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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
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. 6 Soot concentration as a function of FEF for 160 and 180 Fig. 7 Brake specific NO emissions as a function of FEF for
proof hydrous ethanol 160 and 180 proof hydrous ethanol
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
condition for the variable pressure model. The pressure data start-
ing at CA90 was used in conjunction with a range of initial local temperatures, NO is readily converted to NO2 early in the expan-
in-cylinder temperatures and a sweep of unburned ethanol concen- sion stroke, and then “freezes” when the temperature becomes too
trations to predict NO to NO2 conversion. A range of temperatures low to promote conversion. At higher temperatures, NO has a sud-
at CA90 was used because local in-cylinder temperatures were den decrease followed by an increase before settling as in-
unknown and can vary within the cylinder. The in-cylinder tem- cylinder temperatures do not enter the right temperature range to
peratures were calculated using the polytropic relations for each promote conversion. The decrease in NO at high temperatures is
initial CA90 temperature and measured pressure data. caused by the oxidation of ethanol, while the increase right after
Figure 11 illustrates the conditions under which the model was is because the reversion of NO2 to NO is more favored at high
run. The symbols on the plot are for clarity between the trends temperatures. The model suggests that unburned ethanol will not
and are not indicative of actual data. The TCA90 surface represents be evident in regions of high in-cylinder temperatures, preventing
the isentropic temperature curve fits for initial temperatures from the conversion of NO to NO2. Instead, unburned ethanol evident
1000 to 2000 K at 50 K increments. A larger lower range of tem- in low local in-cylinder temperature regions will readily convert
peratures was chosen because the introduction of water is well NO to NO2.
known to decrease in-cylinder temperatures. The mean in- Figure 13 shows the NO2/NOx ratio at the end of expansion,
cylinder temperature curve starting at CA90 was calculated to plotted as a contour against the initial temperature at CA90 and
validate the TCA90 range used for the model. The initial exhaust the ratio of unburned ethanol concentration normalized against
composition points were taken from a CDC mode (1400 rpm, initial NOx concentration. A clear island can be seen for TCA90
250 Nm), and a range of ethanol (500–4000 PPM) was added to between 1150 and 1250 K where unburned ethanol in the exhaust
the mixture at the start of the model. Similar results were obtained promotes the conversion of NO to NO2. At local in-cylinder tem-
when running the model at different engine testing modes and peratures greater than 1400 K, complete ethanol conversion is pre-
were not included for brevity. dicted, preventing the conversion. In addition, higher local
The NO conversion trajectory as a function of crank angle for temperatures favor the reduction of NO2 to NO, while the con-
two different CA90 temperatures is shown in Fig. 12. At lower 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
Fig. 12 NO conversion trajectory as a function of CAD starting charge cooling lowers the diesel combustion temperature. It was
at CA90 also found that both 160 and 180 proof hydrous ethanol follow the