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<a href=Fuel Processing Technology 96 (2012) 237 249 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 article info Article history: Received 23 June 2011 Received in revised form 28 December 2011 Accepted 30 December 2011 Available online 30 January 2012 Keywords: Biodiesel NOx Emissions FAME Contents abstract Compared to conventional diesel fuel, use of biodiesel is generally found to reduce emissions of hydrocarbons (HC), carbon monoxide (CO), and particulate matter (PM); but to increase oxides of nitrogen (NOx) emissions. This paper reviews and summarizes relevant literature regarding the so-called “ biodiesel NOx effect, and pre- sents theories ” to explain this effect. In modern diesel engines, several factors related to fuel composition and engine control strategies are important, though no single theory provides an adequate explanation of the bio- diesel NOx effect under all conditions. There is evidence to suggest that effects on injection timing, ignition delay, adiabatic fl ame temperature, radiative heat loss, and other combustion phenomena all play some role. The biodiesel NOx effect can be mitigated by modifying engine control settings — particularly by retard- ing injection timing and increasing exhaust gas recirculation (EGR). The absolute magnitude of the biodiesel 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 signi fi cantly 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. 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 fl 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 Engine effects . 4.2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 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 modi fi cations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243 5.2. Fuel modi fi cations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 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 " id="pdf-obj-0-7" src="pdf-obj-0-7.jpg">

Contents lists available at SciVerse ScienceDirect

Fuel Processing Technology

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

<a href=Fuel Processing Technology 96 (2012) 237 249 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 article info Article history: Received 23 June 2011 Received in revised form 28 December 2011 Accepted 30 December 2011 Available online 30 January 2012 Keywords: Biodiesel NOx Emissions FAME Contents abstract Compared to conventional diesel fuel, use of biodiesel is generally found to reduce emissions of hydrocarbons (HC), carbon monoxide (CO), and particulate matter (PM); but to increase oxides of nitrogen (NOx) emissions. This paper reviews and summarizes relevant literature regarding the so-called “ biodiesel NOx effect, and pre- sents theories ” to explain this effect. In modern diesel engines, several factors related to fuel composition and engine control strategies are important, though no single theory provides an adequate explanation of the bio- diesel NOx effect under all conditions. There is evidence to suggest that effects on injection timing, ignition delay, adiabatic fl ame temperature, radiative heat loss, and other combustion phenomena all play some role. The biodiesel NOx effect can be mitigated by modifying engine control settings — particularly by retard- ing injection timing and increasing exhaust gas recirculation (EGR). The absolute magnitude of the biodiesel 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 signi fi cantly 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. 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 fl 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 Engine effects . 4.2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 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 modi fi cations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243 5.2. Fuel modi fi cations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 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 " id="pdf-obj-0-17" src="pdf-obj-0-17.jpg">

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

article info

Article history:

Received 23 June 2011 Received in revised form 28 December 2011

Accepted 30 December 2011 Available online 30 January 2012

Keywords:

Biodiesel

NOx

Emissions

FAME

Contents

abstract

Compared to conventional diesel fuel, use of biodiesel is generally found to reduce emissions of hydrocarbons (HC), carbon monoxide (CO), and particulate matter (PM); but to increase oxides of nitrogen (NOx) emissions. This paper reviews and summarizes relevant literature regarding the so-called biodiesel NOx effect, and pre- sents theoriesto explain this effect. In modern diesel engines, several factors related to fuel composition and

engine control strategies are important, though no single theory provides an adequate explanation of the bio-

diesel NOx effect under all conditions. There is evidence to suggest that effects on injection timing, ignition delay, adiabatic ame temperature, radiative heat loss, and other combustion phenomena all play some role. The biodiesel NOx effect can be mitigated by modifying engine control settings particularly by retard- ing injection timing and increasing exhaust gas recirculation (EGR). The absolute magnitude of the biodiesel 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.

  • 1. Introduction

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238

  • 2. NOx formation mechanisms

 

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238

  • 2.1. Thermal NOx .

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238

  • 2.2. Prompt NOx .

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239

  • 2.3. Fuel NOx

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239

  • 3. Theories of biodiesel's impacts on NOx

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239

  • 3.1. Speed of sound and bulk modulus of compressibility

 

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239

  • 3.2. Decreased radiative heat loss

 

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239

  • 3.3. Higher adiabatic ame temperature .

 

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240

  • 3.4. Combustion phasing theories

 

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240

  • 3.5. Engine control/calibration theories

 

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240

  • 4. Experimental evidence of biodiesel's impacts on NOx emissions

 

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240

  • 4.1. Fuel effects .

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240

4.1.1.

Fuel composition effects

 

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240

4.1.2.

Combustion phasing effects

 

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241

4.1.3.

Other fuel effects .

 

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242

Engine effects .

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242

4.2.1.

Injection parameters

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242

4.2.2.

Engine calibration .

 

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242

4.2.3.

Engine load .

 

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243

  • 5. Mitigation of NOx increases

 

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243

  • 5.1. Engine modications

 

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243

  • 5.2. Fuel modications .

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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.

  • 238 S.K. Hoekman, C. Robbins / Fuel Processing Technology 96 (2012) 237249

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

 

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  • 7. Conclusions

 

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Acronyms and abbreviations

 

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Acknowledgments

 

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References

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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 biodieselrefers 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

Percent Change in Emissions
Percent Change in Emissions

Percent Biodiesel

Fig. 1. Average emission impacts of biodiesel for HD highway engines. Figure taken from EPA [4].

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 NO 2 . Under most conditions, other oxides of nitrogen such as N 2 O, N 2 O 5 , NO 3 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, N 2 and O 2 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 y =5.0264ln(x) - 13.795 R 2 = 0.2353 20 10 0 -10 -20 0
40
30
y =5.0264ln(x) - 13.795
R 2 = 0.2353
20
10
0
-10
-20
0
20
40
60
80
100
Change from Base Fuel, %

Biodiesel Blend Level, %

Fig. 2. NOx emissions effects of biodiesel fuels compared to petroleum diesel fuel in 4-stoke HD diesel engines (1987 and newer). Data taken from Hoekman et al. [5].

S.K. Hoekman, C. Robbins / Fuel Processing Technology 96 (2012) 237249

239

12 B20 (n = 88) Total (n) = 207 Above line= 154 10 B100 (n =
12
B20 (n = 88)
Total (n) = 207
Above line= 154
10
B100 (n = 69)
other (n = 49)
Below line = 45
Online = 8
8
6
4
2
0
0
2
4
6
8
10
12
Biodiesel NOx Emissions, g/bhp-hr

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 CH 2 reacting with N 2 in the combustion cham- ber [16]. The resulting C\N containing species then proceed through reaction pathways involving O 2 to produce NOx. Prompt NOx is only prevalent under fuel rich conditions, where there is an abundance of hydrocarbon fragments to react with N 2 . 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.

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

of theories have been developed to help understand these factors and

help explain the predominance of test data showing increased NOx

with use of biodiesel. The literature contains several reports that pro-

vide useful summaries of these theories, in particular, reports by

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.

Several of the most common theories are briey described below;

experimental evidence to support them is discussed in Section 4. It

should be emphasized that these theories are not mutually exclusive.

Rather, they should be regarded as inuential factors that partially 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 1[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 railelectronic-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 T 90 ); 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

241

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 cleanbase fuels as com- pared to averagebase fuels [4]. Cleanbase fuels generally had lower aromatics, higher cetane number, lower density, and lower dis- tillation temperatures as compared to averagebase 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

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 O 2 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 T 90 speci- cation of 360 °C [1], as compared to the conventional diesel standard, ASTM D975, which has a maximum T 90 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 mapsof 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

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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 1[88]. Subse- quently, Choi and Reitz demonstrated the NOx reduction benets of both retarded and split injection techniques when using biodiesel in

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 H 2 O and CO 2 ). 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

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hydrocarbon base fuels were used to produce the B20 blends: (1) fed- eral certication fuel (31.9% aromatics; 0.04% sulfur), (2) 10% low ar- omatics diesel (7.5% aromatics; 0.01% sulfur), and (3) FT diesel (0% aromatics; b 0.01% sulfur). Based upon results of HD FTP testing, it was demonstrated that NOx emissions from B20 blends were reduced considerably when using either the 10% low aromatics diesel or the FT diesel in place of conventional diesel fuel. Using linear extrapolation of the results, the authors concluded that a base fuel having 25.8% ar- omatics would provide a NOx neutralB20 blend relative to use of the certication base fuel. When using the FT diesel as base fuel, a biodie- sel blend as high as B55 was predicted to be NOx neutral. Also in this study, the effects of cetane improvers upon NOx were determined. Both di-t-butyl peroxide (DTBP) and 2-ethylhexyl nitrate (2-EHN) were shown to be effective. The authors concluded that use of cetane improvers was a practical strategy for NOx reduction in the short term. In a related study, McCormick et al. again demonstrated the effec- tiveness of cetane improvers, DTBP and 2-EHN, in reducing NOx emis- sions from biodiesel blends [41]. They also observed NOx reduction with use of the anti-oxidant additive, t-butyl-hydroquinone (TBHQ). 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, reducing the certication diesel fuel's aromatics content from 32% to 25%, combined with use of DTBP, did meet the CARB fuel's perfor- mance. The authors also reported that B20 NOx emissions were higher with soy-derived FAME than with yellow grease-derived FAME. This was attributed to higher unsaturation of the soy material, which had an iodine value of 127, compared to 79 for the yellow grease. Several other groups have reported benecial effects of cetane im- provers in reducing NOx emissions from biodiesel and biodiesel blends, with DTBP and 2-EHN being the two most frequently employed additives. Positive effects have been found in single cylinder laboratory test engines [119,120] as well as production HD engines [48,121123], although the effectiveness varied depending upon spe- cic engine and operating conditions. In some cases, DTBP was found to be more effective than 2-EHN [48,59,122]. Nuszkowski et al. recent- ly evaluated the effect of DTBP and 2-EHN in ve HD engines spanning a range of technology types [123]. They observed that the cetane im- provers were effective in reducing NOx from the older technology en- gines, but had little benet with newer engines equipped with higher compression ratios and use of EGR. Also, these additives were most ef- fective under low engine power condition, but offered little benet at high power. Finally, Yanowitz and McCormick concluded that the ben- ets of cetane improvers appeared to diminish with newer engine technologies that already met lower NOx emission requirements [6]. 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 with some amines under certain conditions, although NOx increased under other conditions. However, challenges with respect to amine solubilities and costs are likely to restrict commercial application of this SNCR approach. Another common fuel modi