ETHANOL ULTILIZATION IN A DIESEL ENGINE

Final Contract Report

Summarizing Research during the Period May 31, 2007 through December 31, 2009






Prepared by:




Anil Singh Bika, Luke Franklin, Andr L. Olson, Winthrop Watts, and David Kittelson




University of Minnesota
Department of Mechanical Engineering
Power and Propulsion Laboratory and
Center for Diesel Research
111 Church St. SE
Minneapolis, MN, 55455




2
SUMMARY

In May 2007 the Minnesota Corn Growers Association funded a research project
to investigate the combustion of ethanol in a diesel engine. Contractual issues resulted in
a second contract being issued in March 2009 to complete the original project. The
objective of both contracts was to develop a means of using nearly pure ethanol as a
diesel fuel. To facilitate ethanol combustion a small fraction of ethanol would be directed
to an on-board autothermal reformer to produce hydrogen rich gases
1
. The gas stream
would be introduced into the combustion chamber through intake ports while the ethanol
would enter through the normal fuel injectors. Although our initial findings were
promising we decided that resource limitations did not allow us to pursue this line of
research to the next level so we refocused the project to emphasize fumigation using
lower cost blends of hydrous ethanol. For this work diesel fuel was used to ignite a
premixed ethanol air mixture. The project was completed in December 2009 and this
report summarizes the findings.
Goals of the research were to demonstrate how hydrogen may provide the means
to facilitate the combustion of ethanol in a CI engine with minimal modifications (i.e.
operating at real world compression ratios and intake air temperatures), and to evaluate
fumigation as a method of introducing ethanol into a diesel engine.
It was discovered that as predicted hydrogen injection allowed direct use of 100%
ethanol as a Diesel fuel under moderate compression ratio and intake pressure conditions.
This suggest that it will be possible to run a Diesel engine with ethanol as the sole fuel if
a suitable low cost system for onboard conversion of a small fraction of the ethanol into
hydrogen rich gases can be developed.
The fumigation work revealed that ethanol can be used to offset 40% of Diesel
fuel use with only slight losses in thermal efficiency. Ethanol fumigation significantly
reduced particle emission, but increased hydrocarbon emissions, and under some
conditions NO
x
emissions.

BACKGROUND

There are incentives for increasing the usage of ethanol as a transportation fuel.
These include variability in fossil fuel costs, greater fuel independence, sustainability,
and greenhouse gas emission reduction. Ethanol is a first generation, oxygenated, high
octane, renewable biofuel. It is easily blended with gasoline (up to 85% in the U.S.) and
used to fuel spark ignition (SI) engines.
Ethanol is not used as a diesel fuel primarily because of insufficient fuel lubricity,
low cetane number, lack of miscibility in diesel fuel, and the propensity of alcohol to mix
with water (Hardenberg, et al., 1981; King, et al., 1992; Goering, et al., 1998; Nagarajan,
et al., 2002; Yilmaz, et al. 2005). Diesel fuel not only powers the engine but also
lubricates the fuel injection components, and inadequate fuel lubricity can result in a
deterioration of these components, which effects fuel metering and delivery
characteristics. Ethanol has an extremely low cetane rating (<10) while U.S. diesel fuel
has a cetane rating ranging from 40 to 50. This means that the ignition delay period of

1
On-board auto-thermal reforming is being investigated in the Chemical Engineering Department by Prof.
Lanny Schmidt. For our experiments bottled gas was used.
3
ethanol operation at conventional compression ratios would be too long and compression
ignition (CI) would not occur without engine modification. Ethanol miscibility in diesel
fuel is a problem especially at lower temperatures or when the ethanol has higher water
content. Despite these issues, ethanol remains of interest as a potential diesel fuel. More
highly oxygenated fuels like ethanol reduce particulate matter (PM) in diesel exhaust, and
production of corn-based ethanol reduces dependence on imported petroleum.
Additionally, diesel engines are 20 to 30% more efficient than spark ignition (SI)
engines, thus using ethanol as a diesel fuel is more efficient than using ethanol in
conventional SI engines.

Lubricity

Goering, et al (1998) investigated anhydrous (without water) and hydrous (with
water) ethanol in a two-stroke CI engine. To overcome problems with lubricity, a
proprietary Lubrizol additive was used. It was found that the hydrous ethanol reduced
oxides of nitrogen (NOx), carbon monoxide (CO), and hydrocarbon (HC) emissions. The
lower ethanol fuel energy content resulted in reduced engine power output. After
completing a 454 hr test, the only engine related issues were with sticking fuel injectors.
Nagarajan, et al. (2002) tested the performance of a CI engine running on ethanol
with 1% castor oil used as a lubricity additive. Diethyl ether (DEE) was introduced into
the intake manifold to serve as an ignition improver, so there was no need for intake air
heating. Stable operation was achieved with 3% DEE by ethanol mass share; however the
ignition delay period of ethanol was lengthened by 8 crank angle degrees (CAD)
compared to diesel fuel.
Researchers have investigated the lubricity of alcohols and low-sulfur diesel fuels
(Estefan, et al. 1990; Lacey, et al., 1997, 1998, 2000; Barbour, et al., 2000). A review
paper on fuel lubricity can be found by Lacey et al. (1998) that describes the various
lubricity testing methods applicable to CI engines, and describes details of the different
wear mechanisms commonly seen in various diesel fuel injection systems. A range of
commercially available additives are also given, however information on ethanol specific
lubricity is lacking.
Estefan et al. (1990) investigated 106 different compounds in concentrations of
1% by volume in methanol. Although the application was for SI engines, the testing
approach utilized the ball on cylinder machine (BOCM), whose data can also be applied
to CI engines.

Ignition

Another issue limiting the use of ethanol as a diesel fuel relates to difficulty in
autoignition required by CI engines. Alcohol autoignition and ignition improvers have
been investigated (Schaefer, et al., 1981; Lee, et al., 1993; Bollentin, et al., 1996). Nearly
pure ethanol (E95) is used in Scania engines to power buses in Stockholm, Sweden, but
an expensive ignition improver and extremely high compression ratios (~28:1) are
required to facilitate operation. Such high compression ratios reduce engine efficiency,
thus reducing to some extent, the efficiency advantage that CI engines have over SI
engines.
4
Hydrogen has also been suggested and tried as an ignition improver to assist in
promoting ethanol as a diesel fuel. A possible method of using small amounts of
hydrogen in transportation applications is through on-board reforming of ethanol to
produce hydrogen (Nilesen, et al., 1987; Tsolakis, et al., 2005; Panuccio, et al., 2006;
Bika, et al. 2009).
Another way of hydrogen utilization is with CI dual fuel engines. With dual fuel
engines, the engine operates on two fuels; the primary fuel source is a gaseous fuel such
as hydrogen or natural gas, which is injected into the intake manifold, and a small pilot
quantity of diesel fuel is injected into the combustion chamber using the standard fuel
injection equipment used to ignite the mixture (Karim, et al., 1989; Liu, et al., 1995;
Gunea, et al., 1998).
Liu et al. (1995) investigated the ignition delay period of CI dual fuel engines
using various gaseous fuels including hydrogen with a diesel pilot fuel. It was found that
as the hydrogen fuel admission was increased, the length of the diesel ignition delay
period also increased. Nielsen et al. (1997) also investigated the ignition delay of a CI
dual fuel engine, but used n-heptane and cetane, along with diesel as pilot fuels. With all
three fuels, hydrogen addition into the intake manifold caused an increase in the ignition
delay.
Thus, previous research has shown that hydrogen addition into the intake
manifold of a dual fuel engine operating on diesel fuel increases the ignition delay period.
Research at the University of Minnesota differs from dual fuel engine operation, because
the gaseous fuel is not the primary fuel source, but instead is used to modify the
combustion of the primary fuel. The present work shows both experimentally and with
numerical simulations, how small amounts of hydrogen in the intake manifold can reduce
the ignition delay period of a CI engine operating on ethanol. One goal of the current
research was to demonstrate how hydrogen may provide the means to facilitate the
combustion of ethanol in a CI engine with minimal modifications (i.e. operating at real
world compression ratios and intake air temperatures).

Fumigation

A second goal was to evaluate fumigation as a method of introducing ethanol into
a diesel engine. Fumigation allows an additional fuel to be introduced into the intake air
manifold of a diesel engine. The fuel is premixed with air and the charge air is injected
and ignited by CI in the cylinder. This is similar to the injection of hydrogen and ethanol
described above, except that in the case of fumigation usually a much larger fraction of
the fuel is introduced with the intake air, and the fuel (usually diesel) injected directly
into the cylinders by the fuel injectors, serves to ignite the combined air, ethanol and
diesel fuel mixture. With ethanol fumigation ethanol is the additional fuel, and may
represent a very significant fraction of the fuel input energy. Ethanol fumigation offers
several advantages including minimal engine modification and inexpensive and
uncomplicated hardware. For instance, a spray nozzle can be used to deliver ethanol
continuously into the manifold and a simple device can be used to meter the flow of
ethanol into the engine.
Broukhiyan and Lestz (1981) investigated the effect of ethanol fumigation on
engine performance at 12 steady-state operating conditions in ethanol fractions up to 50%
5
of the total fuel energy. For most of the conditions, slight gains in thermal efficiency
were observed, and brake specific NOx concentrations decreased for all conditions tested.
Engine misfire and severe knock limited the amount of ethanol that could be fumigated.
Chen et al. (1981) showed that thermal efficiency was slightly increased at high loads but
there was a small decrease at low loads. The ignition delay and maximum rate of pressure
rise increased significantly with ethanol. This increase in the rate of pressure rise was
also addressed by Baranescu (1986). In that study, ethanol fumigation was tested on a 6-
cylinder turbocharged Navistar engine and the results showed a dramatic increase in CO
and HC emissions when compared to regular diesel operation. In addition, the maximum
rate of pressure rise and peak cylinder pressure was substantially increased with ethanol
fumigation.
Abu-Qudais et al. (1998) showed that the optimum fraction for ethanol fumigation
was 20%. That percentage also resulted in a 7.5% increase in brake thermal efficiency
and a 51% reduction in soot mass concentration. However, the CO and HC levels
increased by 55% and 36% respectively. Baranescus study concluded that the maximum
proportion of alcohol that can be fumigated without severe knock was very small: only
25% to 30% (in terms of fuel energy) for ethanol. In the literature, the maximum fraction
of fuel energy obtained with ethanol fumigation varies between 25% and 75%. This wide
range can be attributed to the differences in the systems tested and also to the different
criteria used to determine the maximum amount of fumigated ethanol. Furthermore, the
timing of ethanol fumigation into the intake manifold also affects the maximum fraction
of fuel energy from ethanol, as described by Savage et al. (1986). That study investigated
the variations in the ethanol fumigation injection cycle, and those variations led to
significant differences in the pressure-volume history of the engine and the ethanol
energy displacement tolerance. A study on the effect of the diesel fuel injection timing on
an engine fumigated with ethanol was described by Schroeder et al. (1988). Their study
showed that an increase in thermal efficiency could be obtained by advancing the diesel
injection timing. Advancing injection timing significantly reduced the emissions of CO
and HC.
The effects of ethanol proof on ethanol-fumigated diesel engines have also been
investigated. A study on the fumigation of hydrous ethanol and its effects on engine
performance and emissions was carried out by Heisey and Lestz (1981). Their study
reported a slight increase in thermal efficiency at moderate and heavy loads with hydrous
ethanol. The ignition delay increased at all conditions. Fumigation of hydrous ethanol
also decreased NO
x
levels with increasing water content while CO levels remained
unchanged. Another interesting study on fumigation of different ethanol proofs was
carried out by Hayes et al. (1988). Their results showed that lower proofs reduced the
maximum rate of pressure rise relative to absolute (200 proof or 100%) ethanol. The peak
in-cylinder pressure was also slightly reduced. NO emissions were reduced with lower
ethanol proofs. However, CO and HC concentrations were not affected by the ethanol
proof. Those findings suggest the advantages of using hydrous ethanol for fumigation
purposes. This type of ethanol is cheaper than absolute ethanol and can be produced
economically in small distillation plants: alcohol production at the farm level typically
produces proofs in the 150 range (75% ethanol, 25% water) (Savage et al., 1986).
Lastly, with ethanol fumigation it is possible to achieve a combustion process
resembling that of an HCCI (homogeneous charge compression ignition) engine, with
6
high efficiency and very low NO
x
emissions. In this case, the heat release can be
controlled by the diesel injection and the heating of the intake air is not necessary. A
recent study on HCCI-like combustion with ethanol fumigation of a 12-L, 6-cylinder
heavy-duty Volvo engine is presented by Ekholm et al. (2008). Their results
demonstrated that with a dedicated fumigation system it is possible to operate an engine
with HCCI like combustion over a large load range without preheating the intake air.

EXPERIMENTAL METHODS

This research was carried out on two test stands a single cylinder cooperative
fuels research (CFR) engine used for hydrogen injection and a 1.9 L VW TDI engine for
the fumigation experiments. Each test stand is described below.

CFR Test Stand

For hydrogen injection a single cylinder CFR cetane engine was used for this
study. The CFR engine is an industry standard that is used to measure the ignition quality
(cetane number) of diesel fuels. It is an indirect injection (IDI) engine, with fully variable
compression ratio, intake air heating, and injection timing control. This engine has a
displacement of 611 cm
3
with a variable compression ratio from 8:1 to over 24:1. The
engine is coupled to a synchronous motor which maintains a constant engine speed of
900 RPM during both motoring and firing conditions. A 2 kW resistive heater was used
to heat the intake air.
Cylinder pressure was measured using a 6125B Kistler in-cylinder pressure
transducer with a 5010 Kistler charge amplifier. A rotary shaft encoder made by US
Digital with 1000 counts per revolution (CPR) resolution was mounted on the crankshaft
and used as the external clock signal for the Labview 8.6.1 code written to acquire and
process the in-cylinder pressure data. Hamlin Hall-effect sensors were used for crankshaft
TDC and camshaft signals. A Wolff Controls needle lift sensor was used to determine
injector motion.
A Quantum gaseous fuel injector was controlled by a Motec M800 fuel injection
controller to inject hydrogen into the intake manifold. Hydrogen was only injected during
the intake stroke, to minimize mixture stratification and any build up of hydrogen within
the intake system. This system allowed for precise control of injection timing and
quantity with the only on-engine hardware needed being two Hall-effect sensors mounted
on the crankshaft and camshaft, respectively. Hydrogen flowrates were measured with an
Alicat M-series mass flow meter.

CFR Engine Test Procedure

Non-denatured anhydrous ethanol was used as the fuel in this testing. As
mentioned above diesel fuel is typically used to lubricate the injection system
components, therefore it was necessary to evaluate lubricity additives to avoid damage to
the injection pump and nozzle. Three additives at various proportions in ethanol were sent
to a laboratory for testing according to ASTM: D 6079-04. The additives were ricinoleic acid
(castor oil), soy methyl ester (biodiesel), and lauric acid (coconut oil), and it was determined
that a blend of 2% lauric acid in ethanol was the least amount of additive necessary to meet
7
the ASTM minimum lubricity requirement and prevent injector and fuel pump wear. Further
details are found in Appendix A in a paper based on this work by Bika, et al. (2009). High
purity (>99.9%) bottled hydrogen (H
2
) gas was used for the hydrogen addition tests.
Before beginning testing, the engine and intake system, were brought up to
operating temperature while running the engine on diesel fuel at a compression ratio of
16.5:1. After reaching the desired operating temperatures, the engine was switched off
and the diesel fuel was completely purged from the injection pump and fuel lines, using
ethanol. The compression ratio was then increased to the desired level and the engine was
motored with the synchronous motor. The intake temperature was once again allowed to
stabilize, and when it reached the correct value, the ethanol injection was started and the
engine was fired.
A wide sweep of engine tests was performed by varying the compression ratio,
ethanol injection timing and fueling amount, and varying the hydrogen flowrate. The
hydrogen flowrates were varied from 0 10 sL/min with the overall equivalence ratio
ranging from 0.5 to 0.7 and the hydrogen energy fraction ranging between 5 20% of the
total energy. It was determined that a compression ratio of 24:1 and an intake temperature
of 120C was necessary to achieve stable ethanol only operation. This condition was then
taken as the baseline condition. If either the compression ratio or the intake temperature
were reduced below those values, the engine began to misfire and run unstably using
straight ethanol. Once this baseline condition was established, we began to investigate the
effect of hydrogen both at this high compression ratio and high temperature condition,
and also at lower compression ratios and lower temperatures. After analyzing these test
data, the test conditions shown in Table 1 were selected for evaluation.

Table 1. CFR engine test conditions
Test # Compression ratio Intake air temperature, C Hydrogen flow sL/min
24:1 120 0
24:1 120 5
24:1 120 0
24:1 80 5
24:1 120 0
19:1 80 10
1
2
3


The injection timing and fuelling amounts varied between the different test
conditions, but were kept constant within each test condition. This means that
comparisons made between the no-hydrogen and hydrogen-assist conditions at a given
test condition will have the same ethanol injection timing and fueling amount. The lower
compression ratio and intake air temperature of 19:1 and 80C, respectively, were chosen
as real-world diesel engine conditions, which have the potential of being achievable with
little to no engine modification.

VW Engine Test Stand

For the fumigation tests a 4-cylinder, 1.9 L, 66 kW, 1999 VW turbocharged direct
injection (TDI) engine was used. This engine is a popular member of the large TDI
engine family used to power the diesel versions of the VW New Beetle, J etta, Golf, and
Passat models. For our tests the exhaust gas recirculation (EGR) system was disabled, in
8
an attempt to eliminate a variable affecting NOx emissions. Engine characteristics are
given in Table 2.

Table 2. VW engine characteristics
Engine type 4-stroke diesel
Number of cylinders 4 in-line
Displacement, cm
3
1896
Bore x stroke, mm 79.5 x 95.5
Compression ratio 19.5
Induction turbocharged
Turbocharger VNT (Garrett)
Valve configuration OHC 2 valves/cyl.
Injection pump Bosch VE VP 37
Maximum output 66 kW at 3759 rpm
Maximum torque 210 N-m at 1900 rpm
Maximum MEP, kPa 1400


The engine was coupled to an Eaton Dynamatic (model AD-806) DG eddy-
current dynamometer rated at 75 HP (56 kW) at 3400 rpm. The dynamometer is not
capable of motoring the engine. The dynamometer was controlled by a Digalog (model
1022A-STD) dynamometer controller. The flow rate of diesel fuel into the engine was
measured with a Brooks (model BM01ARSPA2RVA) micro-oval flowmeter. The
volumetric flow rate of air (in sL/min) inducted into the engine was measured with a
Meriam laminar flow element (model 50MC2-4).
Either water or ethanol was fumigated into the intake air manifold using a
Spraying Systems atomizing nozzle (SU1A). This nozzle has two ports, to which both
liquid and compressed air lines are fitted. The two streams are mixed to create a fine
ethanol or water spray, which was introduced into the intake manifold. The system
provided a continuous spray of pressurized liquid from a vessel kept at a constant
pressure of about 138 kPa. Flow rate was controlled by both a metering valve and
flowmeter. The flow rate of fumigated ethanol or water was measured with an Omega
model FL-2045 liquid-flow rotameter.
Range finding experiments were conducted to observe engine behavior as ethanol
was introduced into the intake manifold so that the engine and fuel test conditions could
be established. Anhydrous ethanol was used in these tests. The engine was initially
operated at a speed of 1400 rpm and a load of 25 N-m. Ethanol was introduced slowly
into the intake manifold, and as the additional fuel was added the engine speed increased,
thus the load was adjusted (increased) until the speed returned to 1400 rpm. Additional
ethanol fumigation caused the engine to speed up again resulting in a further adjustment
of the load (increase) to maintain constant speed. This procedure was repeated until an
audible engine knock was perceived at 1400 rpm and 90 N-m. At this condition, the
fraction of the fuel energy from ethanol was roughly 72% of the total NET fuel energy
(i.e., not considering the energy used to overcome frictional losses). These preliminary
results suggest that fairly high ethanol fuel energy fractions can be obtained on the VW
engine when operating with ethanol fumigation.
Additional tests were conducted at 1700 rpm. At this speed the dynamometer is
able to absorb up to about 152 N-m, whereas the engine can deliver a maximum torque of
about 208 N-m as shown in Figure 1. Thus, the maximum engine load attainable at 1700
9
rpm was limited by the dynamometer absorbing capability and was equal to 73 % of the
maximum engine torque at this condition. Based upon these tests the conditions in Table
3 were chosen for evaluation. Information in Table 3 is interpreted as follows. For the
baseline condition (diesel fuel only) no fumigant was introduced and tests were
conducted at 1700 rpm and 40, 80, and 120 N-m load. For the 100% (200 proof) ethanol
condition the ethanol volumetric flow rates necessary to reduce the Diesel fuel flow rate
by 25 and 40% were determined. These same flow rates were used for testing with 50%
ethanol (100 proof hydrous ethanol) and straight water. Straight water was tested to help
to understand the relative effects of the water and ethanol on performance and emissions
of hydrous ethanol fumigation.

Table 3. VW engine fuel test conditions. Fractions based on the volumetric diesel fuel
flow rate under baseline (diesel fuel only) operation.

Fuel/Fumigant Fumigant fraction Engine condition
pct 1700 rpm, N-m
Baseline (diesel fuel only) None 40, 80, 120
Water 25 40, 80, 120
Water 40 80
50 % (100 proof) ethanol 25 40, 80, 120
50 % (100 proof) ethanol 40 80
100 % (200 proof) ethanol 25 80
100 % (200 proof) ethanol 40 80


Figure 1. VW TDI map (Source: Bosch, et al., 1998)

The same test protocol was used for each set of tests. After startup and a brief
warm-up period the engine was brought to the 1700 rpm, 120 N-m for a period of about 5
min. This step was repeated in-between every different load condition. The purpose of
this procedure was to remove any excess volatile material that might have collected in the
exhaust system that might impact the particle measurements and test repeatability
(Kittelson, et al., 2006b; Swanson, et al., 2009). Following the burn-off period, the engine
load was set to the test condition. Once a steady-state of engine operation was attained
10
testing began. Parameters such as exhaust temperature, oil temperature, and raw NOx
emissions were used to determine steady-state operation. Typically, a period of 15 min
was sufficient to steady-state operation.

Aerosol and Gas Sampling

The instrumentation used to determine the exhaust aerosol concentration was
unable to sample directly from raw exhaust, therefore a dilution system was used to dilute
the sample to a range suitable for the instruments. To determine the dilution ratio
multiple gas analyzers were used to monitor the raw and diluted NO concentration. NO is
a stable gas that does not change during the dilution process.
A two-stage ejector dilutor system developed in our laboratory was used to dilute
the exhaust sample. This system is similar to those described previously, and extensively
evaluated during the Coordinating Research Council (CRC) E-43 project (Abdul-Khalek,
et al., 1999; Kittelson, et al., 2002, 2006a). Exhaust enters the system through a short
probe immersed in the exhaust flow, and passes through a short section of stainless steel
tubing referred to as the transfer line. An Air-Vac TD 260H air ejector pump with a
critical flow orifice provided the first stage of dilution. Dilution air was filtered and dried.
The system was designed to give a primary dilution ratio (DR) ranging from 25 to 30:1
with a regulated, total dilute exhaust mixture flow rate of about 230 L/min, and a total
dilution ratio of about 600:1. It is critical that the orifice not be allowed to plug with soot
as this will increase the dilution ratio and impact the resulting measurements. Diluted
aerosol then passed into a residence time chamber with internal flow distribution cone.
The chamber was designed for a residence time of 1 s at 100 L/min. With the above
aerosol flow rate, the chamber provides a residence time of about 0.43 s.
Aerosol size distributions were determined using a TSI 3080 Scanning Mobility
Particle Sizer (SMPS). The SMPS consists of a control platform, a 3081 long column
Differential Mobility Analyzer (DMA) and a 3782 Condensation Particle Counter (CPC).
The SMPS was configured to size particles from about 8 nm to 300 nm with a response
time of 120 s, and the CPC is operated in the high flow mode. The SMPS classifies
particles based upon electrical mobility. The electrically-classified aerosol then passes to
the CPC where particles are counted.
The SMPS measures the number concentration within classified size bins
resulting in a particle number size distribution. These data can later be manipulated to
determine the particle volume, surface area or mass size distributions. Particle volume is
a surrogate measure for particle mass. Figure 2 illustrates the relationship between
particle number and particle mass for a typical diesel aerosol (Whitby, et al., 1976;
Kittelson, 1998). The curves have a lognormal, trimodal form and the concentration in
any size range is proportional to the area under the corresponding curve in that range. The
nucleation mode (3-30 nm) typically contains <10% of the particle mass but >90% of
the particle number. Nucleation mode particles are usually composed of nearly all-
volatile compounds typically composed of hydrocarbons and sulfates. Most of the DPM
mass is found in the accumulation mode (roughly 30-500 nm size particles), and is
composed of carbonaceous agglomerates and adsorbed materials. The coarse mode
consists of particles larger than 500 nm in diameter and contains 5-20% of the mass.
These large particles are formed by reentrainment of DPM, which has been deposited on
11
cylinder and exhaust system surfaces, and crankcase fumes are also in this range. The
boundaries between these modes depend upon engine type, operating conditions and fuel
and are better defined by their formation mechanisms than by rigid size boundaries
(Kittelson 1998; Kittelson, et al., 2002, 2006a).
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
1 10 100 1,000 10,000
Diameter (nm)
N
o
r
m
a
l
i
z
e
d

C
o
n
c
e
n
t
r
a
t
i
o
n


(
C
t
o
t
a
l
-
1
)
d
C

d
l
o
g
D
p
-
1
Number Mass
FineParticles
Dp <2.5 m
UltrafineParticles
Dp <100 nm
Nanoparticles
Dp <50 nm
Nuclei Mode
Accumulation Mode
CoarseMode
PM10
Dp <10 m

Figure 2. Relationship between particle number and particle mass for a typical
diesel aerosol. (Source: Whitby and Cantrell, 1976; Kittelson, 1998)

Emissions of unburned hydrocarbons (HC) were measured using a Beckman
model 400A flame ionization detection (FID). Concentrations of CO and carbon dioxide
(CO
2
) were measured using a Horiba (model PIR-2000) infra-red absorption, gas
analyzer. Oxides of nitrogen and nitric oxide (NO) were measured using three
instruments. This was required to allow determination of the sample dilution ratio
determined from the NO concentration. The analyzers all operated using the
chemiluminescence principle. A California Analytical Instruments (CAI) (model 600
HCLD) analyzer fitted with a heated line measured raw exhaust concentrations. A Horiba
(model CLA-510SS/ES-C510SS) analyzer was used to measure NO concentrations after
the first stage of dilution and a Monitor Labs (model 8840/8850) high-sensitivity analyzer
was used to measure NO concentrations after the secondary dilution.
A 16-bit, 200 kS/s National Instruments model SCXI-1600 USB data acquisition
module mounted on a National Instruments model SCXI-1001 chassis was used to
acquire data, and National Instruments LabVIEW 8.6 software was used to process these
data. Before engine testing began particle instruments were operated with a high
efficiency air filter at the inlet to the system to ensure the system was leak free. Gas
analyzers were zeroed and spanned daily according to manufacturers protocols to insure
proper operation.



12
RESULTS AND DISCUSSION

Complete details of all results are found in a publication by Bika, et al. (2009)
attached as Appendix A and in a M.S. Thesis in preparation by Olson (2010). The paper
by Bika, et al. covers the hydrogen assisted combustion of ethanol and the thesis by
Olson covers the fumigation of ethanol into the VW engine. The M.S. thesis will be
forwarded to the Minnesota Corn Growers Association upon completion and approval by
the University of Minnesota thesis committee. A summary of the findings from the paper
by Bika, et al. (2009) found in Appendix A and the ethanol fumigation experiments is
given below.

Ethanol Combustion in a Diesel Engine

An understanding of combustion terminology is useful when trying to understand
the results discussed below. Figure 3 shows the relationship of three important
combustion parameters in-cylinder pressure, needle lift, and heat release rate (HRR) from
the CFR engine when operating on diesel fuel. It also shows the ignition delay. A good
diesel fuel has a low ignition delay, thus a high cetane number. The in-cylinder pressure
is measured on the engine and used to derive combustion parameters. The injector needle
lift is used to determine start of injection (SOI) and the HRR indicates how and when fuel
energy is released and gives the start of combustion (SOC).


Figure 3. Important combustion parameters

One goal of this research was to demonstrate the ability of hydrogen injection to
facilitate the combustion of ethanol in a CI engine. To accomplish this, the engine had to
first operate on ethanol alone without any hydrogen addition. Stable combustion in the
CRF engine was obtained when the intake air temperature was heated to 120C and the
compression ratio was raised to 24:1. When 5 sL/min was added at this condition there
was a significant advance in the SOC as illustrated in Figure 4a and 4b. For both graphs
the ethanol fueling rate and injection timing were kept constant as hydrogen was added
but the ethanol injection timing was varied from -13 crank angle degrees (CAD) at top
dead center (ATDC) to 11 CAD (ATDC). Thus, injection of hydrogen shortened the
ignition delay period of the ethanol fuel as we had hoped. The hydrogen had a stronger
effect in the second case where the timing was less advanced and the ignition delay with
straight ethanol was longer.
13
Figure 4a Figure 4b
-5
5
15
25
35
45
55
65
75
85
-20 -15 -10 -5 0 5 10 15 20
CAD (ATDC)
P
r
e
s
s
u
r
e

(
b
a
r
)
,

H
R
R

(
J
/
C
A
D
)

a
n
d

N
e
e
d
l
e

L
i
f
t

(
V
)
Injector Needle Lift
Straight EtOH in Solid Line
H2 in Dashed Line
Pressure
Heat Release Rate
-5
5
15
25
35
45
55
65
75
-20 -15 -10 -5 0 5 10 15 20
CAD (ATDC)
P
r
e
s
s
u
r
e

(
b
a
r
)
,

H
R
R

(
J
/
C
A
D
)

a
n
d

N
e
e
d
l
e

L
i
f
t

(
V
)
Injector Needle Lift
Straight EtOH in Solid Line
H2 in Dashed Line
Pressure
Heat Release Rate


Figure 4. Engine operating at a compression ratio of 24:1 and intake temperature of
120C, with and without 5 sL/min of hydrogen addition with an ethanol injection timing
of -13 crank angle degrees (CAD) at top dead center (ATDC) (Figure 4a) and with an
ethanol injection timing of -11 CAD (ATDC) (Figure 4b).

However, operating at a compression ratio of 24:1 and an intake air temperature
of 120C are not suitable for real-world diesel engine operation, thus additional
experiments were conducted at a lower compression ratio and an intake air temperature
as indicated in Table 1 above. Although many diesel engine manufacturers maintain
diesel engine intake air manifold temperatures between 30-45C, minor modification to
the aftercooler setting or alteration of the exhaust gas recirculation (EGR) input can
typically bring the manifold temperature to near 80C, thus a compression ratio of 120
and an intake air temperature of 80C was selected as test condition 2 and the results are
shown in Appendix A Figures 4 and 5. From these figures it can be seen that the SOC of
both the ethanol only and the hydrogen assisted ethanol cases are in virtually the same
position. Thus the addition of 5 sL/min of hydrogen, about 5% of the fuel energy input
enabled the ethanol combustion at a much lower intake temperature of 80C; an intake
temperature condition where ethanol only operation could not be sustained.
Test condition 3 is the most representative of real-world diesel engine operation
conditions. In this case the compression ratio was lowered to 19:1 and the intake air
temperature was kept constant at 80C. At this condition the hydrogen flow rate was
increased to 10 sL/min, about 10% of the fuel energy input. This flow rate was chosen,
because 10 sL/min was the maximum hydrogen addition that was possible at the lower
intake temperature and lower compression ratio condition, compared to the 5 sL/min at
the higher compression ratio conditions. These results are shown in Appendix A Figures
6 and 7. At this condition, just as in the high compression ratio and high intake
temperature condition, it can be seen that there is a significant start of combustion
advance when the hydrogen is added. In fact Appendix A Figures 6 and 7 show advances
in SOC timing compared to base case of 6 and 4 CAD, respectively, with hydrogen
addition. This is more than is necessary for good combustion suggesting that further
reduction of inlet temperature would have been possible while maintaining good
combustion. During these tests, as in all the previous conditions tested, the overall
ethanol fueling rate and injection timing were kept constant while hydrogen was added.
The advancing SOC seen during hydrogen assisted ethanol combustion is the
opposite trend of what is seen from hydrogen assisted diesel combustion (Nilesen, et al.,
14
1987; Gunea, et al. 1998; Karim, et al., 1989; Liu, et al., 1995). To understand this
phenomenon, the ignition delay period must be understood. The ignition delay period is
the time period between the start of injection and the start of combustion. For this work,
the start of injection is considered to be when the injector needle lift sensor first senses
motion, and the start of combustion is when the heat release rate first crosses zero.
The greatest factors affecting the ignition delay period are thermal, physical, or
chemical kinetic in nature. The temperature of the inlet charge during compression will
vary, depending on the mixture specific heat ratio. If the added gaseous fuel has a
specific heat ratio close to that of air, the compression temperatures will remain relatively
unchanged. Karim et al. (1989) show how the calculated mean charge temperature at
TDC does not vary significantly with hydrogen addition up to 10% of the air volume. It is
suggested that the combination of the mixture specific heat ratio and the rate of heat
transfer with the hydrogen addition balances causing no change in compression
temperatures.
The physical aspect of the ignition delay period have to do with mixing
characteristics and volatility of the injected fuel, where a fuel such as ethanol will have
superior atomization, vaporization, and mixing characteristics compared to a heavier
diesel fuel (Henein, et al., 1987). This superior mixing and atomization may contribute to
an increased interaction between the ethanol and the hydrogen-air mixture. Also, the fuel
injection quantity has an effect in determining the ignition delay period in dual fuel
engines (Guinea, et al., 1998). Larger injection quantities tend to demonstrate smaller
changes to the delay, while relatively smaller injection quantities show increased ignition
delay. The CHEMKIN model (see Appendix A) assumes a premixed condition and thus
cannot capture mixing differences.
The chemical kinetic effect of the interaction between the ethanol fuel vapor and
the hydrogen may be very important and is difficult to fully understand. During the
compression stroke, the gaseous fuel can experience many pre-reactions, forming various
radicals to aid in the ignition of the main fuel. The exhaust residuals may also contribute,
not only to the thermal effect of adding heat to the mixture, but also the kinetic effect of
the supplying radicals in the form of exhaust residuals. Although the CHEMKIN
simulations performed (see Appendix A) show that hydrogen addition may reduce the
ignition delay of an ethanol-air mixture in a constant volume chamber, the reductions,
especially at low temperature, are modest. The temperature in the cylinder when the
ethanol in injected is less that 1000 K and at this temperature predicted changes in
ethanol ignition delays, with hydrogen injection are predicted to be much less than
actually observed.
Westbrook (2000) has reported that for practically all hydrocarbons, ignition
begins when there is a significant presence of OH radicals. This means that a method that
may cause an early presence of OH radicals may also enable early ignition.
Marinov (1999) has reported on a kinetic model for high temperature ethanol
oxidation. In his work, he shows that ethanol oxidation exhibits a strong sensitivity
towards the hydroperoxyl (HO
2
) radical. He shows that the following reaction:

CH
3
+HO
2
CH
3
O +OH (reaction 1),

15
followed by the CH
3
O decomposition to CH
2
O +H atom is the main supply route for H
atoms and OH radicals.
In our experimental work, hydrogen was injected with the intake air, comprising
roughly 2-5% of the mixture volume. At these concentrations of hydrogen addition, and
at the temperatures and pressures seen during compression, it would be expected that
some of the hydrogen in the hydrogen-air mixture would be converted to HO
2
, along with
H
2
O
2
. It would be expected that higher concentrations of HO
2
around the ethanol fuel
spray, would increase the rate of reaction 1, causing the advancing start of combustion
seen with hydrogen addition.
Direct comparison of the experimental and numerical data presented in this paper
cannot be made with the diesel engine dual fuel tests made by other researchers, because
in this testing, the compression ratio and intake temperatures were slightly elevated.
Also, in this work only a small amount of the energy (5-20%) was derived from the
gaseous hydrogen fuel. It is clear, however, that the start of combustion advances when
hydrogen is added to the intake mixture. The chemical effect of the increased HO
2

concentration with hydrogen addition may have a greater role than just the affect
attributed to the thermal properties of the charge or the physical characteristics of the
ethanol spray.
Regardless of the exact mechanism, it is clear that the presence of a small amount
of hydrogen in the cylinder facilitates the combustion of ethanol in a Diesel engine and
allows reliable combustion under conditions easily obtained in a conventional Diesel
engine. The next steps indicated are the development of an onboard ethanol reforming
system and control system to produce hydrogen from ethanol. Such systems have been
developed on a bench scale (Salge, et al., 2005) but are not yet available commercially.

Fumigation of Ethanol in a Diesel Engine

Table 4 summarizes the aerosol data obtained during the fumigation experiments
and the average dilution ratio for each test condition. The dilution ratio does not impact
the gaseous measurements because they are measured in the raw exhaust, however, the
aerosol measurements are made after dilution so to determine engine out concentrations
the aerosol concentrations are multiplied by the dilution ratio. The dilution ratios shown
are the overall averages for each test condition and they serve to illustrate the actual
dilution ratios used in the calculations used to determine the aerosol concentrations,
which are the dilution ratios determined for each individual test period. The individual
test period concentrations are then averaged to determine the concentrations shown in
Table 4.
The aerosol baseline concentrations shown in Table 4 are reasonable. As the
engine load increased the volume concentration (a surrogate measure of mass) increased
from 6.5 x 10
3
to 1.6 x 10
4
m
3
/cm
3
. As illustrated by Figure 5, the particle volume
concentration at the 1700 rpm 80 N-m condition decrease when water or ethanol are
added except for the 25% water addition where no statistically significant trend is
observed.
Figure 5 illustrates the trend in particle volume for the 1700 rpm 80 N-m
condition for the different fuels. The addition of ethanol results in a statistically
significant reduction in the particle volume concentration for all test conditions.
16

Table 4. Average aerosol number and volume concentrations with standard deviations for
the fumigation experiments
Condition
Avg Std Avg Std Avg Std
1700/40 Diesel 600 31 8.69E+07 1.03E+07 6.50E+03 4.74E+02
1700/40 25% Water 601 23 9.87E+07 8.82E+06 6.19E+03 4.12E+02
1700/40 25% 50% Ethanol 619 24 9.54E+07 1.06E+07 6.04E+03 4.82E+02
1700/80 Diesel 606 69 1.78E+07 1.82E+06 7.07E+03 5.83E+02
1700/80 25% Water 610 73 1.90E+07 1.08E+06 7.25E+03 5.49E+02
1700/80 40% Water 540 5 1.13E+07 7.13E+05 4.75E+03 3.40E+02
1700/80 25% 50% Ethanol 627 80 1.33E+07 7.94E+05 5.66E+03 4.32E+02
1700/80 40% 50% Ethanol 541 5 7.78E+06 5.03E+05 3.73E+03 2.96E+02
1700/80 25% 100% Ethanol 555 2 7.97E+06 4.39E+05 3.63E+03 2.79E+02
1700/80 40% 100% Ethanol 566 9 8.00E+06 4.99E+05 3.64E+03 2.88E+02
1700/120 Diesel 649 45 2.98E+07 3.99E+06 1.58E+04 1.28E+03
1700/120 25% Water 646 46 2.11E+07 1.36E+06 1.24E+04 8.63E+02
1700/120 25% 50% Ethanol 674 44 1.85E+07 1.42E+06 1.26E+04 1.17E+03
Number, part/cm
3
Volume, m
3
/cm
3
Dilution ratio


0.0E+00
1.0E+03
2.0E+03
3.0E+03
4.0E+03
5.0E+03
6.0E+03
7.0E+03
8.0E+03
9.0E+03
1.0E+04
Diesel 25% Water 40% Water 25% 50 %
Ethanol
40% 50 %
Ethanol
25% 100 %
Ethanol
40% 100 %
Ethanol
Fuel
d
V
/
d
l
o
g
D
p
,

m
3
/
c
m
3
1700 RPM 80 N-m

Figure 5. Average particle volume concentration for the different fuels at the 1700 rpm
80 N-m engine test condition.

The aerosol data shown above are obtained from particle size distribution
measurements like those shown in Figures 6 and 7. Figure 6 shows particle number
weighted size for the 1700 rpm 80 N-m condition for different fuels and fumigation
conditions. Number distributions like these are typically converted to volume weighted
17
distributions assuming spherical particles. Figure 7 shows the volume weighted
distributions obtained in this manner from the number distributions shown in Figure 6.

0.0E+00
5.0E+06
1.0E+07
1.5E+07
2.0E+07
2.5E+07
3.0E+07
3.5E+07
10 100 1000
Dp, nm
d
N
/
d
l
o
g
D
p
,

p
a
r
t
/
c
m
3
Diesel
25% Water
40% Water
25% 50% Ethanol
40% 50% Ethanol
25% 100% Ethanol
40% 100% Ethanol
1700 RPM 80 N-m

Figure 6. Average particle number weighted size distributions for different fumigation
conditions at 1700 rpm 80 N-m test condition.
0.0E+00
2.0E+03
4.0E+03
6.0E+03
8.0E+03
1.0E+04
1.2E+04
1.4E+04
1.6E+04
10 100 1000
Dp, nm
d
V
/
d
l
o
g
D
p
,

m
3
/
c
m
3
Diesel
25% Water
40% Water
25% 50% Ethanol
40% 50% Ethanol
25% 100% Ethanol
40% 100% Ethanol
1700 RPM 80 N-m

Figure 7. Average particle volume weighted size distributions for different fumigation
conditions at 1700 rpm 80 N-m test condition.
18
Table 5 summarizes the exhaust data for NOx, NO and hydrocarbons (HC)
obtained during the fumigation experiments. Data for NOx and HC are illustrated
graphically in figures 8 and 9 for the 1700 rpm 80 N-m test condition. Water fumigation
leads to decreases in NOx and small decreases in hydrocarbons. Hydrous ethanol
fumigation leads to a NOx decrease at the lower, 25% fumigation rate, but an increase at
the 40% rate. Pure ethanol fumigation leads to a modest NOx increase at both fumigation
rates. Hydrocarbons increase significantly with both hydrous and 100% ethanol,
presumably due to unburned ethanol. This engine had no exhaust aftertreatment. The
addition of a low cost Diesel oxidation catalyst should allow control of these hydrocarbon
emissions.

Table 5. Average dilution ratios, NOx, NO and hydrocarbon concentrations with standard
deviations for the fumigation experiments
Condition
Avg Std Avg Std Avg Std
1700/40 Diesel 198 2.0 182 2.1
1700/40 25% Water 152 1.6 136 1.6
1700/40 25% 50% Ethanol 119 2.4 95 2.4
1700/80 Diesel 467 8.2 441 18.8 35 4.5
1700/80 25% Water 382 5.5 356 5.6 29 2.9
1700/80 40% Water 392 7.5 343 6.9 23 4.4
1700/80 25% 50% Ethanol 409 3.7 351 3.8 68 3.2
1700/80 40% 50% Ethanol 483 5.5 355 7.9 71 4.3
1700/80 25% 100% Ethanol 499 6.6 329 5.6 120 5.7
1700/80 40% 100% Ethanol 504 4.4 301 4.4 195 8.2
1700/120 Diesel 610 9.6 605 10.2
1700/120 25% Water 460 8.3 453 8.2
1700/120 25% 50% Ethanol 531 3.7 520 4.5
NOx, ppm NO, ppm Hydrocarbons, ppm


19
0
100
200
300
400
500
600
700
800
Diesel 25% Water 40% Water 25% 50 %
Ethanol
40% 50 %
Ethanol
25% 100 %
Ethanol
40% 100 %
Ethanol
Fuel
E
x
h
a
u
s
t

N
O
x
,

p
p
m
1700 RPM 80 N-m

Figure 8. Average exhaust NOx concentration for the different fuels at the 1700 rpm 80
N-m engine test condition.

0
50
100
150
200
250
Diesel 25% Water 40% Water 25% 50 %
Ethanol
40% 50 %
Ethanol
25% 100 %
Ethanol
40% 100 %
Ethanol
Fuel
E
x
h
a
u
s
t

H
y
d
r
o
c
a
r
b
o
n
s
,

p
p
m

1700 RPM 80 N-m

Figure 9. Average exhaust hydrocarbon concentration for the different fuels at the 1700
rpm 80 N-m engine test condition.
20
Table 6 summarizes the percent reduction or increase (indicated by a sign) from
the diesel fuel baseline condition for the major pollutants as calculated from data in
Tables 4 and 5. Overall ethanol has the largest impact on particle emissions, which
decrease, and HC emissions, which increase.

Table 6. Percent reduction or increase (indicated by a sign) from the diesel fuel baseline
condition for the major pollutants as calculated from Tables 4 and 5
Condition
NOx NO HC Number Volume
1700/40 25% Water 23.2 25.6 -13.6 4.7
1700/40 25% 50% Ethanol 39.7 48.0 -9.8 7.0
1700/80 25% Water 18.2 19.3 16.3 -6.5 -2.5
1700/80 40% Water 16.0 22.2 32.8 36.7 32.8
1700/80 25% 50% Ethanol 12.4 20.3 -93.9 25.2 19.9
1700/80 40% 50% Ethanol -3.5 19.4 -102.0 56.4 47.2
1700/80 25% 100% Ethanol -6.8 25.3 -243.0 55.3 48.7
1700/80 40% 100% Ethanol -7.9 31.6 -459.2 55.1 48.5
1700/120 25% Water 24.6 25.1 29.3 21.3
1700/120 25% 50% Ethanol 12.9 14.0 37.9 20.2
Percent reduction

NOx oxides of nitrogen, NO nitric oxide, HC hydrocarbons, Number and Volume refer to particle number
concentration and particle volume concentration.

The thermal efficiency is a performance measure of an engine. When expressed as
a percentage, the thermal efficiency must be between 0% and 100%, but due to
inefficiencies such as friction, heat loss, and other factors, an engines efficiency is
typically much less than 100%. For example, a typical gasoline automobile engine
operates at around 25% efficiency, while a diesel engine is between 30 and 35 %
efficient.
Figure 10 shows the calculated average brake thermal efficiencies for the most
stable condition, 1700 rpm, 80 N-m. The efficiency values obtained with fumigation of
both aqueous (100-proof) and absolute (200-proof) ethanol are compared to the baseline
efficiency value.
It is evident from Figure 10 that at 1700 rpm and 80 N-m, the brake thermal
efficiencies resulting from ethanol fumigation are slightly lower than the efficiency
obtained with baseline operation. The issue of the variation of thermal efficiency with
ethanol fumigation was addressed in the works by Chen et al. (1981), Hayes et al. (1988),
and J iang et al. (1990). According to those studies, the increase in ignition delay brought
about by ethanol at sufficiently low loads causes the overall combustion to extend further
into the expansion stroke, thus lowering thermal efficiency. At higher loads, however, the
longer ignition delay increases the rate of in-cylinder pressure rise, which, in turn, can
result in combustion that more closely approaches constant-volume combustion. This is
the reason that, at high engine loads, ethanol fumigation can indeed result in slightly
higher thermal efficiencies, when compared to baseline. In the present case, the load of
80 N-m was not high enough to increase the rate of pressure rise, and combustion
expanded further past cylinder top dead center (TDC) which may explain the decrease in
efficiency. A related factor is the lower in-cylinder temperatures associated with lighter
21
load operation. This likely leads and incomplete combustion of the fumigated ethanol
resulting in reduced efficiency and increased unburned fuel emissions.
Another result worth noting is the fact that ethanol proof did not seem to affect the
ignition delay (Chen et al., 1981). This is consistent with the insensitivity of thermal
efficiency to the proof of the fumigated ethanol observed here, about 33.7% regardless of
proof. These findings are in accordance with results obtained by others (Chen et al.,
1981; Hayes et al., 1988); these results are of considerable practical importance, because
the fumigation of cheaper, lower-proof alcohols will not likely result in the worsening of
thermal efficiency when compared with the more expensive absolute ethanol fumigation.
30
31
32
33
34
35
36
37
38
39
40
Diesel 25% 50% ethanol 40% 50% ethanol 25% 100% ethanol 40% 100% ethanol
Fuel
A
v
e
r
a
g
e

b
r
a
k
e

t
h
e
r
m
a
l

e
f
f
i
c
i
e
n
c
y
1700 RPM 80 N-m

Figure 10. Average brake thermal efficiency for the different fuels at 1700 rpm 80-N-m
test condition

Fumigation is a relatively simple and inexpensive way of using ethanol in a
Diesel engine to partially offset Diesel fuel use. It offers substantial benefits in terms of
reduction in particle emissions. On the other hand, at least for the conditions tested here,
thermal efficiency decreased slightly, while hydrocarbon emissions increased. These
emissions could be controlled by the addition of a Diesel oxidation catalyst. NOx
decreased at low ethanol use rates but increased slightly at higher rates.
22
REFERENCES

Abdul-Khalek, I., D.B. Kittelson, and F. Brear. 1999. The Influence of Dilution
Conditions on Diesel Exhaust Particle Size Distribution Measurements. SAE Technical
Paper Series, 1999-01-1142, Warrendale, PA.
Abu-Qudais, M., Haddad, O., and Qudaisat, M. 1998. The Effect of Alcohol
Fumigation on Diesel Engine Performance and Emissions. SAE Technical Paper 1998-
25-0238.
Barbour, R. H., Rickeard, D. J ., and Elliot, N. G. 2000. Understanding Diesel
Lubricity, SAE Technical Paper 2000-01-1918.
Baranescu, R.A. 1986. Fumigation of Alcohols in a Multicylinder Diesel Engine
Evaluation of Potential. SAE Technical Paper 860308.
Bika, A. S., L. M. Franklin, and D. B. Kittelson. 2009. Hydrogen as a Combustion
Modifier of Ethanol in Compression Ignition Engines. SAE Technical Paper 2009-01-
2814.
Bollentin, J . W., and Wilk, R. D. 1996. Autoignition Characteristics of Ethanol,
SAE Technical Paper 961175.
Bosch, D., U. Drges, G. Goergens, S. Hunkert, and J . R. Liang. 1998. The New
Diesel Engine in the the New Beetle. SAE Technical Paper 981950, 13 pp.
Broukhiyan, E.M.H., and Lestz, S.S. 1981. Ethanol Fumigation of a Light Duty
Automotive Diesel Engine. SAE Technical Paper 811209.
Chen, J ., Gussert, D., Gao, X., Gupta, C., and Foster, D. 1981. Ethanol
Fumigation of a Turbocharged Diesel Engine. SAE Technical Paper 810680.
Ekholm, K., Karlsson, M., Tunestl, P., J ohansson, R., and J ohansson, B. 2008.
Ethanol-Diesel Fumigation in a Multi-Cylinder Engine. SAE Technical Paper 2008-01-
0033.
Estefan, R. M., and Brown, J . G. 1990. Evaluation of Possible Methanol Fuel
Additives for Reducing Engine Wear and/or Corrosion, SAE Technical Paper 902153.
Goering, C. E., Parcell, R. T., and Ritter, C. P. 1998. Hydrated Ethanol as a Fuel
for a DI, CI Engine, Transactions of the ASAE, 41 (5): 1255-1260.
Gunea, C., Razavi, M. R. M, and Karim, G. A.1998. The Effects of Pilot Fuel
Quality on Dual Fuel Engine Ignition Delay, SAE Technical Paper 982453.
Hardenberg, H. O., and Schaefer, A. J . 1981.The Use of Ethanol as a Fuel for
Compression Ignition Engines, SAE Technical Paper 811211.
Hayes, T.K., Savage, L.D., White, R.A., and Sorenson, S.C. 1988. The Effect of
Fumigation of Different Ethanol Proofs on a Turbocharged Diesel Engine. SAE
Technical Paper 880497.
Henein, N. A., and Y. Akasaka, Y. 1987.Effect of Physical Properties and
Composition on Fuels on Autoignition and Cetane Rating, SAE Technical Paper 871617.
Heisey, J .B., and Lestz, S.S. 1981. Aqueous Alcohol Fumigation of a Single-
Cylinder DI Diesel Engine. SAE Technical Paper 811208.
Karim, G. A., J ones, W., and Raine, R. R. 1989. An Examination of the Ignition
Delay Period in Dual Fuel Engines, SAE Technical Paper 892140.
King, L. J ., and Prakash, C. B. 1992. Field Trials of Ethanol in Transit Buses,
SAE Technical Paper 922272.
23
Kittelson, D. B. 1998. Engines and Nanoparticles: A Review. J . Aerosol Sci.,
29(5/6): 575-588.
Kittelson, D., W. Watts, and J . J ohnson. 2002. Diesel Aerosol Sampling
Methodology. CRC E-43 Final Report, pp. 181 , NTIS Accession No. PB2003-102418l,
available from CRC, Alpharetta, GA. Available at
http://www.crcao.com/reports/recentstudies00-02/E-43%20Final%20Report.pdf
Kittelson, D. B., W.F. Watts, J .P. J ohnson. 2006a. On-road and Laboratory
Evaluation of Combustion Aerosols. Part 1: Summary of Diesel Engine Results. J .
Aerosol Science, 37(8): 913-930.
Kittelson, D. B., W. F. Watts, J . P. J ohnson, C. Rowntree, M. Payne, S. Goodier,
C. Warrens, H. Preston U. Zink, M. Ortiz, C. Grsmann, M. V. Twigg, A. P. Walker and
R. Caldow. 2006b. On-Road Evaluation of Two Diesel Exhaust Aftertreatment Devices.
J . Aerosol Science, 37:1140 1151.
Lacey, P. I., and Westbrook, S. R. 1997. Fuel Lubricity Additive Evaluation, U.S.
Army TARDEC Contract Interim Report TFLRF No. 323.
Lacey, P. I., and Howell, S. A. 1998. Fuel Lubricity Reviewed, SAE Technical
Paper 982567.
Lacey, P. I., Naegeli, D. W., De La Cruz, J . L., and Whalen, M. V. 2000.
Lubricity of Volatile Fuels for Compression Ignition Engines, SAE Technical Paper
2000-01-1804.
Lee, D., Hochgreb, S., and Keck, J . C. 1993. Autoignition of Alcohols and Ethers
in a Rapid Compression Machine, SAE Technical Paper 932755.
Liu, Z., and Karim, G. A. 1995. The Ignition Delay period in Dual Fuel Engines,
SAE Technical Paper 950466.
Marinov, N. M. 1999. A Detailed Chemical Kinetic Model for High Temperature
Ethanol Oxidation. Int. J . Chem. Kinetics, 31: 183 220.
Nagarajan, G., Rao, A. N., and Renganarayanan, S. 2002. Emission and
Performance Characteristics of Neat Ethanol Fuelled DI Diesel Engine, Int. J . of Ambient
Energy, 23(3): 149-158.
Nilesen, O. B., Qvale, B., and Sorenson, S. 1987. Ignition Delay in the Dual Fuel
Engine, SAE Technical Paper 870589.
Olson, A. L. 2010. The Effect of Water and Ethanol Fumigation on the
Performance and Emissions from a Light-Duty Direct-Injection Diesel Engine. Master of
Science Thesis submitted to the University of Minnesota, in preparation
Panuccio, G. J ., Williams, K. A., Schmidt, L. D. 2006. Contributions of
Heterogeneous and Homogeneous Chemistry in the Catalytic Partial Oxidation of Octane
Isomers and Mixtures on Rhodium Coated Foams, Chem. Eng. Sci., 61: 42074219.
Salge, J .R., G.A. Deluga, and L.D. Schmidt, 2005. Catalytic partial oxidation of
ethanol over noble metal catalysts, J ournal of Catalysis 235 (2005) 6978
Savage, L.D., White, R.A., Cole, S., and Pritchett, G. 1986. Extended
Performance of Alcohol Fumigation in Diesel Engines Through Different Multipoint
Alcohol Injection Timing Cycles. SAE Technical Paper 861580.
Schaefer, A. J ., and Hardenberg, H. O. 1981. Ignition Improvers for Ethanol
Fuels, SAE Technical Paper 810249.
24
Schroeder, A.R., Savage, L.D., White, R.A., and Sorenson, S.C. 1988. The Effect
of Diesel Injection Timing on a Turbocharged Diesel Engine Fumigated With Ethanol.
SAE Technical Paper 880496.
Swanson, J . J ., D. B. Kittelson, W. F. Watts, D. D. Gladis, M.V. Twig. 2009.
Influence of Storage and Release on Particle Emissions from New and Used CRTs.
Atmospheric Environment, 43:3998-4004.
Tsolakis, A., Hernandez, J . J ., Megartitis, A. and Crampton, M. 2005. Dual fuel
diesel engine operation using H
2
. Effect on particulate emissions, Energy & Fuels, 19:
418 425.
Westbrook, C. K. 200. Chemical Kinetics of Hydrocarbon Ignition in Practical
Combustion Systems, Proceedings of the Combustion Institute, 28 (Part 2), 1563 1577.
Whitby, K. T., and B. K. Cantrell. 1976. Atmospheric Aerosols: Characteristics
and Measurement. Proceedings of the International Conference on Environmental
Sensing and Assessment (ICESA), Institute of Electrical and Electronic Engineers
(IEEE). IEEE #75-CH 1004-1, ICESA paper 29-1, pp. 6, IEEE, Washington, DC.
Yilmaz, N., Donaldson, A. B., and J ones, A. 2005. Some Perspectives on Alcohol
Utilization in a Compression Ignition Engine, SAE Technical Paper 2005-01-3135.

APPENDIX A

Bika, A. S., L. M. Franklin, and D. B. Kittelson. 2009. Hydrogen as a Combustion
Modifier of Ethanol in Compression Ignition Engines. SAE Technical Paper Series 2009-
01-2814, 9 pp.




The Engineering Meetings Board has approved this paper for publication. It has successfully completed SAEs peer review process under the supervision of the
session organizer. This process requires a minimum of three (3) reviews by industry experts.
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic,
mechanical, photocopying, recording, or otherwise, without the prior written permission of SAE.
ISSN 0148-7191
Positions and opinions advanced in this paper are those of the author(s) and not necessarily those of SAE. The author is solely responsible for the content of
the paper.
SAE Customer Service: Tel: 877-606-7323 (inside USA and Canada)
Tel: 724-776-4970 (outside USA)
Fax: 724-776-0790
Email: CustomerService@sae.org
SAE Web Address: http://www.sae.org
Printed in USA
2009-01-2814
Hydrogen as a Combustion Modifier of Ethanol in Compression Ignition Engines
Anil Singh Bika, Luke M. Franklin, and David B. Kittelson
University of Minnesota

Copyright 2009 SAE International
ABSTRACT
Ethanol, used widely as a spark-ignition (SI) engine fuel,
has seen minimal success as a compression ignition (CI)
engine fuel. The lack of success of ethanol in CI
engines is mainly due to ethanols very low cetane
number and its poor lubricity properties. Past
researchers have utilized nearly pure ethanol in a CI
engine by either increasing the compression ratio which
requires extensive engine modification and/or using an
expensive ignition improver.

The objective of this work was to demonstrate the ability
of a hydrogen port fuel injection (PFI) system to facilitate
the combustion of ethanol in a CI engine. Non-
denatured anhydrous ethanol, mixed with a lubricity
additive, was used in a variable compression ratio CI
engine. Testing was conducted by varying the amount
of bottled hydrogen gas injected into the intake manifold
via a PFI system. The hydrogen flowrates were varied
from 0 10 slpm. The engine was operated at
compression ratios varying from 19:1 to 24:1 and intake
air temperatures ranging from 80C to 120C.

To prevent injection system lubrication failure, castor oil
and lauric acid were tested in various blends with
ethanol according to ASTM D975. It was found that 2%
by volume of lauric acid provided a wear scar diameter
of 200 m, very close to the diesel fuel wear scar
diameter of 195 m at 25C, and was chosen as the
lubricity additive.

Small amounts of hydrogen enabled ethanol operation at
a compression ratio of 19:1 and an intake temperature of
80C. This was a condition that was not sustainable
without hydrogen injection. Adding hydrogen with the
intake air advanced the start of combustion (SOC) timing
for many of the conditions tested. The relatively small
amounts of hydrogen necessary could be provided by an
onboard ethanol reformer. Further work is necessary to
determine why the hydrogen injection causes this SOC
advance.

INTRODUCTION
Traditionally, internal combustion engine (ICE) research
has focused on increasing power output; however in
recent years this focus has changed to encompass
issues such as energy resources and its impact on the
environment. A key thrust area is the increased
utilization of alternative fuels such as ethanol.

Ethanol, being an oxygenated high octane fuel, has seen
much success as an SI engine fuel, with many
government regulations requiring 10% blends of ethanol
in gasoline and newer flexible-fuel vehicles operating on
85% ethanol. In CI engines, however, ethanols success
has been limited mainly due to lubricity, ignitibility, and
miscibility issues [1-5].

Goering et al. investigated anhydrous and hydrous
ethanol in a two-stroke CI engine. To overcome
problems with lubricity, a Lubrizol additive was used. It
was found that the hydrous ethanol reduced NOx, CO,
and HC emissions. The engine power output was also

reduced, due to the lower ethanol fuel energy content.
After completing the 454 hour test, the only engine
related issues were with sticking fuel injectors.

Nagarajan et al. tested the performance of a CI engine
running on ethanol with 1% castor oil used as a lubricity
additive. Diethyl ether (DEE) was introduced into the
intake manifold to serve as an ignition improver, so there
was no need for intake air heating. Stable operation was
achieved with 3% DEE by ethanol mass share, however
the ignition delay period of ethanol was lengthened by 8
crank angle degrees (CAD) compared to diesel fuel.

Many researchers have investigated the lubricity of
alcohols and low-sulfur diesel fuels [6 10]. A review
paper on fuel lubricity can be found by Lacey et al. which
describes the various lubricity testing methods
applicable to CI engines. They also go into the details of
the different wear mechanisms commonly seen in
various diesel fuel injection systems. A range of
commercially available additives are also given, however
information on ethanol specific lubricity is lacking.

Estefan et al. investigated 106 different compounds in
concentrations of 1% by volume in methanol. Although
the application was for SI engines, the testing approach
utilized the ball on cylinder machine (BOCM), whose
data can also be applied to CI engines.

Apart from lubricity, another major problem with ethanol
use in CI engines is its difficulty to autoignite in diesel
engine conditions. Alcohol autoigntion and ignition
improvers have been investigated by many researchers
[11 - 13]. Hydrogen, however, as a combustion modifier
for an ethanol CI engine has not been investigated.

There has been significant interest in hydrogen because
of its clean burning properties and the prospect of
producing it from various renewable resources. A
possible method of using small amounts of hydrogen in
transportation applications is through on-board reforming
[14 16]. Another way of hydrogen utilization is with CI
dual fuel engines. With dual fuel engines, the engine
operates on two fuels; the primary fuel source is a
gaseous fuel such as hydrogen or natural gas which is
injected into the intake manifold and small pilot quantity
of diesel fuel injected into the combustion chamber using
the standard fuel injection equipment used to ignite the
mixture [17 19].

Liu et al. investigated the ignition delay period of CI dual
fuel engines using various gaseous fuels including
hydrogen with a diesel pilot fuel. It was found that as the
H
2
fuel admission was increased, the length of the diesel
ignition delay period also increased.

Nielsen et al. also investigated the ignition delay of a CI
dual fuel engine, but they used n-heptane and cetane,
along with diesel as pilot fuels. With all three fuels,
hydrogen addition into the intake manifold caused an
increase in the ignition delay.
Thus, previous research has shown that hydrogen
addition into the intake manifold of a dual fuel engine
operating on diesel fuel increases the ignition delay
period. The present work differs from dual fuel engine
operation, because the gaseous fuel is not the primary
fuel source, but instead is used to modify the combustion
of the primary fuel. The present work shows both
experimentally and with numerical simulations, how
small amounts of hydrogen in the intake manifold can
reduce the ignition delay period of a CI engine operating
on ethanol.

The goal of this work was not to optimize the conditions
for ethanol or hydrogen use in CI engines, but instead to
demonstrate how hydrogen may provide the means to
facilitate the combustion of ethanol in a CI engine with
minimal modifications (i.e. operating at real world
compression ratios and intake temperatures).

EXPERIMENTAL SETUP

ENGINE TEST STAND

A single cylinder cooperative fuels research (CFR)
cetane engine was used for this study. This engine has
a displacement of 611 cm
3
with a variable compression
ratio from 8:1 to over 24:1. The engine is coupled to a
synchronous motor which maintains a constant engine
speed of 900 RPM during both motoring and firing
conditions. A 2 kW resistive heater was used to heat the
intake air.

Cylinder pressure was measured using a 6125B Kistler
in-cylinder pressure transducer with a 5010 Kistler
charge amplifier. A rotary shaft encoder made by US
Digital with 1000 counts per revolution (CPR) resolution
was mounted on the crankshaft and used as the external
clock signal for the Labview 8.6.1 code written to acquire
and process the in-cylinder pressure data. Hamlin Hall-
effect sensors were used for crankshaft TDC and
camshaft signals. A Wolff Controls needle lift sensor
was used to determine injector motion.

A Quantum gaseous fuel injector was controlled by a
Motec M800 fuel injection controller to inject hydrogen
into the intake manifold. Hydrogen was only injected
during the intake stroke, to minimize mixture stratification
and any build up of hydrogen within the intake system.
This system allowed for precise control of injection
timing and quantity with the only on-engine hardware
needed being two Hall-effect sensors mounted on the
crankshaft and camshaft, respectively. Hydrogen
flowrates were measured with an Alicat M-series mass
flow meter.








ENGINE TEST PROCEDURE

Non-denatured anhydrous ethanol was used as the fuel
in this testing. To increase fuel lubricity and prevent fuel
injection system failure, 2% by volume of lauric acid was
added. High purity (>99.9%) bottled H
2
gas was used
for the H
2
addition tests.

Before beginning testing, the engine, along with the
intake system, was brought up to operating temperature
while running the engine on diesel fuel at a compression
ratio of 16.5:1. After reaching the desired operating
temperatures, the engine was switched off and the
diesel fuel was completely purged from the injection
pump and fuel lines, using ethanol. The compression
ratio was then increased to the desired level and the
engine was motored with the synchronous motor. The
intake temperature was once again allowed to stabilize,
and when it reached the correct value, the ethanol
injection was started and the engine was fired.

A wide sweep of engine tests were performed by varying
the compression ratio, ethanol injection timing and
fueling amount, and varying the hydrogen flowrate.
The hydrogen flowrates were varied from 0 10 slpm
with the overall equivalence ratio ranging from 0.5 to 0.7
and the H
2
energy fraction ranging between 5 20% of
the total energy. It was determined that a compression
ratio of 24:1 and an intake temperature of 120C was
necessary to achieve stable ethanol only operation. This
condition was then taken as the baseline condition. If
either the compression ratio or the intake temperature
were reduced below those values, the engine began to
misfire and run unstably using straight ethanol. Once
this baseline condition was established, we began to
investigate the effect of hydrogen both at this high
compression ratio and high temperature condition, and
also at lower compression ratios and lower
temperatures.

After compiling the test data, the following test conditions
were chosen for analysis.

Comp. Ratio Int. Temp (C) H
2
Flow (slpm)
24:1 120 0
Test 1
24:1 120 5
24:1 120 0
Test 2
24:1 80 5
24:1 120 0
Test 3
19:1 80 10

Table 1: Engine Test Matrix
The injection timing and fuelling amounts varied between
the different test conditions, but were kept constant
within each test condition. This means that comparisons
made between the no-hydrogen and hydrogen-assist
conditions at a given test condition will have the same
ethanol injection timing and fueling amount. The lower
compression ratio and intake air temperature of 19:1 and
80C, respectively, were chosen as real-world diesel
engine conditions, which have the potential of being
achievable with little to no engine modification.

RESULTS

RESULTS OF ETHANOL LUBRICITY ADDITIVES

Before beginning any hydrogen testing the issue of
lubricity had to be assessed. To prevent injection pump
and nozzle failure, diesel fuel must meet the ASTM
D975 lubricity standard. This method uses a High
Frequency Reciprocating Rig (HFRR) to test the diesel
fuel wear scar diameter, which can be performed at
25C, or the more typical 60C. For the ethanol tests we
had two additives tested; castor oil and lauric acid.
These additives were tested in blends of 1%, 2% and
3% by volume. During the HFRR tests at 60C, the
ethanol began to evaporate and a reliable wear scar
diameter could not be obtained, therefore the tests had
to be performed at the lower 25C temperature. Figure 1
shows a plot of the different wear scar diameters of the
various blends in ethanol, along with straight diesel fuel
which was tested at both 60C and 25C shown as the
straight lines and the ASTM limit.



Figure 1: Lubricity testing results showing wear scar diameters
of various proportions of castor oil and lauric acid in ethanol at
25C


Figure 1 shows that all of the blends fall below the ASTM
limit at 60C of 520 m. However, the castor oil and
lauric acid blends were tested at 25C and it is unclear
exactly how that correlates to the testing at 60C. The
figure shows a standard diesel fuel tested at 60C gave
a much higher wear scar diameter of 360 m compared
to the 195 m of the same diesel fuel tested at 25C.
For this reason, we chose to err on the side of safety,
and use the blend that provided the same wear scar
diameter under the same testing conditions as the
standard diesel fuel, hence tests conducted at 25C. It
was found that 2% by volume of lauric acid provided a
wear scar diameter of 200 m, very close to the diesel
fuel wear scar diameter of 195 m at 25C, and was
chosen as the blending additive.


RESULTS OF H
2
ADDITION IN ETHANOL CI ENGINE

High Compression Ratio with High Intake Temperature

The objective of this work was to demonstrate the ability
of hydrogen injection to facilitate the combustion of
ethanol in a CI engine. To accomplish this, the engine
had to first operate on ethanol alone without any
hydrogen addition. To achieve stable combustion, the
intake air temperature had to be increased to 120C and
the compression ratio was raised to 24:1. Figure 2 and
Figure 3 show the in-cylinder pressure trace, heat
release rate (HRR), and injector needle lift plot of the
engine operating on ethanol alone and with hydrogen
assist at a compression ratio of 24:1 and intake air
temperature of 120C.


Figure 2: Engine operating at a compression ratio of 24:1 and
intake temperature of 120C, with and without 5 slpm of H
2
addition with an ethanol injection timing of -13 CAD (ATDC)

Figure 3: Engine operating at a compression ratio of 24:1 and
an intake temperature of 120C, with and without 5 slpm of H
2

addition with an ethanol injection timing of -11.5 CAD (ATDC)
Figure 2 shows a plot with data taken at an injection
timing of -13 CAD (ATDC) and overall ethanol injection
duration of 20 CAD. The data shown in Figure 3 were
obtained with an injection timing of -11.5 CAD (ATDC)
and an overall injection duration of 16 CAD. For both of
these conditions, the hydrogen assisted flowrate was
limited to 5 slpm, because as the flowrate was
increased, the engine began to frontfire and the
hydrogen was igniting within the intake manifold.

It can be seen that there is a significant SOC advance
when the hydrogen is added. SOC in this case is
defined as the point where the HRR crosses zero. In
Figure 2, the ethanol only condition shows a SOC
advance of 6 CAD with hydrogen addition. In Figure 3
when the ethanol injection is slightly retarded and the
injection duration is reduced, the hydrogen addition
advances the SOC by 8 CAD. In both conditions, the
overall ethanol fueling rate and injection timing was kept
constant while hydrogen was added.

High Compression Ratio with Low Intake Temperature

The high compression ratio and high intake temperature
conditions described above are not suitable for real-
world diesel engine operation. Consequently we
decided to investigate the effect of hydrogen addition at
a more applicable diesel engine intake temperature of
80C, while keeping the compression ratio at 24:1.
Although many diesel engine manufacturers maintain
diesel engine intake manifold temperatures between 30-
45C, minor modification to the aftercooler setting or
alteration of the exhaust gas recirculation (EGR) input
can typically bring the manifold temperature to near
80C.

Figure 4: Ethanol injection timing and duration of -11 and 23
CAD (ATDC), respectively, at a CR 24:1 and an ethanol only
intake temperature of 120C, compared with the H
2
addition
condition at 5 slpm and an intake temperature of 80C


Figure 5: Ethanol injection timing and duration of -11 and 21
CAD (ATDC), respectively, at a CR 24:1 and an ethanol only
intake temperature of 120C, compared with the H
2
addition
condition at 5 slpm and an intake temperature of 80C
Figure 4 and Figure 5 show the in-cylinder pressure
trace, heat release rate (HRR), and injector needle lift
plot of the engine operating on ethanol alone an intake
temperature of 120C and a compression ratio of 24:1
compared to the hydrogen assisted cases operating at a
compression ratio of 24:1 and the lower intake air
temperatures of 80C.

Figure 4 shows the results of tests conducted with an
injection timing of -11 CAD (ATDC) and overall ethanol
injection duration of 23 CAD. The data shown in Figure
5 were obtained with an injection timing of -11 CAD
(ATDC) and an overall injection duration of 21 CAD. For
both of these conditions again, the hydrogen assist
flowrate was limited to 5 slpm, because as the flowrate
was increased, the hydrogen was igniting within the
intake manifold.

From the above figures it can be seen that the SOC of
both the ethanol only and the hydrogen assisted ethanol
cases are in virtually the same position. This means that
the hydrogen enabled the ethanol combustion at a much
lower intake temperature of 80C; an intake temperature
condition where ethanol only operation could not be
sustained.

Low Compression Ratio and Low Intake Temperature

Once it was determined that engine operation was
possible at the real-world applicable intake temperatures
of 80C, a more conventional compression ratio was
also tried. Figure 6 and Figure 7 show the in-cylinder
pressure trace, heat release rate (HRR), and injector
needle lift plot of the engine operating on ethanol alone
an intake temperature of 120C and a compression ratio
of 24:1 compared to the hydrogen assisted cases
operating at a compression ratio of 19:1 and the lower
intake air temperatures of 80C.


Figure 6: Ethanol injection timing of -13 CAD (ATDC), with
straight ethanol at CR 24:1 and intake temperature of 120C,
compared to H
2
addition of 10 slpm at CR 19:1 and intake
temperature of 80C
The data shown in Figure 6 was tested with an injection
timing of -13 CAD (ATDC) and overall ethanol injection
duration of 19 CAD. The data shown in Figure 7 was
tested with an injection timing of -12 CAD (ATDC) and
an overall injection duration of 21 CAD. For both of
these conditions, the hydrogen assist flowrate was 10
slpm. This flowrate was chosen, because 10 slpm was
the maximum hydrogen addition that was possible at the
lower intake temperature and lower compression ratio
condition, compared to the 5 slpm at the higher
compression ratio conditions.

Figure 7: Ethanol injection timing of -12 CAD (ATDC), with
straight ethanol at CR 24:1 and intake temperature of 120C,
compared with H
2
addition of 10 slpm at CR 19:1 and intake
temperature of 80C
At this condition, just as in the high compression ratio
and high intake temperature condition, it can be seen
that there is a significant start of combustion (SOC)
advance when the hydrogen is added. Figure 6 shows
there is a SOC advance of 6 CAD with hydrogen
addition. Figure 7 shows that when the ethanol injection
is slightly retarded and the injection duration is
increased, the hydrogen addition advances the SOC by
4 CAD. During these tests, as in all the previous
conditions tested, the overall ethanol fueling rate and

injection timing was kept constant while hydrogen was
added.

KINETIC SIMULATIONS OF H
2
ADDITION

To examine the kinetic effect of H
2
addition on ignition
delay time, simulations using CHEMKIN 4.1 were
conducted. The CHEMKIN software has a wide variety
of applications ranging from internal combustion engines
to chemical reactors that are useful in solving kinetic
problems. For these simulations, the 0-D homogeneous
reactor application was used. This application is a
constant volume closed adiabatic system, where the
initial pressure, temperature, and equivalence ratio must
be specified, along with the reaction mechanism and
thermodynamic property data. Although this simulation
approach is not representative of actual diesel in-
cylinder combustion, it does shed light into the
reactivitys of the mixture and gives some indication on
the kinetic behavior with and without hydrogen.

The simulations were conducted using two fuels; n-
Heptane and ethanol. n-Heptane is commonly
considered in kinetic simulations as a diesel fuel
surrogate, and was simulated in this case, because
there is a significant amount of experimental data on
H
2
+diesel dual fuel engines [16 19] showing a
lengthening of the ignition delay period. The reaction
mechanism used was found on the Lawrence Livermore
National Laboratory (LLNL) website [20]. For the
ethanol simulations, the mechanism developed by
Marinov was used [21].

A pressure of 30 atm was selected as the initial
pressure, because that is near the in-cylinder pressures
achieved during ethanol fuel injection. Equivalence
ratios of 0.3 and 0.9 were simulated as the baseline for
both the ethanol and heptane fuels to represent a wide
range that may be present in CI engines. Hydrogen
addition was simulated in two quantities of 2.5% and 5%
of total air volume. Depending on the condition tested,
the H
2
energy fraction varied from 7 to 35%. These
values were chosen, because they corresponded closely
to the 5 slpm and 10 slpm experimental conditions
tested. For the hydrogen addition cases, the main
ethanol or heptane fuelling amounts were kept constant
and the added hydrogen was assumed to displace the
molar air concentration. This means that as the
hydrogen was added the O
2
and N
2
concentrations
decreased, effectively increasing the equivalence ratio.
The initial temperatures were varied from 750 K to 1200
K to give a wide range of data.

Figure 8 shows the ignition delay times of ethanol with
hydrogen addition at an equivalence ratio of 0.3 at
various temperatures. It can be seen that ethanol
displays a linear ignition delay time curve with respect to
the inverse temperature, which is representative of
single-stage auto-ignition. An interesting trend that is
seen, which agrees with the experimental data
presented earlier, is a reduction in the ignition delay time
with hydrogen addition. This reduction is more profound
at the higher temperatures and diminishes at the lower
temperatures.


Figure 8: The ignition delay times of ethanol with hydrogen
addition at an equivalence ratio of 0.3 at various temperatures
Figure 9 shows the ignition delay times of ethanol with
H2 addition at an equivalence ratio of 0.9 at various
temperatures. The higher equivalence ratio does not
seem to have a significant impact on the ignition delay
times, because the values are close to those seen at the
lower equivalence ratio condition. The addition of
hydrogen also does not make as large of an impact on
the ignition delay time as the 0.3 equivalence ratio
condition, however slight reductions can be seen at the
higher temperatures.


Figure 9: The ignition delay times of ethanol with H
2
addition at
an equivalence ratio of 0.9 at various temperatures
Figure 10 shows the ignition delay times of n-heptane
with hydrogen addition, at an equivalence ratio of 0.3 at
various temperatures. The ignition delay curve is non-
linear, which means there are multiple stages of burning
that occur with heptane ranging from the
intermediate/cool-flame region seen towards the right of
Figure 10, to the high temperature region seen on the
left.



Figure 10: The ignition delay times of n-heptane with hydrogen
addition, at an equivalence ratio of 0.3 at various temperatures

Figure 11 shows the ignition delay times of n-heptane
with various amounts of H
2
addition, at an equivalence
ratio of 0.9. Again, the cool-flame/intermediate region
can be seen towards the right of the figure with the high
temperature region on the left. The ignition delay times
are much less at an equivalence ratio of 0.9 compared to
the 0.3 conditions. This is different from the ethanol
simulations.


Figure 11: The ignition delay times of n-heptane with various
amounts of H
2
addition, at an equivalence ratio of 0.9
The high-temperature and low-temperature regions
shown in Figure 10 and Figure 11 also exhibit varying
behavior to hydrogen addition. It can be seen that
during the low-temperature region, the hydrogen addition
actually increases the ignition delay period at both
equivalence ratios. At the high-temperature region, the
hydrogen addition begins to reduce the ignition delay
period.


DISCUSSION

The advancing SOC seen during hydrogen assisted
ethanol combustion is the opposite trend of what is seen
from hydrogen assisted diesel combustion [16-19]. To
understand this phenomenon, the ignition delay period
must be understood. The ignition delay period is the
time period between the start of injection and the start of
combustion. For this work, the start of injection is
considered to be when the injector needle lift sensor first
senses motion, and the start of combustion is when the
heat release rate first crosses zero.

The greatest factors affecting the ignition delay period
are thermal, physical, or chemical kinetic in nature. The
temperature of the inlet charge during compression will
vary, depending on the mixture specific heat ratio. If the
added gaseous fuel has a specific heat ratio close to that
of air, the compression temperatures will remain
relatively unchanged. Karim et al. show how the
calculated mean charge temperature at TDC does not
vary significantly with H
2
addition up to 10% of the air
volume. It is suggested that the combination of the
mixture specific heat ratio and the rate of heat transfer
with the H
2
addition balances causing no change in
compression temperatures.

The physical aspect of the ignition delay period have to
do with mixing characteristics and volatility of the
injected fuel, where a fuel such as ethanol will have
superior atomization, vaporization, and mixing
characteristics compared to a heavier diesel fuel [22].
This superior mixing and atomization may contribute to
an increased interaction between the hydrogen-air
mixture. Also, the fuel injection quantity has an effect in
determining the ignition delay period in dual fuel engines
[18]. Larger injection quantities tend to demonstrate
smaller changes to the delay, while relatively smaller
injection quantities show increased ignition delay. The
Chemkin model assume a premixed condition and thus
cannot capture mixing differences.

The chemical kinetic effect of the interaction between the
ethanol fuel vapor and the hydrogen may be very
important and is difficult to fully understand. During the
compression stroke, the gaseous fuel can experience
many pre-reactions, forming various radicals to aid in the
ignition of the main fuel. The exhaust residuals may also
contribute, not only to the thermal effect of adding heat
to the mixture, but also the kinetic effect of the supplying
radicals in the form of exhaust residuals. Although the
CHEMKIN simulations performed show that H
2
addition
may reduce the ignition delay of an ethanol-air mixture in
a constant volume chamber, the reductions, especially at
low temperature, are modest. The temperature in the
cylinder when the ethanol in injected is less that 1000 K
and at this temperature predicted changes in ethanol
ignition delays, with hydrogen injection are predicted to
be much less than actually observed.

Westbrook has reported that for practically all
hydrocarbons, ignition begins when there is a significant
presence of OH radicals [23]. This means that a method
which may cause an early presence of OH radicals may
also enable early ignition. Marinov has reported on a
kinetic model for high temperature ethanol oxidation [21].

In his work, he shows that ethanol oxidation exhibits a
strong sensitivity towards the hydroperoxyl (HO
2
) radical.
He shows that the following reaction:

CH
3
+ HO
2
CH
3
O + OH (reaction 1),

followed by the CH
3
O decomposition to CH
2
+ H atom is
the main supply route for H atoms and OH radicals.

In our experimental work, hydrogen was injected with the
intake air, comprising roughly 2-5% of the mixture
volume. At these concentrations of hydrogen addition,
and at the temperatures and pressures seen during
compression, it would be expected that some of the H
2

in the H
2
-air mixture would be converted to HO
2
, along
with H
2
O
2
. It would be expected that higher
concentrations of HO
2
around the ethanol fuel spray,
would increase the rate of reaction 1, causing the
advancing start of combustion seen with hydrogen
addition.

Direct comparison of the experimental and numerical
data presented in this paper cannot be made with the
diesel engine dual fuel tests made by other researchers,
because in this testing, the compression ratio and intake
temperatures were slightly elevated. Also, in this work
only a small amount of the energy (5-20%) was derived
from the gaseous H
2
fuel. It is clear, however, that the
start of combustion advances when H
2
is added to the
intake mixture. The chemical effect of the increased
HO
2
concentration with H
2
addition may have a greater
role than just the affect attributed to the thermal
properties of the charge or the physical characteristics of
the ethanol spray.


CONCLUSION
The focus of this work was to demonstrate how small
amounts of H
2
injected into the intake manifold can
facilitate the combustion of ethanol in a CI engine. Non-
denatured anhydrous ethanol mixed with a lubricity
additive was used in a variable compression ratio CI
engine.

Testing was conducted, with a focus on the start of
combustion (SOC) timing, by varying the amount of
bottled hydrogen gas injected into the intake manifold via
a PFI system. The hydrogen flowrates were varied from
0 10 slpm with the overall equivalence ratio ranging
from 0.5 to 0.7 and the H
2
energy fraction ranging
between 5 20% of the total energy. The engine was
operated at compression ratios varying from 19:1 to 24:1
and intake air temperatures ranging from 80C to 120C.
The following conclusions can be drawn from this work:

Castor oil and lauric acid were tested as lubricity
additives for ethanol use in a CI engine using
proportions of 1%, 2%, and 3% by volume. It
was found that lauric acid was much more
effective than castor oil and than 2% lauric acid
provided sufficient protection to the diesel fuel
injection equipment, meeting the ASTM D975
lubricity standard.
Stable engine operation was achieved using
ethanol, without the use of an ignition improver.
This was accomplished by increasing the
compression ratio and intake temperature to
24:1 and 120C respectively, and using 2% by
volume of lauric acid as a lubricity additive.
The addition of 5 10 slpm of H
2
with the intake
air advances the SOC of ethanol CI engine
operation at various compression ratios and
intake temperatures.
The addition of 10 slpm of H
2
in the intake
manifold enabled stable engine operation at a
compression ratio and intake temperature of
19:1 and 80C, respectively. These are
compression ratios and intake temperatures that
can be achieved in conventional CI engines with
minimal modification.

Further work, both experimental and modeling, is
needed to determine the exact cause of the SOC
advance with H
2
addition. Also, testing with blends of H
2

and CO would be of interest to see if the same trends
can actually be seen with an on-board reformer.


ACKNOWLEDGMENTS
This work has been funded by the Minnesota Corn
Growers Association. We would also like to thank the
undergraduate students Mathew Schumacher and
Andrew Simon for help in running the experiments.
REFERENCES
1. Yilmaz, N., Donaldson, A. B., and Jones, A., Some
Perspectives on Alcohol Utilization in a Compression
Ignition Engine, SAE Technical Paper 2005-01-
3135, 2005.
2. Goering, C. E., Parcell, R. T., and Ritter, C. P.,
Hydrated Ethanol as a Fuel for a DI, CI Engine,
Transactions of the ASAE, 41 (5): 1255-1260, 1998.
3. Nagarajan, G., Rao, A. N., and Renganarayanan, S.,
Emission and Performance Characteristics of Neat
Ethanol Fuelled DI Diesel Engine, Int. J. of Ambient
Energy, 23(3): 149-158, 2002.
4. Hardenberg, H. O., and Schaefer, A. J., The Use of
Ethanol as a Fuel for Compression Ignition
Engines, SAE Technical Paper 811211, 1981.
5. King, L. J., and Prakash, C. B., Field Trials of
Ethanol in Transit Buses, SAE Technical Paper
922272, 1992.
6. Estefan, R. M., and Brown, J. G., Evaluation of
Possible Methanol Fuel Additives for Reducing
Engine Wear and/or Corrosion, SAE Technical
Paper 902153, 1990.
7. Lacey, P. I., and Howell, S. A., Fuel Lubricity
Reviewed, SAE Technical Paper 982567, 1998.

8. Lacey, P. I., Naegeli, D. W., De La Cruz, J. L., and
Whalen, M. V., Lubricity of Volatile Fuels for
Compression Ignition Engines, SAE Technical
Paper 2000-01-1804, 2000.
9. Barbour, R. H., Rickeard, D. J., and Elliot, N. G.,
Understanding Diesel Lubricity, SAE Technical
Paper 2000-01-1918, 2000.
10. Lacey, P. I., and Westbrook, S. R., Fuel Lubricity
Additive Evaluation, U.S. Army TARDEC Contract
Interim Report TFLRF No. 323, June 1997.
11. Lee, D., Hochgreb, S., and Keck, J. C., Autoignition
of Alcohols and Ethers in a Rapid Compression
Machine, SAE Technical Paper 932755, 1993.
12. Bollentin, J. W., and Wilk, R. D., Autoignition
Characteristics of Ethanol, SAE Technical Paper
961175, 1996.
13. Schaefer, A. J., and Hardenberg, H. O., Ignition
Improvers for Ethanol Fuels, SAE Technical Paper
810249, 1981.
14. Tsolakis, A., Hernandez, J. J., Megartitis, A. and
Crampton, M., Dual fuel diesel engine operation
using H2. Effect on particulate emissions, Energy &
Fuels, 19: 418 425, 2005.
15. Panuccio, G. J., Williams, K. A., Schmidt, L. D.,
Contributions of Heterogeneous and Homogeneous
Chemistry in the Catalytic Partial Oxidation of
Octane Isomers and Mixtures on Rhodium Coated
Foams, Chem. Eng. Sci., 61: 42074219, 2006.
16. Nilesen, O. B., Qvale, B., and Sorenson, S., Ignition
Delay in the Dual Fuel Engine, SAE Technical
Paper 870589, 1987.
17. Liu, Z., and Karim, G. A., The Ignition Delay period
in Dual Fuel Engines, SAE Technical Paper
950466, 1995.
18. Gunea, C., Razavi, M. R. M, and Karim, G. A., The
Effects of Pilot Fuel Quality on Dual Fuel Engine
Ignition Delay, SAE Technical Paper 982453, 1998.
19. Karim, G. A., Jones, W., and Raine, R. R., An
Examination of the Ignition Delay Period in Dual
Fuel Engines, SAE Technical Paper 892140, 1989.
20. Curran, H. J., Gaffuri, P., Pitz, W. J., and Westbrook,
C. K. A Comprehensive Modeling Study of n-
Heptane Oxidation, Combustion and Flame, 114:
149 177, 1998.
21. Marinov, N. M. A Detailed Chemical Kinetic Model
for High Temperature Ethanol Oxidation, Int. J.
Chem. Kinetics, 31: 183 220, 1999.
22. Henein, N. A., and Akasaka, Y., Effect of Physical
Properties and Composition on Fuels on Autoignition
and Cetane Rating, SAE Technical Paper 871617,
1987.
23. Westbrook, C. K., Chemical Kinetics of
Hydrocarbon Ignition in Practical Combustion
Systems, Proceedings of the Combustion Institute,
28 (Part 2), 1563 1577, 2000.
CONTACT
Anil Singh Bika University of Minnesota
bika0007@umn.edu