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PAST M I S T A K E S AND FUTURE OPPORTUNITIES OF E T H A N O L IN DIESEL

Galen J. Suppes
Department of Chemical & Petroleum Engineering
The University of Kansas, Lawrence, KS 66045-2223
gsuppes@ukans.edu

ABSTRACT
Due to the oxygen content of ethanol, ethanol has the potential to significantly lower
particulate matter emissions from diesel engines. Unfortunately, this has not been
systematically observed since ethanol simultaneously both increases oxygen content and
decreases the cetane number of a fuel. In some cases, the adverse impacts of a lower
cetane number outweigh the benefits of an increased oxygenate content.
Ethanors high vapor pressure can also lead to both vapor lock and cavitation--leading to
performance problems that are often incorrectly attributed to the fuel rather than to the
fuel delivery system. To further complicate matters, ethanol has miscibility problems
with some types of diesel. Many formulations of ethanol in diesel include emulsifier
additives that can add more to the cost of the fuel blend than the ethanol.
This paper summarizes the factors impacting phase behavior and provides procedures for
selecting diesel stocks that enhance formation of homogeneous solutions. Safety issues
associated with the low flash point of ethanol are also discussed. Finally, the impact on
cetane number and approaches for the successful application of cetane improvers are
discussed.

Key Words: Ethanol, Diesel, Cetane, Solution, Oxygenate

INTRODUCTION
Addition of ethanol or similar blend stocks to petroleum-based diesel has been
investigated by several researchers. Unlike mixtures of oxygenates with gasoline,
mixtures of oxygenates with diesel have not been accepted on a widespread basis as
providing performance advantages that justify commercialization.
Eckland et al (1984) present a "State-of-the-Art Report on the Use of Alcohols in Diesel
Engines". Techniques that have been evaluated for concurrent use of diesel and alcohols
in a compression-ignition engine include (1) alcohol fumigation, (2) dual injection (3)
alcohol/diesel fuel emulsions, and (4) alcohol/diesel fuel solutions.
Of these four options, fumigation and dual injection require additional and separate fuel
handling systems including additional injectors for either manifold injection (for
fumigation) or direct injection. Accordingly, these alternatives represent both a
significant incremental cost for vehicle production and increased operational
inconvenience related to refilling two fuel tanks rather than one. In the case of
fumigation, Heisey and Lestz (811208) report significant reductions in particulate
generation; however, NOx generation increases. The incremental vehicular costs and
increased NOx associated with fumigation have limited its acceptance.
By definition, alcohol/diesel fuel emulsions are fuels with two liquid phases in
equilibrium where a substantial portion of the ethanol is in a hydrophilic phase that is
entrained in a continuous diesel phase. To maintain stable fuel emulsions of alcohol and
diesel, large amounts of costly emulsifiers are typically required. Baker (1981) reported
that 9:10 and 3:2 parts by volume of alcohol to emulsifier were required by methanol and
ethanol, respectively, to create stable emulsions. Emulsifiers are always needed with
methanol to maintain the entrainment of the methanol phase. They are needed with
ethanol when the water content of ethanol is greater than -0.1%.
Likos et al (1982) reports increased NOx and hydrocarbon emissions for diesel-ethanol
emulsions. Khan and Gollahalli (811210) report decreased NOx and hydrocarbon
emissions with increased particulate emissions for diesel-ethanol emulsions. Lawson et
al (810346) report increased NOx and decreased particulate emissions with dieselmethanol emulsions. This type of inconsistent performance is what has hindered the use
of ethanol in diesel.
Alcohol-diesel fuel solutions form a homogenous phase rather than two liquid phases.
Methanol is substantially insoluble in diesel, and so, most solution work has been
performed with ethanol. A disadvantage of solutions is that two liquid phases form when
the alcohol-diesel mixture is contacted with water. Although this can manifest into
operating difficulties, similar problems occur when straight diesel is contacted with
water.
Baker (1981) reports diesel-ethanol emulsions produce similar NOx, hydrocarbon, and
particulate emulsions as compared to baseline runs with straight diesel. Khan and
Gollahalli (1981) report increased particulate emissions with ethanol-diesel mixtures.

Test results of ethanol-diesel solutions are inconclusive and mixed as are reported data
for emulsions.
When pursuing an understanding of the performance and potential of ethanol in diesel
through a comprehensive survey of literature, the presence of at least four different
approaches and mixed results within each of these approaches confuses the issues and
makes definitive conclusions essentially impossible.
The present paper considers only ethanol-in-diesel solutions since these alone have
neither a significant incremental vehicular cost nor high emulsifier fuel-additive cost
(often rivaling the cost of the ethanol in the fuel). The most pertinent topics are discussed
based on fundamentals and several recent engine tests performed with knowledge of
common performance pitfalls encountered when testing ethanol-in-diesel fuels.
ETHANOL-IN-DIESEL PHASE BEHAVIOR
As illustrated by Figure l, the phase behavior of the ethanol-diesel system is a strong
function of ethanol content and temperature. Most petroleum-based diesel fuels will
exhibit the indicated phase behavior. Increasing volatility and increasing aromatic
contents will tend to decrease the two-phase region by lowering the curve up to 15 C - the curve illustrated by Figure 1 is characteristic of US-2D fuel. Trace amounts of water
will sharply increase the two-phase region. Data and models quantifying these trends are
available elsewhere (Suppes and Gerdes, 2000).
Based on these trends, the following observations can be made on performance
limitations and the best application opportunities:

40
30

1 Liquid Phases

20
10

io
~-10
-20

~15 C

-30

2 Liquid Phases

-40
0

0.1

0,2

0.3
0.4
0.5
Ethanol (volume fraction)

0.6

0.7

0.8

Figure 1. Typical ethanol/diesel phase behavior.

lower ethanol concentrations have reduced tendencies toward immiscibility


problems,

at about 5% ethanol (- <0.005% water) in diesel, the low-temperature


miscibility limitations are substantially similar to those of the pure diesel, and

reduced low-temperature miscibility limits can be achieved by using a diesel


with a lower cloud point (winter grades),

By following these guidelines, two-phase regions can be avoided leading to stable


ethanol-in-diesel solutions. The primary advantage of solutions over emulsions is the
elimination or reduction of costs associated with emulsifiers.
EXHAUST EMISSIONS OF ETHANOL-IN-DIESEL FUELS
The diesel engine and diesel fuel combustion within a diesel engine are very complex
processes, and as such, relating changes in exhaust emissions to changes in fuel
properties is less than straight-forward. The evaluation of fuel performance becomes
even more complex when attempting to compare the best possible performance of a
diesel fuel with and without ethanol blend stock. Recognizing these disclaimers, the first
step to evaluating the performance of ethanol-in-diesel solutions is the definition of how
performance is to be determined.
EPA regulations for diesel engines are based primarily on particulate matter (PM) and
NOx emissions per amount of work performed by the diesel engine (g/bhp/hr). In the
U.S., hydrocarbon emissions are considered cumulative with NOx emissions. However,
the NOx emissions are typically much greater than hydrocarbon emissions, and
hydrocarbon emissions can be effectively reduced with catalytic converters. Thus, the
relative performance of a diesel fuel can be quantified for most applications based on
reductions in PM without an increase in NOx or a reduction in NO~ without an increase in
PM.
Oxygenates tend to impact PM and NOx as follows:
. Oxygenates, including ethanol, generally have the capacity to reduce PM
emissions. This is normally observed during engine tests and is
fundamentally corroborated by the fact that the chemically-bound oxygen in
fuels reduce the amount of diatomic oxygen that needs to diffuse to the fuel
droplets for complete combustion. In practice, PM emissions depend
considerably both on the fuel properties and engine operation. Table 1
summarizes ethanol-in-diesel engine particulate matter and some opacity
emissions for tests performed in our lab and by VTT Energy.
. Oxygenates typically do not have a large impact on NOx emissions. Unlike
PM emissions, engine operation including injector timing tends to have a
greater impact on NOx emissions than the fuel. The exception to this rule is
when the cetane number of the fuel is low.

Table 1. Emissions data for ethanol-in-diesel fuels and ethanol in Fischer-Tropsch liquid
(FTL) fuels.
Volkswagen 1.9L TDI Engine (Laborato~ of Suppes)
Opacit7
FTL + 25% EtOH
0.59
FTL + 10% EtOH
0.71
FTL + 10% Methoxyethyl Ether
0.88
US-1D with 10% EtOH
0.57
US- 1D with 10% EtOH + 1% EHN
0.74
FTL + 20% EtOH
0.86
FTL
1.03
US-1D
1.11
US-2D
1.31

Detroit Diesel 453T (Suppes et al., 1999)


Fuel
US 2D diesel
US 1D diesel
FTL-2 + 25% Gasoline
FTL-2
FTL-2 + 20% Ethanol
FTL-2 + 16.5% Ethanol + 16.5% Diethyl Ether
FTL-2 + 10% Ethanol + 10% Diethyl Ether
FTL-2 + 25% Ethanol

PM ~m~)

0.58
0.53
0.87
0.96
0.98
1.40
1.39

50%
Load
151%
100%
120%
95%
60%
72%
70%
51%

80%
Load
88%
100%
77%
82%
51%
31%
49%
37%

Heavy-Duty Volvo En[ine, ECE R49 Test ~Aakko and Nylund, 1997)
PM
Fuel
CEC-United Nation Reg. No. 49 Reference Fuel
ASTM US 2D Diesel
Scandinavian Low-Emission Diesel
RME20-CEC with 20% Rape Seed Methyl Ester
TME20-CEC with 20% Tall Oil Methyl Ester
EtOH15-Diesel Fuel with 15% Ethanol*
EtRE-Diesel Fuel with 15% Ethanol & 4.3% RME*
* contains <1% Etamix 15 Emulsifier, Emulsion

(g/kWh)
0.220
0.210
0.186
0.200
0.250
0.135
0.148

0.35
0.30
1991

0.25

4=

Base Fuel

Q- 0.20

.Q

Fuel

0.15

1994

1998

a. 0.10
0.05
0.00

0.0

1.0

2.0
NOx

3.0
(g I bhp-hr)

4.0

5.0

Figure 2. Performance curve of improved diesel fuel.


Engine operating parameters such as injector timing and exhaust gas recirculation (EGR)
can (1) decrease PM at the expense of increasing NOx or (2) decrease NOx at the expense
of increasing PM. Figure 2 illustrates how engine parameters such as injector timing or
EGR can be used to generate a performance curve relative to meeting EPA regulated PM
and NOx emissions. The arrows indicate the type of reductions in emissions that can be
achieved based on a change in fuel. When evaluating the potential of ethanol in diesel,
the specific changes in emissions (represented by different arrows) are not as important
as the new performance curve of the improved fuel (diesel with oxygenate).
When properly used, ethanol improves the performance curve of a diesel fuel. To realize
this improved performance curve without compromising other aspects of performance or
safety, several operating and equipment constraints must be followed.
OPERATING AND EQUIPMENT CONSTRAINTS
FOR OPTIMAL ETHANOL-IN-DIESEL PERFORMANCE
Over-Sized Fuel Injectors - The volumetric heating value of ethanol is less than diesel,
and so, injectors must deliver more of an ethanol-in-diesel solution to achieve the same
power (as compared to the volume of neat diesel that must be delivered). For some
engines, the injectors may have excess capacity that can be utilized; however, if this
excess fuel delivery capacity is not provided a reduction in engine power will typically
result. Ideally, new engines should be designed with excess fuel delivery capacity based
on the anticipation of cleaner-burning lower-heating-value fuels such as ethanol-in-diesel
solutions and Fischer-Tropsch fuels. If a larger fuel injector is required, this can impact
fuel performance and may diminish the advantages of adding ethanol to diesel.
Cetane Number Correction - For typical application rates, ethanol will reduce the cetane
number of diesel - 7 points for every 10% ethanol in diesel. If this reduction in cetane
number results in a fuel cetane < 40, the fuel is no longer within specifications and the
engine may not be able to properly change injection timing to compensate for the
increased ignition delay time. As a result, more fuel can accumulate prior to ignition

leading to a high-temperature premix combustion that produces excess NOx emissions.


The best way to correct this problem is to add cetane improver fuel to the extent
necessary to bring the fuel within specifications.
Vapor Lock and Cavitation - The vapor pressure of an ethanol-in-diesel fuel is
considerably greater than that of neat diesel. In addition, the viscosity is lower--the
lower viscoity results in a lower static pressure in the fuel delivery system. As a result of
these combined traits, ethanol-in-diesel has a significantly greater tendency to evaporate
and form erratic locations of vapor lock in the fuel delivery system. This vapor lock will
happen at the locations of lowest static pressure, such as the fuel intake of the injector,
resulting in too little fuel being delivered to the injector and subsequent cavitation inside
the injector. Both the vapor lock and cavitation can be detrimental to fuel performance.
To prevent the vapor lock and subsequent cavitation, the static pressure of the fuel
delivery system must be increased. This can be achieved by either (1) reducing the size
of the restrictive orifice on the diesel fuel return line or (2) introducing a backpressure
regulator to the diesel fuel return line. The good performances of ethanol-in-diesel fuels
of Table 1 were achieved only after vapor lock problems were corrected.
Vapor Pressure & Safety - Ethanors high polarity and tendency toward hydrogen
bonding cause ethanol to have a high activity in gasoline and diesel. This high activity
leads to both limited miscibilities and high vapor pressures. In ethanol-gasoline blends
(< 20% ethanol), the activity (yixi) of ethanol reaches a maximum of-0.5 at - 4 % ethanol
in gasoline (based on data published in Owen and Coley, 1995)--the activity remains at
this level at 2%-20% ethanol in gasoline. Since ethanol has an even higher activity in
diesel it would typically have activities between about 0.7 and 0.9 at diesel blending
ratios. These activity estimates allow the flash point temperature of ethanol blends in
diesel to be estimated as summarized in Table 2.

Table 2. Flash points of gasoline, diesel, ethanol, and ethanol blends.


Fuel

Flash Point

ASTM D 975

US-2D Diesel

52 C min.

ASTM D 975

US-1D Diesel

38 C min.

Typical Values

Gasoline

-40 C max.

Ethanol

16 C

Estimate

E85

- 25 C max.

Estimate

2%-20% Ethanol in Diesel

17-20 C

Source of Flash Point Data

The ethanol-in-diesel blends have flash point temperatures estimated to be slightly below
typical ambient temperatures; this translates to fuel tanks having ignitable mixtures of
fuel and air during most operating conditions. By comparison, vapor spaces of diesel
storage tanks are typically too fuel lean for ignition while vapor spaces over gasoline and
E85 are typically too fuel rich for ignition. This is a safety issue that should be addressed
for both ethanol-in-diesel solutions and ethanol-in-diesel emulsions. One method for
solving potential vapor pressure problems of ethanol-in-diesel solutions is to add an
additional volatile component to the system so as to increase the vapor pressure into a
fuel-rich regime that is outside ignition limits--candidate blend stocks include hexane,
pentane, naphtha, and diethyl ether.
Liquid Phase Stability -Based on the phase behavior (Figure 1) of ethanol in diesel,
diesel grades (volatility and aromaticity) and ethanol contents can be selected that lead to
homogeneous fuel solutions; however, this homogeneous phase behavior can and will
change when the fuel contacts water. When ethanol-hydrocarbon solutions are initially
introduced into a system accustomed to handling gasoline or diesel, the presence of water
can cause problems. However, once the free water is removed from these systems, the
ethanol-hydrocarbon fuels have increased solubilities for water and can continuously
dissolve small amounts of water, carrying the water through the engine without difficulty.
And so, while water can cause problems with ethanol-hydrocarbon fuels, the continuous
use of these solutions in a system tends to minimize the likelihood that sufficient water
will accumulate to cause problems.
When proper quality control measures are taken, ethanol-in-diesel solutions can be
continually used without incident; however, proactive/preventative measures can be of
significant value. Such proactive measures are more important in diesel than in gasoline
since phase separation in diesel will lead to an ethanol-rich hydrophilic phase that will
stall the diesel engine. Ethanol-rich hydrophilic phases of gasoline can continue to power
a gasoline engine and avoid stalling.
Two proactive approaches that can lead to avoiding incidents of stalled diesel engines
due to phase separation problems include (1) use of hydrophilic cetane improvers that
would migrate to a hydrophilic phase (if formed) and boost the cetane to allow the
ethanol phase to continue to power the diesel engine and (2) use of emulsifiers that would
emulsify a hydrophilic phase formed if water contacts the system. Of these, the
emulsifier approach is the most viable since several emulsifiers have been demonstrated
and are available for forming ethanol-in-diesel emulsions.
With proactive emulsifier approaches, the application rate can be much lower than is
required with typical emulsions. In general, the higher the emulsifier application rate the
more water tolerable (toward avoiding engine stalling) the ethanol-in-diesel solution.
Emulsifier application rates that provide the proper balance of (1) lower cost with lower
application rates and (2) increased protection with higher application rates have yet to be
determined and would depend on many factors specific to the application. An ethanol-indiesel solution that contains an optimal amount of emulsifier would have considerably
lower emulsifier costs than ethanol-in-diesel emulsions. As a result of these lower

emulsifier costs, the cost of using the fuel would be less and a greater fraction of the cash
flow is routed to the ethanol industry,
CONCLUSIONS
Ethanol-in-diesel solutions provide an effective approach to reducing particulate matter
emissions in diesel engines, and ethanol may be the most cost effective oxygenate for this
application. However, unlike most fuel additives and blend stocks, the benefits of
ethanol-in-diesel may not be realized by simply adding ethanol to the diesel for use in an
unmodified diesel engine. A multitude of pitfalls exist with the use of ethanol in diesel
solutions, Fortunately, these pitfalls can be overcome with low or no incremental cost.
To avoid miscibility problems, anhydrous ethanol must be used and its application rate
should be determined based on the volatility and aromatic content of the diesel blend
stock as well as the ambient temperatures where the fuel is to be used. The diesel fuel
delivery system should be modified to provide increased fuel pressures at the injector
pump inlet--this often translates to placing a smaller restrictive orifice or a backpressure
regulator at the diesel fuel return. Cetane improvers should be added as necessary to
keep the cetane number >40 and emulsifiers should be added as a proactive measure for
preventing phase separation if the fuel inadvertently contacts water. Over-sized fuel
injectors may also be necessary to compensate for the lower heating value of the ethanol
blend so as to avoid reduced maximum power abilities of the engine. Finally, operators
should be aware that the ethanol blends may have reduced flash points that can increase
fire and explosion hazards--additional blend stocks can be added to avoid this potential
problem.
ACKNOWLEDGEMENTS
This work was performed as part of activities related to the NRI Competitive Grants
Program/USDA award numbers 97-35504-4244 and 99-35504-8673. Their support is
appreciated.
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Likos, B.; T. J. Callahan; and C. A. Moses. Performance and Emissions of Ethanol and
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