spreen, K. E. and Mason, R. L., Soc.
Automotive Eng. Technical Paper No. 941020, 1994.
94. Spreen, K. E., Ullman, T. L. and Mason, R. L., Soc.
Automotive Eng. Technical Paper No. 950250, 1995.
95. Spreen, K. E., Ullman, T. L. and Mason, R. L., Effects of
fuel oxygenates, cetane number, and aromatic content on
emissions from 1994 and 1998 prototype heavy duty diesel
engines. Southwest Research Institute, Final Report, CRC
Contract VE-10, May 1995.
96. Peterson, C. L. and Reece, D. L., Soc. Automotive Eng.
Technical Paper No. 961114, 1996.
97. McDonald, J., Purcell, D. L. and McClure, B. T.,
Methylester oxygenated fuels for diesel mining applica-
tions. In Proceedings of the 7th US Mine Ventilation
Symposium, p. ! 16, 1994.
98. Schumacher, L. G., Borgelt, S. C. and Hires, W. G.,
Fueling diesel engines with blends of methylester soybean
oil and diesel fuel. Agricultural Engineering Department,
University of Missouri, Columbia, MO, 1994.
99. Krahl, J., Munack, A., Bahadir, M., Schumacher, L. and
Elser, N., Soc. Automotive Eng. Technical Paper No.
962096, 1996.
1130. Signer, M., Heinze, P., Mercogliano, R. and Stein, H. J.,
Soc. Automotive Eng. Technical Paper No. 961074, 1996.
101. Parker, T. E., Private communication, 1996.
102. Sato, J., Konishi, K., Okada, H. and Nioka, T., 21st
Symposium on Combustion, p. 695, 1986.
103. Miller, J. A. and Bowman, C. T., Prog. Energy Combust.
Sci., 1989, 15, 287.
104. Hiroyasu, H., in Diagnostics and Modeling of Combustion
in Reciprocating Engines, COMODIA, Proceedings of
Symposium, Tokyo, 4 - 6 September 1985, pp. 53-75.
105. United States Code of Federal Regulation, Vol. 40, Part
86, Subpart I.
106. Fosseen manufacturing and development, five seasons
transportation Linn County lifts methyl soyate demonstra-
tion. Report to Iowa Soybean Promotion Board, Des
Moines, IA, 19 December 1995.
107. Shafer, A., Environmental and health concerns at
Mercedes Benz. Presented at Commercialization of
Biodiesel: Environmental and Health Benefits, Mammoth
Hot Springs, Yellowstone National Park University of
Idaho and DOE, 21-22 May 1996.
108. Kado, N., Toxic compound studies with ethyl and methyl
esters. Presented at Commercialization of Biodiesel:
Environmental and Health Benefits, Mammoth Hot
Springs, Yellowstone National Park University of Idaho
and DOE, 21-22 May 1996.