Efficacy of Add-On Hydrous

Ethanol Dual Fuel Systems to

Jeffrey T. Hwang
Mechanical Engineering,
University of Minnesota,
111 Church Street SE,
Minneapolis, MN 55455
e-mail: hwang183@umn.edu
Alex J. Nord
Mechanical Engineering,
University of Minnesota,
111 Church Street SE,
Minneapolis, MN 55455
e-mail: nord0537@umn.edu
William F. Northrop
Mem. ASME
Mechanical Engineering,
University of Minnesota,
111 Church Street SE,
Minneapolis, MN 55455
e-mail: wnorthro@umn.edu
Reduce NOx Emissions From
Diesel Engines
Aftermarket dual-fuel injection systems using a variety of different fumigants have been
proposed as alternatives to expensive after-treatment to control NOx emissions from leg-
acy diesel engines. However, our previous work has shown that available add-on systems
using hydrous ethanol as the fumigant achieve only minor benefits in emissions without
recalibration of the diesel fuel injection strategy. This study experimentally re-evaluates
a novel aftermarket dual-fuel port fuel injection (PFI) system used in our previous work,
with the addition of higher flow injectors to increase the fumigant energy fraction (FEF),
defined as the ratio of energy provided by the hydrous ethanol on a lower heating value
(LHV) basis to overall fuel energy. Results of this study confirm our earlier findings that
as FEF increases, NO emissions decrease, while NO2 and unburned ethanol emissions
increase, leading to no change in overall NOx. Peak cylinder pressure and apparent rates
of heat release are not strongly dependent on FEF, indicating that in-cylinder NO forma-
tion rates by the Zel’dovich mechanism remain the same. Through single zone modeling,
we show the feasibility of in-cylinder NO conversion to NO2 aided by unburned ethanol.
The modeling results indicate that NO to NO2 conversion occurs during the early expan-
sion stroke where bulk gases have temperature in the range of 1150–1250 K. This work
conclusively proves that aftermarket dual fuel systems for fixed calibration diesel engines
cannot reduce NOx emissions without lowering peak temperature during diffusive com-
bustion responsible for forming NO in the first place. [DOI: 10.1115/1.4036252]

Introduction gas [9–14], and all have similar impacts on avoiding in-cylinder
NOx formation.
Diesel engines are known for reliability, durability, low manu-
Although RCCI is an attractive method for in-cylinder emis-
facturing cost, and high power density. Given their longevity, leg-
sions reduction, it must be implemented in new engines due to the
acy diesels regulated to older emissions levels will continue to be
requirement for significant modifications to engine hardware and
used in practice for decades to come. New diesel engines have
software. To date, manufacturers have chosen to employ NOx
27% lower NOx emissions than engines of a decade ago [1] in
aftertreatment like SCR to meet stringent emissions standards for
part due to selective catalytic reduction (SCR) aftertreatment sys-
new engines and rely less on advanced in-cylinder techniques like
tems. Although aftertreatment is an effective method for reducing
dual fuel RCCI.
emissions, in-cylinder techniques are also attractive to reduce
For legacy diesel engines regulated to older emissions stand-
SCR urea dosing rate requirements or to possibly eliminate the
ards, add-on SCR and lean NOx trap aftertreatment systems have
need for NOx aftertreatment altogether.
been marketed to meet new in-use NOx regulations [15]. Dual
In-cylinder NO is primarily formed during combustion through a
fuel retrofit kits are available which also claim to reduce NOx
combination of chemical pathways including the extended Zel’do-
emissions without aftertreatment while also substituting diesel
vich, prompt (Fenimore) and N2O mechanisms [2–4]. NO in diesel
fuel for lower carbon fuels like compressed natural gas or partially
engines mainly arises through the thermally controlled Zel’dovich
renewable ethanol [16,17]. These aftermarket systems incorporate
mechanism in lean to stoichiometric regions found near the periph-
a separate fuel system and fumigate the secondary fuel directly
ery of the diffusive flame front. NO is oxidized to NO2 and concen-
into the intake plumbing, retaining the stock engine calibration
trations “freeze” short of thermodynamic equilibrium soon after the
and hardware. Therefore, these systems cannot achieve the emis-
end of injection and mixing of burned gases [5] in the expansion
sions reductions possible with RCCI since they do not change the
stroke.
diesel fuel injection strategy. Fumigation for diesel engines has a
Low temperature combustion modes like dual fuel reactivity
long history [18]. The previous work has examined advancing die-
controlled compression ignition (RCCI) have been shown to
sel injection timing of a mechanically injected engine with fumi-
simultaneously limit in-cylinder NOx and soot production over a
gation of hydrous ethanol [19] to increase the diesel replacement
wide speed and load range [6–8]. RCCI uses fumigation of a low
quantity but this strategy is not applicable to modern electroni-
reactivity fuel like gasoline into the intake manifold and early
cally controlled diesel engines.
direct injection of a high reactivity fuel like diesel to avoid high
Our previous work investigated using hydrous ethanol as the
temperature NOx formation regions found in conventional diesel
fumigant in an add-on configuration both with an existing com-
combustion (CDC). Various fumigants have been investigated for
mercial fumigation system [16] and with a novel port-injection
RCCI including hydrogen, gasoline, hydrous ethanol, and natural
system [20]. This work along with other published literature on
aftermarket dual fuel systems [9,13,21,22] shows that NOx is not
appreciably reduced with increased FEF, defined as the ratio of
Contributed by the Internal Combustion Engine Division of ASME for
publication in the JOURNAL OF ENERGY RESOURCES TECHNOLOGY. Manuscript received
fumigant lower heating value to overall input fuel lower heating
February 13, 2017; final manuscript received February 27, 2017; published online value. Others have shown that when the water content of hydrous
March 30, 2017. Assoc. Editor: Stephen A. Ciatti. ethanol exceeds 50%, NOx can be mitigated through intake charge

Journal of Energy Resources Technology Copyright V

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 Table 1 Engine specifications Table 2 Modified ISO 8178 engine operation conditions

Manufacturer/model John Deere 4045HF475 Mode Engine speed (rpm) Engine load (Nm) BMEP (bar)
Engine type 4-stroke DI diesel
Cylinders 4, in-line 1 2400 450 12.6
Displacement (L) 4.5 2 2400 350 9.77
Bore  stroke (mm) 106  127 3 2400 250 6.98
Compression ratio 17.0:1 4 2400 50 1.40
Maximum power (kW/rpm) 129/2400 5 1400 450 12.6
Aspiration Turbocharged and after cooled 6 1400 350 9.77
Diesel injection system Common rail 7 1400 250 6.98
Ethanol injection system Port fuel injection 8 1000 0 (idle) 0.00
Ethanol heating system None
Emissions certification EPA tier 2 (off-highway)
IVO (CAD ATDCF) 339
EVC (CAD ATDCF) 380
Table 3 Engine performance parameters at maximum FEF
achieved
cooling, lowering peak combustion temperatures in the diffusive
flame [2,23]. Max FEF BSFC BTE CE A/F
Although overall NOx emissions do not significantly decrease Mode Operation (%) (g/kW h) (%) (%) ratio
for add-on dual fuel systems, our work and research by others
1 160 proof 41.7 252 34.0 99.6 28.5
have shown that the NO2 to NOx fraction increases with increas- 180 proof 39.1 210 40.8 99.8 32.6
ing FEF [2,14,16,20]. This suggests that NO formation during Diesel 0 220 39.0 99.9 32.2
combustion remains unchanged for dual fuel operation but that
2 160 proof 61.8 274 31.2 99.3 28.5
NO oxidation to NO2 occurs with more fumigation. 180 proof 60.0 220 39.0 99.5 34.9
Increased unburned hydrocarbon (HC) emissions also increase Diesel 0 226 38.0 99.9 35.2
with FEF, which have been implicated in the NO to NO2 conver-
3 160 proof 51.6 288 29.8 99.3 32.1
sion process. HO2 radicals formed within the cylinder from the 180 proof 49.6 229 37.4 99.5 39.9
oxidation of intermediate species such as CH3CHOH have been Diesel 0 234 36.6 99.9 39.0
shown to be responsible for the conversion of NO to NO2 [3,4]. At
4 160 proof 41.2 630 13.6 98.9 51.3
high temperatures, HO2 is unstable and unable to react; however 180 proof 46.0 590 14.5 98.8 55.7
as temperatures decrease, the HO2 radical becomes stable and Diesel 0 435 19.7 99.9 71.0
begins to promote the reaction of NO to NO2. Hori et al. illustrated
5 160 proof 23.8 214 40.1 99.9 22.0
a kinetic mechanism by which hydrocarbons facilitate the conver- 180 proof 21.6 201 42.6 99.9 23.1
sion of NO to NO2 at temperatures between 600 and 1200 K [24]. Diesel 0 206 41.6 99.9 23.4
As in-cylinder temperatures are generically higher than engine
6 160 proof 27.6 223 38.5 99.9 23.2
exhaust temperatures, it can be concluded that the NO to NO2 con- 180 proof 28.7 205 41.8 99.9 25.0
version via unburned hydrocarbons occurs within the cylinder dur- Diesel 0 209 41.0 99.9 25.6
ing the expansion stroke. Although hydrocarbon assisted NO
7 160 proof 33.4 230 37.2 99.8 27.4
conversion chemistry has been studied with light hydrocarbons 180 proof 26.0 215 39.9 99.9 29.5
like methane and ethane, ethanol has not been investigated. Diesel 0 213 40.3 99.9 31.1
The work presented here provides a thorough set of perform- 8 160 proof 48.9 980 8.74 99.1 80.1
ance and emissions data for an add-on hydrous ethanol port injec- 180 proof 53.0 848 10.1 98.9 90.5
tion dual fuel diesel engine covering a larger range of FEF and Diesel 0 604 14.2 99.9 131
hydrous ethanol water content than our previous work. It also
investigates the effect of unburned hydrocarbons on in-cylinder
NO to NO2 conversion through comparison of experimental data
to a single zone kinetic model.

Experimental
The objective of the experimental work was to investigate a
hydrous ethanol dual fuel PFI system over a large range of engine

Fig. 2 In-cylinder pressure traces and apparent RoHR for

Fig. 1 Diagram of engine test setup mode 3 and 180 proof hydrous ethanol

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 operation using varying hydrous ethanol water content and FEF.
A John Deere 4045HF475 Tier 2 diesel engine was used in the
experiments. The specifications of the engine and PFI system are
shown in Table 1.
The same custom PFI fuel rail from our previous work was
used in this study [20]. The PFI rail was integrated into the exist-
ing intake manifold and incorporated two automotive-grade fuel
injectors aligned to spray directly in between the intake ports of
the cylinders.
Hydrous ethanol injections were controlled using the signal
from the manufacturer-installed camshaft sensor. Analysis of the
signal provided engine speed and the location of cylinder one top
dead center (TDC) to a National Instruments (NI) cRIO controller.
Hydrous ethanol injection pulse width and timing were then out-
put by the cRIO to each injector. Each injector injected twice per
two engine rotations starting at 360 crank angle degree (CAD)
after top dead center firing (ATDCF), 21 CAD after intake valve
open (IVO), to partially mitigate fuel bypass from positive valve
overlap inherent to this engine. The hydrous ethanol was stored in
a secondary container and pumped to the PFI rail at constant flow.
A digital scale was used to determine the time rate change of
mass during a given testing duration for hydrous ethanol while
diesel fuel flow was measured using a CUB5 series mechanical
fuel flow meter.
A laminar flow element (LFE) was used to measure the intake
airflow rate, and after-cooler outlet temperature was maintained
between 40 and 50  C using an air–water heat exchanger. Heated
intake air was required to ensure complete combustion of the
charge due to ethanol’s high latent heat of vaporization.
Gaseous emissions were measured using an AVL (Graz, Aus-
tria) Fourier transform infrared spectrometer (FTIR), while soot
emissions were measured using an AVL microsoot sensor (MSS).
Engine exhaust was first diluted at a ratio of 5–7 in a residence
chamber with compressed air before being measured by the MSS.
The FTIR sampled both raw exhaust and diluted exhaust, where
the ratio of CO2 emissions before and after dilution was used as a
measurement of dilution ratio at every testing point. The experi-
mental setup is given in Fig. 1.
In addition to engine performance and emissions data, high-
speed in-cylinder pressure data were collected at each testing con-
dition. Kistler Type 6065 A pressure transducers were mounted in
custom Kistler 6542Q128 glow plug adapters for all four engine
cylinders. A 0.1 CAD resolution BEI H25 incremental optical
encoder was mounted to the engine crank to trigger data acquisi-
tion using a NI BNC-2110 and PXI-6123 DAQ. A NI LABVIEW
interface was programmed to sample 100 cycles for a total of
720,000 data points per cylinder. Apparent heat release rate was
calculated using a custom postprocessing code and a first law
analysis as outlined in Ref. [25].
Hydrous ethanol with 10% (180 proof) and 20% (160 proof)
water by volume was used in this study. Both proofs of hydrous
ethanol have a lower distillation energy to LHV ratio during the
refining stages and do not require dehydration, thereby signifi-
cantly increasing the renewability of the fuel [26]. Hydrous etha-
nol blends were mixed by volume with lab grade nondenatured
anhydrous ethanol and distilled water. The primary direct injected
fuel used was nonoxygenated #2 ultralow sulfur diesel (ULSD).
The experimental testing plan consisted of operating the engine
over a modified type C1 off-road vehicle ISO 8178 eight point
testing cycle with and without hydrous ethanol PFI [27]. The test-
ing modes are shown in Table 2.
At each testing mode, the engine was first allowed to reach
steady-state diesel fuel only combustion. The PFI system was then
toggled “on” for PFI of hydrous ethanol and data were taken once
emissions, temperature, and pressure data reached steady state.
The stock engine electronic control unit (ECU) was not modified
in any way; all diesel injection parameters followed the original
equipment manufacturer calibration. Data were collected at inter-
vals of 2 min at steady-state operation and then averaged for
reported results.
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Ethanol injector pulse width was varied to increase FEF, while
engine load was held constant by varying the engine pedal posi-
tion, effectively decreasing the diesel fuel flow to accommodate
the increased load during PFI operation. After data collection for
the selected testing mode was completed, the PFI system was
toggled “off” and cycled to the next testing mode under conven-
tional diesel combustion (CDC). Experiments were conducted
over a four-day period, where the eight-point test cycle was con-
ducted in its entirety on each day for 160 proof, 180 proof,
selected repeats (160 and 180 proof), and CDC, respectively. FEF
was determined using the time rate change of mass of hydrous
ethanol and the measured diesel fuel flow rate at each testing con-
dition in conjunction with respective LHV values. The ratio of
ethanol energy input over total energy input was then calculated
as the FEF, where maximum FEF corresponds to the maximum
pulse width achieved at each testing condition.
An uncertainty analysis was conducted using standard devia-
tions of measurements during steady state and between repeated
datasets. Error bars on result figures are based on the root mean
square value of two times the standard deviation, representing the
95% confidence interval. Propagation of error calculations were
estimated using the numerical sequential perturbation approach
[28]. Systemic error was small compared to the standard deviation
error and was only used for the hydrous ethanol time rate change
of mass.
Results and Discussion
Performance and Emissions. The diesel engine equipped with
the PFI hydrous ethanol dual fuel system was operated over a
range of injector pulse widths for each operating mode with 160
proof, 180 proof, and diesel-only modes. Performance results for
the max FEF achieved at each condition are given in Table 3. All
values were calculated on a diesel equivalent basis. Combustion
efficiency (CE) and air/fuel ratio (AFR) decreased very slightly
with increasing FEF for all conditions. The decrease in CE can be
attributed to charge cooling effects from the latent heat of hydrous
ethanol vaporization and the increased amount of water being
introduced to the engine. Brake thermal efficiency (BTE)
decreased with increasing FEF for most cases, but increased
slightly for a few 180 proof cases. This behavior is coupled with
the brake specific fuel consumption (BSFC), which increased with
increasing FEF for most cases, but decreased for the same 180
proof cases with increased BTE.
All testing modes were stability limited, defined as when an
increase in injector pulse width resulted in unstable combustion or
audible engine knock. Around 160 proof hydrous ethanol testing
modes were able to reach higher injector pulse widths as com-
pared to 180 proof, before the onset of knock. The higher knock
tolerance of 160 proof ethanol can be explained by the increased
charge cooling from higher water content. A significant barrier for
diesel fuel replacement at low engine speeds exists as illustrated
in Table 3 especially at high load (modes 5 and 6) where the sta-
bility limit was reached between an FEF of 23–25%.
Figure 2 shows the in-cylinder pressure and calculated apparent
rate of heat release (RoHR) for mode 3 (2400 rpm, 7 bar brake
mean effective pressure (BMEP)) for selected FEF and 180 proof
hydrous ethanol. As FEF increased, the premixed heat release
event and peak pressure increased in magnitude. Combustion
phasing, as measured by CA50 advanced slightly with increasing
FEF, while burn duration, defined as CA90–CA05 decreased with
increasing FEF. For example, for the cases shown in Fig. 2, CA50
advanced from 16.4 deg after top dead center (DATDC) to 13.5
DATDC, while burn duration decreased from 27.5 CAD to 20.0
CAD. These trends are primarily due to the increased premixed
portion of combustion with increased ethanol. The bimodal shape
of the RoHR reflects amplified premixed and diffusion portions of
combustion. This has been previously explained by the combus-
tion of directly injected diesel fuel providing ignition energy for
the combustion of the premixed fumigant [29]. Unlike with RCCI
JULY 2017, Vol. 139 / 042206-3

Fig. 3 Brake specific CO emissions as a function of FEF for
160 and 180 proof hydrous ethanol
that uses advanced diesel injection timing to generate a primarily
premixed combustion event, the mixing controlled mode of heat
release remained present with increasing FEF.
Brake specific CO emissions are shown in Fig. 3 for 160 and
180 proof hydrous ethanol injections over a range of FEF for each
testing mode. The dotted lines depicted on emission plots repre-
sent diesel only combustion. CO emissions increased uniformly
with increasing FEF and were largely independent of ethanol
proof. Incomplete combustion is the primary cause of increased
CO emissions, while low in-cylinder temperatures prevent the oxi-
dation of CO to CO2. The trend also shows CO emissions reaching
Fig. 4 Selected HC emissions on a brake-specific basis as a
function of FEF for 160 and 180 proof hydrous ethanol at
mode 3
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a horizontal asymptote at high FEF where the increased A/F ratio
prevents the formation of CO.
Increases in CO have been shown to directly correlate with an
increase in HC emissions for combustion with alcohols [13]. Fur-
thermore, excess HC emissions in dual fuel modes are known to
arise from the fumigant and not the directly injected diesel fuel
[9]. Figure 4 shows the light HC distribution for 160 and 180
proof hydrous ethanol at mode 3 for a range of FEF as measured
by FTIR. Methane (CH4) and ethylene (C2H4) emissions increase
with FEF indicating incomplete combustion that becomes more
significant. Using 160 proof hydrous ethanol leads to higher light
HC emissions overall. Increased water injection at the same FEF
level leads to additional cylinder charge cooling that lowers in-
cylinder temperature and leads to more incomplete combustion.
This is reflected in the lower CE values for lower ethanol proof
given in Table 3.
Although injected hydrous ethanol proof had a significant impact
on light HC emissions, it did not change brake specific ethanol
emissions as shown in Fig. 5. Similar to our previous work, high
engine load cases exhibit the lowest amount of unburned ethanol
due to higher engine temperatures allowing sufficient heating to
combust the ethanol completely. Unburned ethanol emissions
increase with FEF mainly because it arises from areas in the com-
bustion chamber uninfluenced by the diffusive combustion event.
These areas include the squish and crevice regions. With increasing
FEF, the concentration of ethanol is greater in these regions leading
to higher emissions.
Furthermore, at low engine load conditions, unburned ethanol
emissions increase much more rapidly as a function of FEF due to
fewer sufficiently hot regions in the combustion chamber. Unburned
ethanol concentration is lower for the 1400 rpm modes because low
engine speed conditions operate at higher temperatures than high
engine speed conditions for a given load. Fang et al. have also
shown that ethanol delays ignition and combustion phasing, also
resulting in increased unburned ethanol in the exhaust at higher
Fig. 5 Brake specific unburned ethanol emissions as a func-
tion of FEF for 160 and 180 proof hydrous ethanol
Transactions of the ASME
 engine speed [9]. In addition, the injected ethanol is premixed with
intake air, causing any overlap between exhaust valve close (EVC)
and intake valve open (IVO) events to increase unburned ethanol
emissions through short-circuiting [20]. Although the PFI injection
strategy used in this study injected 21 CAD after IVO to mitigate
this effect, some short-circuiting is still expected. In addition, gases
from crevice volumes are known to increase unburned ethanol
emissions.
Figure 6 shows soot concentration in mg/m3 of exhaust for all
tested conditions. There was no uniform trend in soot emissions as
a function of FEF. High load modes (modes 1, 2, 5, 6) showed
increasing soot emissions with FEF. Of those that achieved high
FEF (modes 1 and 2), the soot eventually decreased. Initial
increases in soot could be due to higher temperature diffusion
combustion and richer mixture around the flame zones due to pre-
mixed ethanol. However, at high FEF, less diesel is injected, and
combustion shifts to a more premixed mode.
For lighter load modes at high speed (modes 2 and 3), premixed
ethanol had a more immediate effect in decreasing soot emissions.
At these conditions, shorter residence time and diesel injection
duration allowed soot to decrease more rapidly with FEF. At idle,
soot emissions were negligible and independent of FEF due to pri-
marily premixed low temperature combustion. Ethanol proof also
had no impact on soot emissions for any mode indicating that any
benefits gained were due to ethanol replacement of diesel and not
through water influence on soot formation.
Ethanol may also chemically play a role in decreasing soot for-
mation at higher FEF. Previous work has shown that dual-fuel
combustion reduces soot concentrations, especially when the sec-
ondary fuel is ethanol where increased OH radicals lead to greater
postcombustion soot oxidation [2,30,31]. Ethanol (C2H5OH) con-
sists of C–H, C–C, C–O, and O–H bonds. During combustion, the
C–C and C–O bonds can be readily broken due to their lower
bond energies. This chemical reaction causes an increased con-
centration of OH radicals within the combustion chamber [14]. If
the theory is accurate, higher OH radical concentration at higher
FEF may result in decreasing exhaust soot concentration.
Fig. 6 Soot concentration as a function of FEF for 160 and 180
proof hydrous ethanol
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NOx Emissions Results. Figure 7 depicts the brake specific
NO emissions for 160 and 180 proof hydrous ethanol. For every
operating mode, NO emissions decreased with increasing FEF, as
might be expected due to the increase in charge cooling lowering
in-cylinder temperatures. However, there was no discernable
change in NO emissions between the use of 160 and 180 proof
hydrous ethanol at a given FEF indicating that the NO formation
is independent of water content in the fuel. This discrepancy is
evidence that other factors besides charge influence NO emissions
for dual fuel combustion, such as the propensity of unburned
hydrocarbons facilitating the conversion of NO to NO2 during the
expansion stroke. The chemical kinetics and mechanisms respon-
sible for this conversion are discussed in the single zone combus-
tion modeling presented later in this work.
As in previous work, increasing FEF had very little impact on
overall NOx emissions as shown in Fig. 8. This indicates that
fumigation with hydrous ethanol for all cases, except for the very
highest FEF conditions, does not have an impact on the NO for-
mation during diffusive diesel combustion and that NO is con-
verted to NO2 at some point during the closed cycle. Only at very
high FEF does charge cooling play a role in mitigating formation
via the thermal Zel’dovich mechanism, especially noticeable dur-
ing mode 4.
The experimental data imply that NO is converted to NO2 while
overall NOx concentration nearly constant. As a measure of the
conversion process, Fig. 9 shows the NO2/NOx ratio for all experi-
mental data points collected in the study as a function of unburned
ethanol measured in the exhaust normalized by the diesel-only
NOx emissions per mode, respectively. The NO to NO2 conver-
sion process occurs rapidly as a function of unburned ethanol until
reaching a horizontal asymptote around 0.72. At this point, no fur-
ther conversion of NO occurs with increasing FEF. Reasons for
this trend are not apparent from the experimental data and require
additional kinetics modeling to investigate.
Fig. 7 Brake specific NO emissions as a function of FEF for
160 and 180 proof hydrous ethanol
JULY 2017, Vol. 139 / 042206-5
 mechanism from Lawrence Livermore National Laboratory
(LLNL) was used in the model [24]. Initial conditions for the
model were the same as for the paper by Hori et al. including
atmospheric pressure and concentrations 20 PPM NO in N2, 50
PPM of HC in N2, and the remainder air.
The constant pressure model was run over a sweep of operating
temperature between 600 and 1200 K at 50 K increments, where
the gases were controlled to a 1.5 s residence time within the reac-
tor. Ethanol, ethylene, and methane were used as hydrocarbons
because these had the highest concentrations in the measured
engine exhaust. Concentrations of NO and NO2 were exported
and the ratio of final NO2/NOx ratio for each operating tempera-
ture can be seen in Fig. 10.
Figure 10 shows that ethanol has a peak NO2/NOx ratio similar
to ethylene but over a smaller temperature window. Hydrocarbons
predominantly oxidize NO to NO2 through the NO þ HO2 $
NO2 þ OH mechanism. Hori et al. have shown that the effective-
ness of a hydrocarbon at converting NO to NO2 is dependent on its
ability to simultaneously produce radicals like OH to sustain fuel
oxidation and HO2 for NO to NO2 conversion [24]. According to
the model, methane does not readily promote the conversion of NO
to NO2. Because the oxidation of methane is relatively slow, there
is a limited amount of HO2 produced, in addition to methyl radicals
reducing NO2 to NO via CH3 þ NO2 $ CH3O þ NO [24].
Ethanol reacts with OH radicals to make CH3CHOH and
CH3CH2O, which can be oxidized to produce HO2 in the follow-
ing reaction scheme:

CH3 CHOH þ O2 $ CH3 HCO þ HO2 (1)

Fig. 8 Brake specific NOx emissions as a function of FEF for CH3 HCO þ O $ CH3 CO þ OH (2)
160 and 180 proof hydrous ethanol
Reaction (1) forms HO2 radicals to promote NO to NO2 conver-
sion, while reaction (2) produces OH radicals to feed the ethanol
Single Zone Combustion Modeling. Our experimental results
consumption reaction. The model shows that ethanol has a high
indicate that NO to NO2 conversion increases with increasing
tendency to convert NO to NO2 at temperatures between 800 and
unburned ethanol in the exhaust. In previous research, Hori et al.
1200 K. This temperature range is greater than engine out exhaust
[24] used an adiabatic constant pressure single zone reactor model
temperatures; however, temperatures during the expansion stroke
and a constant temperature quartz flow experimental reactor to
would fall within this temperature range.
illustrate the mechanism by which hydrocarbons influence the NO
To more closely compare the model to experimental results, a
to NO2 conversion at different temperatures, with ethylene and
variable pressure single zone model was created. This model uses
propane being very effective as compared to methane and ethane.
the recorded in-cylinder pressure data versus time to model NO
However, work conducted by Hori et al. did not consider ethanol.
conversion kinetics occurring during the expansion stroke. The
A single zone constant pressure reactor model was created in
model assumes that the NO formation is complete and the burned
the open-source thermochemistry and kinetics code Cantera to
gases are mixed by the crank angle location of 90% gross heat
compare ethanol’s effectiveness with other hydrocarbons for con-
release (CA90). Therefore, CA90 was chosen as the initial
verting NO to NO2. The C1–C4 hydrocarbon with NO Addition

Fig. 9 NO2/NOx ratio as a function of unburned ethanol for all Fig. 10 NO2/NOx ratio as a function of reaction temperature for
modes and ethanol proofs selected HCs using a constant pressure reactor

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Fig. 11 Apparent RoHR, in-cylinder pressure, mean in-cylinder
temperature, and CA90 temperature range as a function of CAD
condition for the variable pressure model. The pressure data start-
ing at CA90 was used in conjunction with a range of initial local
in-cylinder temperatures and a sweep of unburned ethanol concen-
trations to predict NO to NO2 conversion. A range of temperatures
at CA90 was used because local in-cylinder temperatures were
unknown and can vary within the cylinder. The in-cylinder tem-
peratures were calculated using the polytropic relations for each
initial CA90 temperature and measured pressure data.
Figure 11 illustrates the conditions under which the model was
run. The symbols on the plot are for clarity between the trends
and are not indicative of actual data. The TCA90 surface represents
the isentropic temperature curve fits for initial temperatures from
1000 to 2000 K at 50 K increments. A larger lower range of tem-
peratures was chosen because the introduction of water is well
known to decrease in-cylinder temperatures. The mean in-
cylinder temperature curve starting at CA90 was calculated to
validate the TCA90 range used for the model. The initial exhaust
composition points were taken from a CDC mode (1400 rpm,
250 Nm), and a range of ethanol (500–4000 PPM) was added to
the mixture at the start of the model. Similar results were obtained
when running the model at different engine testing modes and
were not included for brevity.
The NO conversion trajectory as a function of crank angle for
two different CA90 temperatures is shown in Fig. 12. At lower
Fig. 12 NO conversion trajectory as a function of CAD starting
at CA90
Journal of Energy Resources Technology
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Fig. 13 NO2/NOX contour as a function of local in-cylinder
temperatures at CA90 and normalized unburned ethanol
concentrations
temperatures, NO is readily converted to NO2 early in the expan-
sion stroke, and then “freezes” when the temperature becomes too
low to promote conversion. At higher temperatures, NO has a sud-
den decrease followed by an increase before settling as in-
cylinder temperatures do not enter the right temperature range to
promote conversion. The decrease in NO at high temperatures is
caused by the oxidation of ethanol, while the increase right after
is because the reversion of NO2 to NO is more favored at high
temperatures. The model suggests that unburned ethanol will not
be evident in regions of high in-cylinder temperatures, preventing
the conversion of NO to NO2. Instead, unburned ethanol evident
in low local in-cylinder temperature regions will readily convert
NO to NO2.
Figure 13 shows the NO2/NOx ratio at the end of expansion,
plotted as a contour against the initial temperature at CA90 and
the ratio of unburned ethanol concentration normalized against
initial NOx concentration. A clear island can be seen for TCA90
between 1150 and 1250 K where unburned ethanol in the exhaust
promotes the conversion of NO to NO2. At local in-cylinder tem-
peratures greater than 1400 K, complete ethanol conversion is pre-
dicted, preventing the conversion. In addition, higher local
temperatures favor the reduction of NO2 to NO, while the con-
sumption of ethanol yields daughter radicals. Hori et al. have
shown that daughter radicals resistant to oxidation by O2 will
reduce NO2 to NO by the reaction R þ NO2 $ NO þ RO. In con-
trast, at local in-cylinder temperatures lower than 1150 K, limited
OH radicals reduce the production of HO2, slowing down the con-
version of NO to NO2. It is also important to note that this model
only takes into account the unburned ethanol in the expansion
stroke. As shown in Fig. 4, other unburned hydrocarbons such as
ethylene (C2H4) and methane (CH4) increase with increasing FEF,
promoting additional NO to NO2 conversion.
Conclusions
In this study, a comprehensive dataset was presented character-
izing an add-on dual fuel PFI system using hydrous ethanol as the
secondary fuel. Data were collected over a range of FEF for each
point along a modified ISO 8178 eight point testing plan. The
results show that 160 proof hydrous ethanol can achieve up to
61.8% FEF, while 180 proof reaches up to 60% FEF. CO, total
hydro carbons (THC), and unburned ethanol emissions all
increase with increasing FEF, while NOx emissions initially show
no change, but begin to decrease at high FEF where significant
charge cooling lowers the diesel combustion temperature. It was
also found that both 160 and 180 proof hydrous ethanol follow the
JULY 2017, Vol. 139 / 042206-7
 same emissions trends, with a significant difference between simi- PM ¼ particulate matter
lar FEF values. RCCI ¼ reactivity controlled compression ignition
Single-zone reactor models were created using Cantera to RoHR ¼ rate of heat release
investigate the conversion of NO to NO2 due to unburned hydro- SCR ¼ selective catalytic reduction
carbons in the exhaust. The first model found that different hydro- TDC ¼ top dead center
carbons have different propensities for promoting the NO to NO2 THC ¼ total hydro carbons
conversion, a finding in validation with work conducted by Hori ULSD ¼ ultralow sulfur diesel
et al. [24]. Results from this model indicated that unburned etha-
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