Fuel Processing Technology 96 (2012) 237249

Contents lists available at SciVerse ScienceDirect

Fuel Processing Technology

journal homepage: www.elsevier.com/locate/fuproc

Review

Review of the effects of biodiesel on NOx emissions

S. Kent Hoekman , Curtis Robbins
Desert Research Institute, 2215 Raggio Parkway, Reno, NV 89512, USA

a r t i c l e i n f o a b s t r a c t

Article history: Compared to conventional diesel fuel, use of biodiesel is generally found to reduce emissions of hydrocarbons
Received 23 June 2011 (HC), carbon monoxide (CO), and particulate matter (PM); but to increase oxides of nitrogen (NOx) emissions.
Received in revised form 28 December 2011 This paper reviews and summarizes relevant literature regarding the so-called biodiesel NOx effect, and pre-
Accepted 30 December 2011
sents theories to explain this effect. In modern diesel engines, several factors related to fuel composition and
Available online 30 January 2012
engine control strategies are important, though no single theory provides an adequate explanation of the bio-
Keywords:
diesel NOx effect under all conditions. There is evidence to suggest that effects on injection timing, ignition
Biodiesel delay, adiabatic ame temperature, radiative heat loss, and other combustion phenomena all play some
NOx role. The biodiesel NOx effect can be mitigated by modifying engine control settings particularly by retard-
Emissions ing injection timing and increasing exhaust gas recirculation (EGR). The absolute magnitude of the biodiesel
FAME NOx effect appears to be reduced with modern engines, although there are cases where the percentage change
is still substantial. Sophisticated after-treatment systems required to achieve the 2010 diesel engine emissions
standards do not appear to be signicantly affected by use of biodiesel. However, longer term study is war-
ranted, as such systems have only been in commercial use for a short time.
2012 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
2. NOx formation mechanisms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
2.1. Thermal NOx . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
2.2. Prompt NOx. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
2.3. Fuel NOx . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3. Theories of biodiesel's impacts on NOx . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3.1. Speed of sound and bulk modulus of compressibility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3.2. Decreased radiative heat loss . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3.3. Higher adiabatic ame temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
3.4. Combustion phasing theories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
3.5. Engine control/calibration theories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
4. Experimental evidence of biodiesel's impacts on NOx emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
4.1. Fuel effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
4.1.1. Fuel composition effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
4.1.2. Combustion phasing effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
4.1.3. Other fuel effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
4.2. Engine effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
4.2.1. Injection parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
4.2.2. Engine calibration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
4.2.3. Engine load. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
5. Mitigation of NOx increases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
5.1. Engine modications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
5.2. Fuel modications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243

Corresponding author. Tel.: + 1 775 674 7065; Fax: + 1 775 674 7016.
E-mail address: kent.hoekman@dri.edu (S.K. Hoekman).

0378-3820/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2011.12.036
238 S.K. Hoekman, C. Robbins / Fuel Processing Technology 96 (2012) 237249

6. Impacts of biodiesel on exhaust after-treatment systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244

7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
Acronyms and abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246

1. Introduction
Biodiesel is dened by ASTM as a fuel comprised of mono-alkyl
esters of long-chain fatty acids derived from vegetable oils or animal
fats, designated B100 [1]. The U.S. Congress has adopted a similar
denition for biomass-based diesel, with the additional require-
ment that the fuel have life-cycle greenhouse gas (GHG) emissions
that are at least 50% less than baseline life-cycle GHG [2]. The
vegetable- and animal-derived feedstocks used to produce biodiesel
are known as triacylglycerides (TAGs), or more simply, triglycerides.
Biodiesel is commonly produced by a process known as transesteri-
cation, by which the triglycerides are reacted with alcohols, in the
presence of a catalyst, to produce fatty acid alkyl esters. A byproduct
of transesterication is glycerine, also known as glycerol. Since the
most common alcohol used to produce biodiesel is methanol, another
name for biodiesel is fatty acid methyl esters (FAME). Unless other-
wise indicated, the term biodiesel refers to neat materiel i.e.
100% FAME, often designated as B100. Lower concentrations, such
as B20, are properly referred to as biodiesel blends, not biodiesel
itself.
There is considerable interest in biodiesel because of its domestic
and renewable origin, as well as its reduced life-cycle emissions of
GHG. Furthermore, there is a substantial body of evidence showing
that use of biodiesel (and biodiesel blends) has a strong and consis-
tent benecial effect on emissions of hydrocarbons (HC), carbon
monoxide (CO), and particulate matter (PM) [3]. The effects of biodie-
sel are smaller and more variable for NOx emissions, although gener-
ally NOx increases slightly with use of biodiesel. This increase is
referred to as the biodiesel NOx effect. Fig. 1 illustrates the effects
of biodiesel blend level upon these four criteria emissions when
used in heavy-duty (HD) diesel engines [4]. This assessment was con-
ducted by EPA nearly a decade ago, and therefore included data from
some engine types now considered obsolete. In an updated assess-
ment limited to engines of model year 1987 and later, we showed
that biodiesel still provided signicant reductions of HC, CO, and
PM, while NOx emissions increased [3,5]. Fig. 2 shows the NOx emis-
sions results from our assessment of 4-stroke HD and medium-duty
(MD) engines when tested on both biodiesel and a petroleum base
fuel. The logarithmic t to these data closely resembles the EPA-
reported NOx effect shown in Fig. 1. Inclusion of the approximately
200 data points illustrates that most test data were generated using
B20 and B100 fuel blends, and highlights the variability of the NOx ef-
fect. Another illustration of this variability is shown in Fig. 3, which
directly compares the measured emission rates expressed as g/
bhp-hr from biodiesel and petroleum diesel when used in the
same engine under the same operating conditions. The 1:1 equiva-
lence line is included, showing that most data points (but certainly
not all) lie slightly above the line.
With the magnitude of the NOx effect generally being much less
than the CO, HC, and PM effects, it is often difcult to quantify or
even condently detect a NOx effect when using low concentration
biodiesel blends, such as B20 or below. McCormick and co-workers
have concluded that the NOx emissions arising from B0 and B20
test fuels across a large number of test cycles and engines are not sig-
nicantly different [6,7].
2. NOx formation mechanisms
In diesel exhaust, NOx is predominantly composed of NO,
with lesser amounts of NO2. Under most conditions, other oxides
of nitrogen such as N2O, N2O5, NO3 are negligible. NOx formation
mechanisms have been studied in some detail, and several literature
references give good summaries of this area [4,811]. In general,
the three formation processes described below are believed to be
important:
2.1. Thermal NOx
At high temperatures, such as those occurring within the combus-
tion chamber of a diesel engine, N2 and O2 can react through a series
of chemical steps known as the Zeldovich mechanism. NOx formation
occurs at temperatures above 1500 C, and the rate of formation in-
creases rapidly with increasing temperature. Under most diesel en-
gine combustion conditions, thermal NOx is believed to be the
predominant contributor to total NOx [8,1114]. The kinetics of the
Zeldovich mechanism are such that the timescale of NOx formation

40

30
Change from Base Fuel, %
Percent Change in Emissions

y =5.0264ln(x) - 13.795
R2 = 0.2353
20

10

-10

-20
0 20 40 60 80 100
Biodiesel Blend Level, %
Percent Biodiesel
Fig. 2. NOx emissions effects of biodiesel fuels compared to petroleum diesel fuel in
Fig. 1. Average emission impacts of biodiesel for HD highway engines. 4-stoke HD diesel engines (1987 and newer).
Figure taken from EPA [4]. Data taken from Hoekman et al. [5].
 S.K. Hoekman, C. Robbins / Fuel Processing Technology 96 (2012) 237249
12
B20 (n = 88) Total (n) = 207
Above line= 154
10 B100 (n = 69)
Below line = 45
Biodiesel NOx Emissions, g/bhp-hr
other (n = 49) Online = 8
8 of theories have been developed to help understand these factors and
6 vide useful summaries of these theories, in particular, reports by
4
2 Several of the most common theories are briey described below;
0 Rather, they should be regarded as inuential factors that partially
0 2 4 6 8 10
Base Diesel Fuel NOx Emissions, g/bhp-hr
Fig. 3. NOx emission rates from 4-stroke HD diesel engines (1987 and newer) using
biodiesel compared to base petroleum fuel.
is comparable to combustion duration in a diesel engine [15]. Because
of this, any effect of biodiesel that increases the residence time of the
in-cylinder mixture, or increases the in-cylinder temperature, could
lead to increased thermal NOx.
2.2. Prompt NOx
The formation of prompt NOx (also known as Fenimore NOx)
involves intermediate hydrocarbon fragments from fuel combustion
particularly CH and CH2 reacting with N2 in the combustion cham-
ber [16]. The resulting C\N containing species then proceed through
reaction pathways involving O2 to produce NOx. Prompt NOx is only
prevalent under fuel rich conditions, where there is an abundance
of hydrocarbon fragments to react with N2. Due to this dependence
on hydrocarbon fragments, prompt NOx is sensitive to fuel chemistry,
whereas thermal NOx is largely insensitive to fuel chemistry. Al-
though it is recognized that thermal NOx generally dominates total
NOx formation, changes in fuel chemistry or combustion conditions
can shift the relative importance of thermal and prompt NOx [17].
Also, combustion modeling studies by Miller and Bowman have
shown that without considering prompt NOx mechanisms, total
NOx is underestimated [9]. In a recent modeling study, Ren and Li
showed an inverse relationship between prompt NOx and soot emis-
sions from combustion of biodiesel [18]. This is explained by compe-
tition for the intermediate CH species that are involved in both
prompt NOx and soot formation mechanisms. Ban-Weiss et al. postu-
lated that due to high levels of unsaturated compounds, combustion
of FAME may produce more hydrocarbon radicals than combustion
of conventional diesel, thus leading to higher NOx formation [19]. Al-
though there is some modeling support for this theory, there is little
experimental evidence for it.
2.3. Fuel NOx
Nitrogen-containing fuel species are oxidized to NOx during the
combustion process within a diesel engine. However, since the natu-
ral nitrogen levels in both diesel fuel and biodiesel are extremely low,
this formation process is generally negligible. Fuel NOx can become
more signicant when nitrogen-containing fuel additives (e.g. deter-
gents/dispersants) are used in high concentration.
239
3. Theories of biodiesel's impacts on NOx
NOx emissions do not show a single, uniform response to the use
of biodiesel. Rather, the results vary depending upon numerous fac-
tors including engine type and conguration, duty cycle, fuel injec-
tion strategy, emissions control strategy, and other factors. A number
help explain the predominance of test data showing increased NOx
with use of biodiesel. The literature contains several reports that pro-
Mueller et al. [15], Cheng et al. [17], and Ban-Weiss et al. [19]. Many
theories relate to differences in the way biodiesel and petroleum die-
sel inuence temperatures within the engine cylinder both maxi-
mum temperature and duration of time at elevated temperature.
This is consistent with the understanding that thermal NOx domi-
nates total NOx formation in diesel engines.
experimental evidence to support them is discussed in Section 4. It
should be emphasized that these theories are not mutually exclusive.
12
explain the overall effect of biodiesel usage upon NOx emissions.
More complete explanations of the biodiesel NOx effect under a vari-
ety of fuel/engine operating conditions invoke portions of several the-
ories. Due to the complexity and variability of combustion processes,
it is not possible to completely describe the NOx effect of biodiesel
usage under all conditions by any single combination of these
theories.
3.1. Speed of sound and bulk modulus of compressibility
In older style pump-line-nozzle (PLN) fuel injection systems, the
uid properties of speed of sound and isentropic bulk modulus have
important impacts on the injection process. The isentropic bulk mod-
ulus is a measure of a uid's compressibility under pressure it af-
fects the amount of pressure rise that will occur from the fuel pump
pulse. The speed of sound in the fuel affects the time required for
the pressure rise to proceed through the fuel line and reach the injec-
tor. Compared to petroleum fuel, biodiesel is less compressible and
has a higher speed of sound [20,21]. Both of these factors contribute
to an advance in fuel injection timing by about 12 [2225]. Injec-
tion timing advance can lead to earlier start of combustion, which
raises peak in-cylinder temperature, thereby increasing thermal
NOx formation [14].
With more advanced common rail electronic-controlled injec-
tion systems that are typically used today, these uid properties of
speed of sound and bulk modulus of compressibility are no longer
very important with respect to the start of fuel injection. However,
even with modern injection systems, a biodiesel NOx effect remains.
Therefore, this theory does not provide a complete explanation of
the NOx effect.
3.2. Decreased radiative heat loss
It is well known that use of biodiesel reduces PM emissions sub-
stantially. Within the combustion chamber, soot particles are effec-
tive in radiative heat transfer, thereby lowering the overall ame
temperature. Therefore, a reduction in soot concentration would
lead to higher combustion chamber temperatures, thus increasing
thermal NOx formation (Zeldovich NOx). Mueller and co-workers
have provided experimental evidence from optical engine work to
support this theory [15,17], and it is consistent with the observation
that use of biodiesel generally reduces PM while increasing NOx.
Yet, this theory does not provide a complete explanation, as Schon-
born et al. have shown that combustion of some FAME species (espe-
cially unsaturates) simultaneously increases both PM and NOx
[26,27].
240 S.K. Hoekman, C. Robbins / Fuel Processing Technology 96 (2012) 237249
3.3. Higher adiabatic ame temperature
Based on combustion of model compounds, Ban-Weiss et al.
showed that unsaturated molecules exhibit higher adiabatic ame
temperature than their saturated counterparts [19]. This has been
used to hypothesize that biodiesel gives higher ame temperature
than conventional diesel, due to the higher concentration of unsatu-
rated compounds in biodiesel. With higher ame temperature, in-
creased thermal NOx formation would be expected. However, there
is little experimental evidence to suggest that changes in adiabatic
ame temperature when using biodiesel is a major contributor to
the observed NOx effect [15].
3.4. Combustion phasing theories
Several researchers have investigated ways in which biodiesel can
affect combustion phasing, thereby inuencing NOx emissions. In
these explanations, it is useful to dene three separate periods within
the overall combustion cycle:
Ignition delay period
Pre-mixed combustion period
Diffusion combustion period
The ignition delay period is the time between start of injection and
start of ignition. This period is related to the cetane number of the
fuel, with higher cetane leading to shorter ignition delay. Typically,
biodiesel fuels have higher cetane numbers than petroleum diesel
[28,29]. A shorter ignition delay could allow the fuel mixture and ini-
tial combustion products to have a longer residence time at elevated
temperature, thereby increasing thermal NOx formation. However, as
cetane improving additives are sometimes used to reduce NOx emis-
sions (discussed later) it is apparent that reduced ignition delay alone
is not an adequate explanation of the biodiesel NOx effect.
During the pre-mixed combustion period, fuel and air that have
already mixed ignite, causing a rapid rise in temperature and pres-
sure. The extent to which these temperature and pressure increases
occur depends upon the amount of fuel that has already been
injected, which is related to the length of the ignition delay. With lon-
ger ignition delays (related to low cetane number), more fuel is
injected and mixed with air before ignition occurs, thus leading to
more extreme temperature and pressure increases.
3.5. Engine control/calibration theories
Modern diesel engines are equipped with electronic engine con-
trol modules (ECMs) that are programmed to control air/fuel ratios,
injection timing, exhaust gas recirculation (EGR), and other impor-
tant parameters. The control strategy typically employs measure-
ments of engine speed and torque, which are used to dene
operating conditions that maximize fuel economy while satisfying
emissions requirements [30]. Programming of the ECM control set-
tings is generally based upon use of conventional diesel fuel. If use
of biodiesel causes perceived changes in speed or torque, the ECM
will make adjustments to operating conditions which could result in
higher emissions.
4. Experimental evidence of biodiesel's impacts on NOx emissions
Although use of biodiesel is usually observed to increase NOx
emissions, this is not universally true. In a recent survey on the emis-
sions effects of biodiesel, Lapuerta et al. stated that about 95% of
the relevant literature indicates a reduction in HC and PM from use
of biodiesel, 90% indicates a reduction of CO, but only 85% indicates
an increase in NOx [31]. From our assessment of the literature (con-
sidering only 4-stroke HD engines of model year 1987 and newer)
74% of testing results showed a NOx increase when using biodiesel
at any blending level (see Fig. 3). This variability of the NOx effect is
understandable, considering the complexity of the combustion pro-
cess and the wide range of factors that inuence emissions. The liter-
ature contains many reports of experimental studies in which use of
biodiesel either reduced NOx emissions, or had no impact. Some of
these involve simple, single-cylinder laboratory test engines, with
rather unsophisticated controls [3236], while others involve labora-
tory engines (and vehicles) more representative of commercial appli-
cations [10,3741]. Several recent studies using modern, highly
instrumented test engines and sophisticated diagnostic systems
have also demonstrated operating conditions whereby use of biodie-
sel resulted in reduced NOx emissions [4244].
In the following sections, we summarize the most signicant ex-
perimental evidence that informs our understanding of biodiesel's
impacts on NOx emissions, and supports the conclusion that under
most conditions, use of biodiesel increases NOx. Clearly, numerous
variable and interacting factors are involved in dening the overall
NOx effect. However, it is helpful to simplify the discussion by divid-
ing these factors into two broad categories of fuel effects and engine
effects, while recognizing that there is substantial overlap between
these areas. Section 4.1 summarizes experimental work and results
focused primarily on understanding how fuel parameters affect NOx
emissions; Section 4.2 summarizes experimental work and results fo-
cused primarily on understanding how engine parameters affect NOx.
4.1. Fuel effects
Biodiesel differs from petroleum diesel in several important as-
pects. Compositionally, the most signicant differences are the high
oxygen content and high degree of unsaturation present in biodiesel
[29]. These compositional factors are responsible for differences in
other physical and chemical properties. For example, compared to pe-
troleum diesel, biodiesel has higher specic gravity, viscosity, and
boiling point (as dened by T90); but lower mass carbon content, hy-
drogen content, and energy content [5,29,45]. Described below are
studies in which the effects of these biodiesel fuel properties upon
NOx emissions have been investigated.
4.1.1. Fuel composition effects
Despite the small and variable effects of biodiesel on NOx emis-
sions, a consensus has developed throughout the literature regarding
the impacts of certain fuel properties. As early as 2003, a report by
Graboski et al. identied FAME unsaturation and chain length as
two key properties affecting NOx [46]. It is generally accepted that
NOx emissions increase with increasing unsaturation, but decrease
with increasing chain length. These effects have been noted in several
reviews of biodiesel emissions [47,48] and have been demonstrated
experimentally in numerous studies involving pure FAME constitu-
ents [26,49,50]; as well as complete biodiesel fuels used in single cyl-
inder test engines [51,52], light-duty engines [53], and heavy-duty
engines [10,50,54,55].
The exact mechanisms responsible for these fuel compositional ef-
fects on NOx are still somewhat controversial, but largely follow the-
ories similar to those discussed above. For example, higher
unsaturation correlates with higher adiabatic ame temperature,
which inuences thermal NOx formation. Also, higher unsaturation
is related to lower cetane number, which affects ignition delay and
changes phasing between pre-mixed and diffusion ame combustion
processes. Iodine value (IV) is a good indicator for unsaturation, and
several researchers have noted the strong relationship between IV
and NOx emissions [38,50,56,57]. Differences in NOx emissions by
biodiesel type have also been noted in the literature, with more high-
ly unsaturated feedstocks (such as soy) producing higher NOx than
less unsaturated feedstocks (such as rapeseed, tallow, and yellow
grease) [3,4,41,48].
 S.K. Hoekman, C. Robbins / Fuel Processing Technology 96 (2012) 237249
There is some evidence that the composition of the base diesel fuel
into which biodiesel is blended has an impact on NOx emissions. In
EPA's 2002 review, it was observed that larger NOx increases oc-
curred when biodiesel was blended into clean base fuels as com-
pared to average base fuels [4]. Clean base fuels generally had
lower aromatics, higher cetane number, lower density, and lower dis-
tillation temperatures as compared to average base fuels. To ad-
dress this concern of larger NOx increases in clean base fuels, the
California Air Resources Board (CARB) is currently conducting an ex-
perimental program to quantify the NOx effects in CARB diesel, and
identify effective mitigation measures [48,58,59]. However, in our re-
cent assessment of the literature, we found only weak evidence that
base fuel had an impact on the observed NOx effect [3,5].
In the 2003 NREL report, both biodiesel methyl esters (FAME) and
ethyl esters (FAEE) were tested in a 1991 DDC HD engine [46]. Differ-
ences in NOx emissions between the FAME and FAEE fuels were var-
iable and inconclusive. The authors concluded that neat FAME and
FAEE originating from the same base stock produced the same NOx
emissions. More recently, using a LD diesel engine with common
rail injection, Lapuerta et al. determined that FAEE (from used cook-
ing oil) gave slightly reduced NOx compared to FAME [60]. This effect
was attributed to FAEE's slightly higher cetane number, or its slightly
lower oxygen content. Using pure compounds in a single-cylinder
test engine, Schonborn et al. also observed a slight decrease in NOx
emissions with FAEE as compared to FAME [26,27].
4.1.2. Combustion phasing effects
Several researchers have studied the effects of biodiesel fuel on
the phasing of combustion events, and how this impacts NOx emis-
sions [11,15,17,25,61,62]. Sophisticated experiments involving modi-
cation and control of injection and combustion processes have been
conducted in an attempt to isolate and test various theories related to
combustion phasing. For example, Cheng at al. used an optically-
accessible engine to permit clearer observation of these processes
[17]. They also modied engine and fuel conditions to maintain a con-
stant start of combustion (SOC) and a constant premixed burn frac-
tion; yet biodiesel was found to give higher NOx emissions than
conventional diesel. Experimental measurements indicated that com-
bustion ame temperatures were higher with biodiesel, even though
there were no signicant differences in stoichiometric adiabatic ame
temperatures among the fuels. This was explained by differences in
soot radiative heat transfer; with biodiesel producing less soot, thus
having higher in-cylinder temperatures. These authors also deter-
mined the fuel mixture stoichiometry at the ame lift-off length,
using an injector spray model. (Flame lift-off length is dened as
the distance from the fuel injector orice at which the observed
ame stabilizes during diffusion combustion.) They showed that the
oxygen equivalence ratio was signicantly lower (less rich) with bio-
diesel as compared to petroleum diesel. This is understandable, since
biodiesel contains oxygen, whereas petroleum diesel does not. It was
hypothesized that this difference in stoichiometry with biodiesel
could be related to the NOx effect, although the exact mechanisms
for this were not explained.
In subsequent work with the same optical engine, Mueller et al.
maintained constant start of injection (SOI) and start of combustion
(SOC), used chemical additives to increase radiative heat transfer,
and used diluted intake air to simulate EGR [15]. Several different bio-
diesel blends were tested, and the engine was operated over a range
of loads. It was shown that regardless of operating condition, the
combustion process was generally faster with biodiesel, which leads
to overall higher in-cylinder temperature and longer residence time
at elevated temperature both of which contribute to higher NOx.
As before, gas mixtures at ame lift-off length were closer to stoichio-
metric (less rich) with biodiesel compared to petroleum diesel. The
authors postulated that reacting gas mixtures that are closer to stoi-
chiometric during both the ignition event and subsequent diffusion
241
ame autoignition zone (AZ) will lead to higher temperatures and
thus, higher NOx emissions. A major conclusion from this study is
that no single mechanism or fuel property can explain the biodiesel
NOx effect under all conditions, but rather, several mechanisms are
important. These different mechanisms can either reinforce or cancel
one another, depending upon specic operating conditions. Two
factors identied as being most important are: (1) combustion
phasing earlier start of combustion with biodiesel, leading to longer
residence times and higher temperatures, and (2) lower radiative heat
loss with biodiesel.
Adi and co-workers compared the performance of soy-FAME with
conventional diesel in a modern, electronically-controlled HD engine
under various operating conditions [63]. Using a combination of ex-
perimental and modeling approaches, they showed that biodiesel
can increase NOx emissions due to high in-cylinder temperatures
under both pre-mixed and diffusion combustion conditions. During
the pre-mixed stage, higher oxygen levels with biodiesel (due to the
fuel oxygen) produce conditions closer to stoichiometric, resulting
in higher in-cylinder temperatures. During diffusion combustion,
greater availability of oxygen with biodiesel leads to higher ame
temperature. An additional factor with EGR-equipped engines is
that EGR gases from biodiesel combustion contain higher O2 levels
than gases from conventional diesel combustion. Consequently, use
of EGR with biodiesel is less effective in reducing in-cylinder temper-
atures; or alternatively, a greater degree of EGR is necessary when
using biodiesel.
In another carefully controlled laboratory study, Schonborn et al.
conducted a series of experiments in which they controlled three pa-
rameters: (1) injection timing, (2) ignition timing, and (3) ignition
delay [26,27]. Individual FAME species were used, rather than com-
plete biodiesel fuels. Results showed that all three parameters were
important, but to different degrees with different FAME structures.
These researchers also demonstrated the important role of unsatura-
tion in determining NOx emissions, with higher unsaturation leading
to higher NOx. It was concluded that the formation of NOx is con-
trolled by several, layered effects, with the most important being igni-
tion delay, which changes heat release behavior and stoichiometry of
the combustion process. Adiabatic ame temperature was regarded
as a secondary effect, which only becomes important when the effect
of ignition delay is removed. Soot-inuenced radiative heat transfer
was regarded as a tertiary effect.
Jacobs and co-workers used a modern medium-duty test engine to
investigate differences in the response of an electronically-controlled,
common rail injection system when using biodiesel and conventional
diesel fuels [64]. They conrmed that the unintended advance in in-
jection timing with biodiesel in pump-line-nozzle systems does not
occur with modern common rail systems. They also demonstrated
that the injection pulse width is longer with biodiesel, since more
fuel must be injected to compensate for its lower volumetric energy
content. From heat release measurements it was shown that biodiesel
had a shorter ignition delay (earlier start of combustion), earlier start
of diffusion burning, and earlier termination of combustion. Consis-
tent with the observations of Mueller at al. [15], biodiesel appeared
to promote a combustion process that is shorter and more advanced
than conventional diesel. These changes would be expected to in-
crease thermal NOx emissions.
The Jacobs research group recently published a review on NOx
emissions from use of biodiesel, in which they discussed how several
differences in biodiesel properties (compared to petroleum diesel)
cause changes in the combustion behavior of diesel engines [11].
They explained that taken together, these complex and interacting
mechanisms make it difcult to fundamentally identify how biodiesel
affects NOx emissions. Nevertheless, it is clear that some factors are
related to the NOx effect. For example, consistent with Mueller's
work, [15] biodiesel's generally shorter ignition delay and faster com-
bustion period contribute to increased thermal NOx formation.
242 S.K. Hoekman, C. Robbins / Fuel Processing Technology 96 (2012) 237249
Parameters that are consistently found to be important include injec-
tion timing, adiabatic ame temperature, radiative heat transfer, and
ignition delay. The authors also concluded that differences in engine
design, technology, and operating conditions may be responsible for
some of the apparent inconsistencies in the literature regarding the
biodiesel NOx effect.
4.1.3. Other fuel effects
Several other fuel-related parameters have been suggested to help
explain the biodiesel NOx effect. For example, it has been hypothe-
sized that the boiling point and volatility of FAME could have an effect
on the injection and combustion processes in such a way as to increase
NOx emissions [65,66]. FAME materials have much narrower distilla-
tion ranges than conventional diesel, and have lower overall volatility.
[The biodiesel standard, ASTM D6751, includes a maximum T90 speci-
cation of 360 C [1], as compared to the conventional diesel standard,
ASTM D975, which has a maximum T90 specication of 338 C [67]].
Boehman et al. have also reported relationships between FAME densi-
ty and NOx emissions [23]. With FAME having higher density than
conventional diesel, equivalent volume injection results in greater
mass injection of biodiesel, although lesser energy injection.
Low temperature operation of biodiesel is a signicant concern
with respect to wax formation, fuel gelling, and the impacts on lter
plugging and general engine operation [5,68,69]. A few researchers
have also investigated the effects of fuel temperature on the injection
process, and by extension, to NOx emissions. Using a mechanically ac-
tivated fuel injection system, Kegl showed that injection delay was
reduced as fuel temperature decreased, with both B0 and B100 [70].
It was also observed that at low temperature, the distribution of bio-
diesel fuel among the 6 injectors comprising the entire fueling system
became quite uneven, while the distribution of conventional diesel
did not. This was attributed to an elevated pressure drop resulting
from increased biodiesel viscosity at low temperature. Such uneven
fuel distribution would be expected to adversely affect exhaust emis-
sions, although this problem is likely minimized with today's modern
electronically controlled injection systems, and by use of lower bio-
diesel blends, such as B20.
Mamat et al. investigated the effect of biodiesel fuel temperature
upon engine operation and emissions from a common rail LD diesel
engine [71]. The objective was not to explore low temperature oper-
ability, but to investigate the impacts of increasing fuel temperature
above ambient. It was shown that increasing the fuel temperature
from 30 C to 40 C reduced NOx emissions in the absence of EGR.
Application of EGR reduced NOx overall, but the benet of fuel tem-
perature increase no longer occurred.
Finally, Bannister et al. conducted a temperature-controlled chas-
sis dynamometer study using a Euro 3, common rail, LD vehicle [72].
Ambient temperature was controlled from 25 C to 5 C, and bio-
diesel blend ratios were explored from B0 to B50. The usual increase
in NOx emissions with increasing B-level was observed, but the mag-
nitude of this increase diminished at lower temperatures.
4.2. Engine effects
Many experimental studies have been reported in which engine
operating parameters were varied, in a controlled manner, to under-
stand their impacts upon NOx emissions. This section discusses sever-
al of these studies, with a focus on how these engine parameters
differ with use of biodiesel.
4.2.1. Injection parameters
The fuel injection process is an important aspect of engine opera-
tion that affects emissions, and is inuenced by biodiesel. As shown
by Tat and Van Gerpen [20,21] the higher speed of sound and isentro-
pic bulk modulus of biodiesel as compared to conventional diesel
leads to advanced injection timing with older engines using
mechanical injection systems. However, Caresana pointed out that
this advanced injection timing may not be as pronounced in some me-
chanical injection systems because use of biodiesel can reduce the re-
sidual pressure in fuel lines after the injection event, thus
compensating for the increased injection pressure [73]. Benjumea et
al. reported that the advanced timings of injection and combustion
when using biodiesel were more pronounced at higher altitudes
above sea level [74]. Careful experimental studies have shown that
biodiesel's inadvertent timing advance does not occur with modern,
common rail injection systems [17,75].
Fluid dynamics of fuel sprays are highly complex, and important in
inuencing combustion phasing [76]. Fuel spray atomization and injector
penetration length also inuence the combustion process and can affect
NOx emissions. Because of its somewhat different properties (viscosity,
density, surface tension, etc.) the use of biodiesel has been shown to af-
fect fuel droplet size and injection penetration [7779]. However, the lit-
erature is not consistent in demonstrating a signicant NOx effect
resulting from changes in fuel spray behavior. In a recent study, Yoon
and coworkers observed that biodiesel gave larger droplet sizes, nar-
rower spray patterns, and longer spray tip penetration into the combus-
tion chamber [80]. Others have used computational uid modeling to
show that narrower, but longer spray penetration would be expected
to increase NOx, due to higher average cylinder gas temperatures [81].
Ye and Boehman investigated the impact of injection strategies
upon the biodiesel NOx effect using a direct injection diesel engine
operated under moderate speeds and loads [62]. Because of biodie-
sel's lower energy content, a greater volume of fuel must be injected,
compared to petroleum diesel, to maintain a xed speed and load.
This can be achieved by increasing the injection pressure or injection
duration, both of which were shown to increase NOx. The authors
also employed a fuel spray model to compute the oxygen equivalence
ratio of the gas mixture at the autoignition zone (AZ) near the ame
lift-off length. Although the lift-off length itself varied with injection
pressure, the oxygen equivalence ratio eld was largely unchanged.
With biodiesel, the gas mixture was closer to stoichiometric at the
AZ, regardless of the injection pressure. This lean combustion with
biodiesel results in higher local temperatures and earlier maximum
cylinder temperature, thus leading to higher NOx emissions.
4.2.2. Engine calibration
Modern diesel engines are equipped with electronic engine con-
trol module (ECM) systems that permit various engine calibration
strategies to be employed. Such systems typically control air/fuel ra-
tios, injection pressure, injection timing, injection phasing, and EGR
to achieve specic target values of engine speed and torque. Each en-
gine manufacturer establishes detailed, proprietary maps of these
parameters to optimize the engine performance and fuel economy
while adhering to the applicable emissions specications.
Engine calibration is generally performed while using convention-
al diesel fuel. Subsequent operation with biodiesel can result in oper-
ational changes that affect NOx emissions either increases or
decreases are possible. A recent paper by Eckerle et al. provides a
thorough discussion of how NOx increases could occur because of
such ECM-related modications [30]. Due to biodiesel's lower volu-
metric energy content, a higher fuel ow is required compared to pe-
troleum diesel to achieve the same power. The ECM interprets this
higher fuel ow as an indicator of higher torque, and therefore
makes adjustments to engine operating parameters that, under cer-
tain operating conditions, increase NOx emissions.
A recent report by Tompkins et al. supports this theory of increased
NOx from biodiesel usage in a modern, ECM-equipped diesel engine
[82]. These authors found an average NOx increase of 20% over nine oper-
ating points when using palm-FAME compared to conventional diesel. It
was noted that when using biodiesel, the ECM adjusted several parame-
ters (boost pressure, EGR level, and start of combustion) to attain the
same torque. The authors suggested that these ECM-directed changes
 S.K. Hoekman, C. Robbins / Fuel Processing Technology 96 (2012) 237249
could be partly responsible for the increased NOx that was observed.
Armas et al. used Euro 2 and Euro 3 LD diesel engines to show that the
biodiesel NOx effect during transient conditions depended upon both
the injection conditions and the EGR strategy employed in engine tuning
[83].
4.2.3. Engine load
In their 2006 report, McCormick et al. noted that the impacts of bio-
diesel blends (B20) upon NOx emissions were highly dependent upon
the test vehicle/engine and the driving cycle being used [10]. Mueller
et al. noted in their optical engine work that the controlling mecha-
nisms leading to higher NOx from biodiesel were different between
low and high engine load conditions [15]. Using a common rail LD diesel
engine, Zhang and co-workers demonstrated that the NOx effect of bio-
diesel was a function of engine load NOx increased under high load
operating conditions, but decreased under low load [75,84]. More re-
cently, Karavalakis et al. noted that NOx increased with biodiesel
usage in LD vehicles under some test cycles, but not under others [85].
In the Cummins HD engine study described above, a combination
of experimental work and modeling showed that the NOx effect of
biodiesel varied signicantly with load [30]. Under high loads, specic
engine calibration strategies that are employed could increase NOx
signicantly; while under low loads, biodiesel could have no effect
on NOx or even reduce NOx emissions. According to these authors,
the total biodiesel NOx effect is determined by the sum of two differ-
ent inuences: (1) engine control effects and (2) fundamental com-
bustion effects. The fundamental combustion effects are driven by
fuel chemistry and uid dynamics, and are applicable to all engines;
while the engine control effects are specic to the particular engine
calibration being employed, and likely differ from one engine type
to another. The relative contributions of these two effects vary
depending upon the specic fuel and engine load. Under high load
conditions, where diffusion ame combustion processes dominate,
it was shown that engine controls had a more signicant inuence
on biodiesel's NOx increase. Under low load conditions, with more
pre-mixed combustion, the fundamental combustion effects were
more inuential.
EPA employed dynamometer testing with a single HD diesel en-
gine (2006 Cummins ISB) to investigate the NOx effects of several
biodiesel blends when tested over 7 different engine cycles [86].
The results showed that NOx emissions increased as a function of av-
erage cycle load using both engine cycles and chassis-based cycles.
In their RFS2 Regulatory Impact Analysis, EPA included retrospective
analysis of other literature-reported NOx effects, and concluded that
they could be understood by analyzing the emissions results as a
function of cycle load [87]. The California Air Resources Board
(CARB) is now also investigating the impacts of test load when
using biodiesel blends in CARB diesel fuel [48,58,59].
5. Mitigation of NOx increases
While use of biodiesel generally provides emissions benets with
respect to CO, HC, and PM, the slight NOx increase usually observed is
regarded by some as a problem requiring mitigation. The numerous
mitigation approaches explored by different investigators can be cat-
egorized broadly into two groups: (1) engine modications and (2)
fuel modications. Examples of both categories are provided below.
5.1. Engine modications
In their 1998 review paper, Graboski and McCormick noted that
use of biodiesel increased NOx emissions in both 2-stroke and 4-
stroke diesel engines, but that these increases could be effectively
mitigated by retarding the fuel injection timing by 14 [88]. Subse-
quently, Choi and Reitz demonstrated the NOx reduction benets of
both retarded and split injection techniques when using biodiesel in
243
a HD Caterpillar engine [89]. The authors argued that these injection
strategies reduced the amount of pre-mixed burning, thereby reduc-
ing in-cylinder temperatures. The NOx reduction benets of split in-
jection techniques were further conrmed by Kim et al. using a
single-cylinder test engine with a common rail injection system,
[90] and by Stringer et al. using an optical access laboratory engine
[91]. Using a 6-cylinder MAN bus engine, Kegl demonstrated that bio-
diesel could produce lower NOx than conventional diesel fuel, if the
injection timing were retarded to achieve maximum torque [92].
A second engine modication to reduce NOx emissions is use of
EGR. The major effect of EGR is reduced cylinder temperature, due to
introduction of diluent gas of high specic heat (containing substantial
levels of H2O and CO2). Additionally, introduction of EGR reduces the
oxygen content in the cylinder. Both factors are believed to contribute
to reduced NOx emissions [93]. Several other investigators have
reported on the benets of EGR in reducing NOx emissions when
using biodiesel in laboratory test engines [9498]. EGR is also common-
ly employed to reduce NOx emissions when using conventional diesel
fuel. Thus, to be effective in a biodiesel situation, a greater degree of
EGR would be utilized. As pointed out by Muncrief et al., the use of
EGR in combination with a diesel particulate lter (DPF) is an effective
way to reduce both NOx and PM from diesel engine exhaust [99].
More effective than either injection timing or EGR alone is the com-
bination of both approaches, utilizing a control system to maximize
the overall benet [8]. Several investigators have demonstrated such
enhanced benets when using biodiesel in single-cylinder laboratory
engines, [93,100,101] and multi-cylinder engines [43,75,102104].
Effective use of such engine strategies in real-world applications
also requires on-line analysis of the fuel composition, and an ability
to adjust parameters depending upon this composition.
In recent years, several investigators have explored a type of com-
bustion process known as low temperature combustion (LTC). Good
descriptions of LTC can be found in the literature [105107]. In gener-
al, LTC involves use of high EGR rates (up to 50%), high injection pres-
sures, multiple fuel injection pulses per cycle, and late main injection
even after top dead center (TDC). With LTC, ignition delay increases,
thus increasing the pre-mixed combustion phase and decreasing
(or eliminating) the diffusion ame combustion phase. The overall
in-cylinder temperature is reduced substantially, thereby reducing
NOx formation. At the same time, PM is reduced due to the dominance
of lean, pre-mixed combustion.
LTC is not appropriate for all operating conditions, and it is known to
increase CO and HC emissions in some situations. Yet, it appears to be an
attractive strategy since it offers simultaneous and signicant reductions
of both NOx and PM. Numerous laboratory applications of LTC have been
published in recent years, with positive results reported from modeling
studies [91,108], single-cylinder test engines [107,109112], and multi-
cylinder production engines [105,106,113115]. One possible concern
with application of LTC when using biodiesel was pointed out by Nor-
throp et al., who showed that condensation of unburned biodiesel can
lead to large increases in PM emissions under some conditions [116].
5.2. Fuel modications
Changes in fuel composition have long been suggested as ways to
mitigate the NOx increase resulting from use of biodiesel (and biodie-
sel blends), while still benetting from the reductions in HC, CO, and
PM that such fuels offer. In 1996, Graboski et al. tested a variety of
biodiesel blends in a 1991 DDC Series 60 engine, using the EPA HD
transient test protocol [117]. The authors concluded that the NOx in-
crease resulting from B20 usage could be eliminated by reducing the
base fuel's aromatic content (from 34.3% to 29.7%) or by increasing
the cetane number (from 46.2 to 52.8).
Some years later, the same DDC Series 60 engine was used in an ex-
perimental program to investigate NOx mitigation when using B20
blends from soy oil and yellow grease [118]. Three different
244 S.K. Hoekman, C. Robbins / Fuel Processing Technology 96 (2012) 237249

hydrocarbon base fuels were used to produce the B20 blends: (1) fed- Table 1
eral certication fuel (31.9% aromatics; 0.04% sulfur), (2) 10% low ar- HD diesel engine emissions standards U.S.

omatics diesel (7.5% aromatics; 0.01% sulfur), and (3) FT diesel (0% Year US emission levels, g/bhp-hra
aromatics; b0.01% sulfur). Based upon results of HD FTP testing, it
HCb CO NOX PM
was demonstrated that NOx emissions from B20 blends were reduced
1988 1.30 15.50 10.70 0.60
considerably when using either the 10% low aromatics diesel or the F
1990 1.30 15.50 6.00 0.60
T diesel in place of conventional diesel fuel. Using linear extrapolation 1991 1.30 15.50 5.00 0.25
of the results, the authors concluded that a base fuel having 25.8% ar- 1994c 1.30 15.50 5.00 0.10
omatics would provide a NOx neutral B20 blend relative to use of the 1998 1.30 15.50 4.00 0.10
certication base fuel. When using the FT diesel as base fuel, a biodie- 2004d,e 0.50 15.50 2.50 0.10
2007f,g 0.14 15.50 1.20 0.01
sel blend as high as B55 was predicted to be NOx neutral. Also in this 2010 0.14 15.50 0.20 0.01
study, the effects of cetane improvers upon NOx were determined. a
Based on U.S. EPA Transient Federal Test Procedure (FTP) engine dynamometer
Both di-t-butyl peroxide (DTBP) and 2-ethylhexyl nitrate (2-EHN)
cycle. Useful life compliance period of 290,000 miles for HHDDE; 185,000 miles for
were shown to be effective. The authors concluded that use of cetane MHDDE; 110,000 miles for LHDDE.
improvers was a practical strategy for NOx reduction in the short term. b
For 2004 and beyond, HC refers to non-methane hydrocarbons (NMHC).
c
In a related study, McCormick et al. again demonstrated the effec- Maximum fuel sulfur level reduced to 500 ppm.
d
tiveness of cetane improvers, DTBP and 2-EHN, in reducing NOx emis- Optional standard of 2.4 g/bhp-hr for NMHC + NOx.
e
Venting of crankcase emissions prohibited except for turbocharged engines.
sions from biodiesel blends [41]. They also observed NOx reduction f
Additional requirements introduced for supplemental emissions test (SET).
with use of the anti-oxidant additive, t-butyl-hydroquinone (TBHQ). g
NOx and PM standards phased-in between 2008 and 2010.
Although both the cetane improvers and anti-oxidants were some-
what effective, no additive combination in B20 blends based on feder-
al certication diesel fuel could match the NOx reductions provided by
a CARB low aromatics (nominally 10% aromatics) diesel fuel. However, criteria emissions standards for HD diesel engines in the U.S. and
reducing the certication diesel fuel's aromatics content from 32% to Europe, respectively. To comply with current standards, sophisti-
25%, combined with use of DTBP, did meet the CARB fuel's perfor- cated exhaust after-treatment systems are being introduced into
mance. The authors also reported that B20 NOx emissions were higher both LD and HD applications. Because standards requiring use of
with soy-derived FAME than with yellow grease-derived FAME. This after-treatment are quite recent, there is little operational experi-
was attributed to higher unsaturation of the soy material, which had ence with such systems reported in the literature particularly
an iodine value of 127, compared to 79 for the yellow grease. with use of biodiesel.
Several other groups have reported benecial effects of cetane im- Two types of after-treatment approaches are commonly employed
provers in reducing NOx emissions from biodiesel and biodiesel to reduce NOx emissions from diesel engines. One involves use of a
blends, with DTBP and 2-EHN being the two most frequently NOx adsorber catalyst (NAC), which is sometimes called a lean-NOx
employed additives. Positive effects have been found in single cylinder trap. A NAC system utilizes an oxidation catalyst to convert all NO
laboratory test engines [119,120] as well as production HD engines to NO2, which is then trapped in an adsorbent bed. Once the adsorber
[48,121123], although the effectiveness varied depending upon spe- is saturated with NO2, the exhaust stream is forced into a fuel-rich
cic engine and operating conditions. In some cases, DTBP was found condition (by injection of excess diesel fuel, or other means) and
to be more effective than 2-EHN [48,59,122]. Nuszkowski et al. recent- the trapped NO2 is reduced to N2, which is exhausted. NAC systems
ly evaluated the effect of DTBP and 2-EHN in ve HD engines spanning are very sensitive to sulfur contamination, since SOx is collected in
a range of technology types [123]. They observed that the cetane im- the adsorbent bed along with NOx. However, the lean operation
provers were effective in reducing NOx from the older technology en- mode used to remove NOx is not effective in removing SOx, thus
gines, but had little benet with newer engines equipped with higher sulfur contamination gradually reduces the trapping capacity for
compression ratios and use of EGR. Also, these additives were most ef- NOx. To improve the effectiveness and durability of modern diesel
fective under low engine power condition, but offered little benet at emissions control systems, use of ultra-low sulfur diesel (ULSD) is
high power. Finally, Yanowitz and McCormick concluded that the ben- now required.
ets of cetane improvers appeared to diminish with newer engine The second NOx after-treatment approach is called selective cata-
technologies that already met lower NOx emission requirements [6]. lytic reduction (SCR). With SCR, a different catalyst bed is used to
Krahl et al. recently reported on addition of amine compounds at
relatively high concentrations (24%) to both conventional diesel
and biodiesel fuels [124]. It was shown that NOx emissions could be
reduced through a selective non-catalytic reduction (SNCR) process Table 2
with some amines under certain conditions, although NOx increased HD diesel engine emissions standards Europe.
under other conditions. However, challenges with respect to amine
Tier Year European emission levels, g/kw-hrh,i
solubilities and costs are likely to restrict commercial application of
HC CO NOX PM
this SNCR approach.
Another common fuel modication for reducing NOx emissions in- Euro 1 1992 1.10 4.50 8.00 0.36j
volves blending with other materials that are inherently low NOx emit- Euro II 1996 1.10 4.00 7.00 0.25
Euro IIIk 2000 0.66 2.10 5.00 0.10l
ting, especially FT fuels [48,118,125]. Other formulation strategies Euro IV 2005 0.46 1.50 3.50 0.02
have also been reported, including blending biodiesel with renewable Euro V 2008 0.46 1.50 2.00 0.02
diesel [48,58,59,126,127], blending soy FAME with pure methyl oleate Euro VI 2013 0.13 1.50 0.40 0.01
(18:1) [119], use of partially hydrogenated soy FAME [13], use of soy h
1.0 g/kW-hr = 0.7457 g/bhp-hr.
polyols [128], and use of water/biodiesel emulsions [129]. i
Based on steady-state engine test ECE R-49 from 1992 to 1998. Based on European
Stationary Cycle (ESC) and European Transient Cycle (ETC) in 1999 and beyond.
j
6. Impacts of biodiesel on exhaust after-treatment systems PM allowed to 0.612 g/kW-hr for engines b85 kW.
k
Voluntary stricter limits apply for extra low emission vehicles known as enhanced
environmentally friendly vehicles (EEV's).
Over the past 20-years, diesel emissions standards have become l
PM allowed to 0.13 g/kW-hr for engines with b0.75 dm3 swept volume per
increasingly stringent. This is shown in Tables 1 and 2, which give cylinder.
 S.K. Hoekman, C. Robbins / Fuel Processing Technology 96 (2012) 237249
directly reduce NOx to N2. However, this requires separate injection
of a chemical reductant into the exhaust stream, ahead of the SCR cat-
alyst. The most commonly used reductant is ammonia, typically used
in the form of an aqueous urea solution. A slight excess of ammonia is
helpful in maximizing reduction of NOx in the SCR catalyst, but this
results in ammonia slip emissions. An additional oxidation catalyst
may be used to treat this ammonia slip.
Both NAC and SCR are generally used as components within more
extensive after-treatment systems that also include components such
as PM traps, diesel oxidation catalysts (DOCs), O2 sensors, and other
devices. Optimized performance of a complete after-treatment system
requires sophisticated monitoring and control. Engine and vehicle
manufacturers employ various proprietary strategies to integrate the
multiple components within a complete after-treatment system, and
control their operation and performance. Other engine parameters,
such as EGR and injection phasing, are also included as part of the
entire emissions control system. Because of the variations in control
strategies, and variations in the performance of after-treatment sys-
tems under different operating conditions, it is not likely that use of
biodiesel will provide a consistent NOx effect in all situations.
A few research groups have performed controlled laboratory ex-
periments to better understand the NOx impacts of biodiesel in
modern engines using advanced after-treatment systems. One re-
search team, consisting of NREL and FEV, Inc., has reported testing
of biodiesel in a light-duty Tier 2 diesel engine and vehicle
[130,131]. ULSD base fuel was used, with biodiesel blends of B5
and B20 (soy-based FAME). Three common chassis dynamometer
test cycles were investigated: FTP-75, US06, and HFET. Two differ-
ent after-treatment systems were independently tested: (1) NAC
followed by a catalyzed diesel particulate lter (CDPF) and (2)
SCR followed by a DPF. From testing of the NAC system it was
shown that engine-out NOx was somewhat higher when using
B20 compared to B0 (by up to 10%), while tailpipe-out NOx was
slightly lower. This was attributed to higher exhaust temperatures
with B0 compared to B20 resulting from calibration of the engine
using B20 rather than B0. As a consequence of the higher exhaust
temperature with B0, the NAC was less effective in trapping NOx.
Engine dynamometer testing of the NAC system showed no impact
of B20 with respect to timing or actuator settings for controlling
lean-rich modulation. With the SCR system, no differences in
tailpipe-out NOx were observed. Overall, the impacts of B20 on
the performance of both emission control systems were considered
negligible. Furthermore, B20 use was not found to affect the dura-
bility of these emissions control systems.
In a laboratory study using a 4-cylinder, 4.0 L diesel engine
equipped with a NAC, Kawano et al. reported that use of 100% biodie-
sel (rapeseed-FAME) under steady-state operating conditions
resulted in much higher NOx compared to use of conventional diesel
fuel [97,132]. (A smaller NOx increase was observed when using B5
or B20.) This increase was attributed to insufcient desorption of
NOx during the fuel-rich spike conditions used for trap regeneration.
Two reasons for this poor performance with biodiesel were suggested:
(1) because of its high oxygen content, a larger fuel spike volume of
B100 is required to achieve the rich conditions necessary to desorb
the NOx trap, and (2) the higher density and viscosity of biodiesel ad-
versely affect atomization and vaporization of the fuel when spiked
into the exhaust system.
Yoshida et al. tested B30 (rapeseed-FAME) in a modern Toyota LD
passenger car equipped with a diesel particulate and NOx reduction
(DPNR) emission control system, which includes a NAC [133]. Com-
pared to the ULSD base fuel, use of B30 was shown to reduce CO,
HC, and PM, but have no effect on NOx. Using the same vehicle
type, Lance et al. explored a range of biodiesel blends from B5 to
B100, with the fuels produced from several different feedstocks
[134]. The New European Drive Cycle (NEDC) was utilized, and nu-
merous emissions species were measured. With blending levels of
245
B30 and below, minimal NOx increases were observed, while larger
increases occurred when using B100.
McWilliam and Zimmermann recently reported on the effect of bio-
diesel usage in a HD Caterpillar engine equipped with a vanadium-
based SCR system [135]. In testing over a non-road transient cycle,
both B20 and B100 exhibited the expected small engine-out NOx in-
crease; but, much larger relative NOx increases were observed after
the SCR unit. (Absolute emission rates, expressed as g NOx/kW-hr,
were an order of magnitude lower after the SCR unit.) It was also
shown that the NOx conversion efciency of the SCR system was re-
duced by 6% when operating on B100. This was explained by changes
in the NO2/NOx ratio of the exhaust stream exiting the diesel oxidation
catalyst (DOC), which preceded the SCR. When using biodiesel, the
NO2/NOx ratio was substantially reduced. This adversely affected the
ammonia-driven reduction reactions within the SCR, and caused an in-
crease in ammonia slip emissions.
Williams et al. reported that use of B20 in a 2004 Cummins ISB en-
gine equipped with a zeolite-based SCR system produced no mea-
sureable difference in overall NOx compared to base fuel, despite
the fact that B20 gave slightly lower catalyst temperatures and higher
NO2/NOx ratios [136]. This was explained by the observation that
space velocity (or residence time) was the dominant variable control-
ling the overall NOx conversion efciency of the SCR system, and this
was not affected by B20.
Williams et al. also investigated how use of biodiesel affects the
performance of a Fe-zeolite SCR catalyst used for NOx reduction
[137]. These catalysts are meant to adsorb NOx during normal opera-
tion, and then release the NOx (as N2) during a fuel rich spike. How-
ever, they also adsorb hydrocarbons during low temperature
conditions, thereby inhibiting the catalyst's NOx reduction ability
until the temperature is increased sufciently to desorb the hydrocar-
bons. These researchers used a combination of laboratory ow reactor
and engine tests with ULSD and B100 fuels. It was demonstrated that
B100 exhibited the same catalyst masking behavior as did ULSD, but
the recovery time was shorter with B100. Using ULSD, NOx conver-
sion was inhibited until the catalyst reached a temperature of
400 C, while only 200 C was needed with B100.
More recently, a consortium of organizations performed an ex-
tensive laboratory study to investigate potential impacts of biodiesel
fuel impurities upon the performance of after-treatment systems
[138]. The B20 test fuel was doped with alkali and alkaline earth im-
purities to achieve the upper limits of these impurities as allowed by
fuel standard, ASTM D6751. Accelerated durability tests were con-
ducted to determine whether the higher ash levels produced from
this doped fuel affected the performance and durability of various
diesel emissions control system components. Results from testing a
2008 HD Caterpillar C9 ACERT engine provided several indications
of adverse impacts including increased pressure drop across the
diesel particulate lter (DPF), reduced catalyst activity of the DOC,
and activity loss of the SCR catalyst, resulting in slight NOx emis-
sions increases. The applicability of the testing conditions and re-
sults from this study to real-world situations is not fully known,
but this work has raised the possibility of concerns with long-term
usage of biodiesel.
7. Conclusions
The literature contains a rich amount of information regarding the
effects of biodiesel on NOx emissions. In most cases though certain-
ly not all use of biodiesel or biodiesel blends increases NOx emis-
sions in comparison with baseline petroleum diesel fuel. One reason
for inconsistency in the literature is that no single factor is responsi-
ble for these NOx effects. Rather, numerous factors contribute, and
their relative importance varies with engine technology and operat-
ing conditions.
246 S.K. Hoekman, C. Robbins / Fuel Processing Technology 96 (2012) 237249

Many theories have been proposed to help explain the effects of 2-EHN 2-Ethylhexyl nitrate
biodiesel on NOx emissions. These relate primarily to biodiesel's ef- EN European Norm
fect on injection timing, ignition delay, adiabatic ame temperature, EPA U.S. Environmental Protection Agency
radiative heat loss, and other combustion phenomena. The extent to FAEE Fatty acid ethyl ester
which these theories apply also varies with engine technology and FAME Fatty acid methyl ester
operating condition. For example, older engines having mechanical FT FischerTropsch
fuel injection systems exhibit an inadvertent advance in fuel injection FTD Fischer Tropsch diesel
timing, due to the higher bulk modulus of compressibility of biodie- FTP Federal test procedure
sel. Modern electronically-controlled diesel engines no longer experi- GHG Greenhouse gas
ence this effect, but they can exhibit other NOx effects (both positive HC Hydrocarbons
and negative) depending upon how the engine control system re- HCCI Homogeneous charge compression ignition
sponds to fuel changes, such as the lower energy content of biodiesel HD Heavy-duty
compared to conventional diesel. ICE Internal combustion engine
Recent laboratory experimental work has demonstrated that with IV Iodine value
modern engines, use of biodiesel typically results in a more advanced LAD Low aromatic diesel fuel
and faster overall combustion event, which leads to elevated in- LCFS Low carbon fuel standard
cylinder temperatures and increased NOx formation. A likely contrib- LD Light-duty
uting factor is the oxygen content of biodiesel, resulting in a charge LTC Low temperature combustion
gas composition that is closer to stoichiometric (less rich) in the LSD Low sulfur diesel
ame autoignition zone. N2O Nitrous oxide
Several approaches for mitigating the biodiesel NOx effect have NAC NOx adsorber catalyst
been investigated. The most effective engine modications involve NEDC New European drive cycle
retarded injection timing and increased use of EGR. Modern engines, NO Nitric oxide
with sophisticated computer control systems, offer the possibility of NO2 Nitrogen dioxide
other mitigation strategies, including a process called low-temperature NOx Oxides of nitrogen
combustion (LTC). Fuel modications including reduced aromatics NREL National Renewable Energy Laboratory
content and use of cetane improvers have been shown to mitigate OBD On-board diagnostics
the biodiesel NOx effect in some situations. However, it appears PM Particulate matter
that with modern engines and fuels (ULSD), the benets of such PM10 PM with diameter 10 m
fuel modications are quite limited. RFS Renewable fuel standard
Exhaust after-treatment systems required to meet the U.S. 2010 SAE Society of Automotive Engineers International
HD engine standards have only been in use for a short time. Conse- SCR Selective catalytic reduction
quently, there is little real-world operational experience with them. SNCR Selective non-catalytic reduction
However, based upon the information currently available, it appears SOC Start of combustion
that use of biodiesel especially at blend levels of B20 and below SOI Start of injection
does not seriously affect the short-term performance of either NAC- SOx Oxides of sulfur
based or SCR-based after-treatment systems. However, there are TDC Top dead center
some indications that long-term usage of biodiesel, and/or use of ULSD Ultra-low sulfur diesel fuel (max. of 15 ppmS)
poor quality fuel, could result in increased NOx emissions. Further
long-term study is warranted.
Acknowledgments
Acronyms and abbreviations
This work was sponsored, in part, by the Coordinating Research
API American Petroleum Institute Council (CRC), as Project AVFL-17a. The authors acknowledge the
ASTM American Soc. for Testing and Materials International entire AFVL-17a Panel for their helpful guidance and suggestions.
B100 Neat (100%) biodiesel We also acknowledge the following DRI colleagues for their contri-
B20 Blend of 20% biodiesel in petroleum diesel butions: Amber Broch, Eric Ceniceros, John Ford, and Elke Seymour.
BHP Brake horsepower
BTU British thermal unit References
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