Environmental Pollution 310 (2022) 119866

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

On reducing the emissions of CO, HC, and NOx from gasoline blended with
hydrogen peroxide and ethanol: Optimization study aided with ANN-PSO☆
Augustine B.V. Barboza, Sooraj Mohan, P. Dinesha *
Department of Mechanical and Industrial Engineering, Manipal Institute of Technology, Manipal Academy of Higher Education, Manipal, 576104, India

A R T I C L E I N F O A B S T R A C T

Keywords: The use of ethanol blending for gasoline has been found to have a significant effect in reducing emissions without
CO any loss in the performance of a spark ignition engine. However, an increase in the emissions of oxides of ni­
Ethanol trogen (NOx) may be seen due to the increased oxygen content in the fuel. On the contrary, emulsifying fuel with
Emission reduction
hydrogen peroxide (H2O2) has shown a substantial effect in reducing all the emissions, including NOx in a
Hydrogen peroxide
NOx
compression ignition (CI) engine. In this study, 10% ethanol is blended with gasoline (E10) and further emul­
PSO sified with H2O2 up to 1.5%. When compared to neat gasoline, a 4.8% increase in brake thermal efficiency (BTE)
is obtained with 10% ethanol and 1.5% H2O2. The corresponding average decrease in the emissions of carbon
monoxide (CO), hydrocarbons (HC), and NOx were 80%, 43%, and 17%, respectively. The results of the
experimental trials are used to model an artificial neural network (ANN) to derive a relationship between the
input factors of ethanol concentration, H2O2 concentration, and engine speeds with the output responses of BTE,
CO, HC, and NOx. The ANN models of each response are optimized using a multi-objective particle swarm
optimization (PSO) for maximizing BTE and minimizing emissions of CO, HC, and NOx. The PSO results showed
that operating the engine at 2000 rpm using ethanol blending between 4 and 6% and H2O2 emulsification of
1.5% are the best optimal conditions.

style of the people. Increased usage of vehicles for personal trans­

1. Introduction
The rising population of the world has led to an increase in energy
demand which in turn contributes to environmental pollution. Clean
energy for a sustainable environment is important to address climate
change issues. Out of seventeen Sustainable Development Goals (SDGs)
adopted by United Nations in 2015, SDGs 7 and 13 describe affordable
and clean energy, and climate action, which are important for trans­
portation and industrial sectors (United Nations, 2020). Energy use in
the transportation sector was 104 quadrillion British thermal units (Btu)
in 2012, and it will extend to 155 quadrillion Btu in 2040. A report
published by Ministry of Petroleum & Natural Gas, Government of India
in 2014 mentions that vehicles consume 99.6% of gasoline and 70% of
diesel (Ministry of Petroleum & Natural Gas, 2014). Diesel consumption
in the industrial sector comprises only 9.02%. The transportation sector
consumes more fuel compared to the industrial and agricultural sectors.
In India, for the year 2021, gasoline-fueled cars accounted for 76% of
market share among the light-duty-vehicles despite increased gasoline
prices (Sun, 2021). This may be attributed to the more affluent living
portation increases the accumulation of toxic pollutants in the atmo­
sphere. Governing authorities impose stringent norms to regulate
vehicular emissions from time to time. These norms can be met with
vehicles using efficient and effective combustion systems. This is a
long-term challenge to automobile vehicle manufacturers to reduce
exhaust emissions without compromising engine performance (Society
of Indian Automobile Manufacturers, 2021). Several technologies are in
practice to reduce exhaust emissions with higher engine efficiency. The
use of alternative green fuels like biodiesel (S Simsek et al., 2022a) and
ethanol (Barboza et al., 2022) is one of the promising and effective
methods which can positively reduce emissions with improved perfor­
mance. In addition, many modeling and optimization studies like arti­
ficial neural networks (ANN) (Simsek et al., 2022c), response surface
methodology (RSM) (Kumar and Dinesha, 2018; Simsek and Uslu,
2020a), particle swarm optimization (PSO) (Dinesha et al., 2022),
Taguchi (Simsek et al., 2021a), etc. are reported in the literature to
improve the engine performance with reduced emissions.
The present alternatives to gasoline in a spark ignition (SI) engines
are alcohols (Göktaş et al., 2021), liquid petroleum gas (Simsek et al.,

☆
This paper has been recommended for acceptance by Prof. Pavlos Kassomenos.
* Corresponding author.
E-mail address: dinesha.p@manipal.edu (P. Dinesha).

https://doi.org/10.1016/j.envpol.2022.119866
Received 27 May 2022; Received in revised form 16 July 2022; Accepted 24 July 2022
Available online 6 August 2022
0269-7491/© 2022 Elsevier Ltd. All rights reserved.
A.B.V. Barboza et al.
Abbreviations
ANN Artificial Neural Networks
BSFC Brake specific fuel consumption
BTE Brake thermal efficiency
CI Compression Ignition
CO Carbon Monoxide
CO2 Carbon dioxide
EGT Exhaust gas temperature
H2O2 Hydrogen peroxide
HC Unburnt hydrocarbons
LCV Lower calorific value
NOx Oxides of Nitrogen
PSO Particle Swarm Optimization
SI Spark Ignition
SDG Sustainable Developmental Goals
2021b), ethers (Awad et al., 2018), and waste oils (Simsek and Uslu,
2020). Ethanol is being used in engines due to its SI engine fuel friendly
properties. Bioethanol is a green and renewable fuel produced from
plant sources such as grains, barley, sugar cane, sweet beet etc. Ethanol
produced from these crops is known as first generation ethanol (Tan
et al., 2020). Ethanol produced from lignocellulosic biomass is known as
second generation ethanol (Pabbathi et al., 2021). The third generation
ethanol is produced using microalgae (de Farias Silva and Bertucco,
2016). Microalgae can be cultivated in ocean or sea water and hence
there is no fertile land requirement compared to the first two genera­
tions of ethanol (Tan et al., 2020). The physico-chemical properties of
ethanol are comparable to gasoline and some properties, such as higher
octane number, and inbuilt oxygen content make it superior to gasoline.
Several studies reported the effects of ethanol on the performance and
emissions characteristics of SI engines at varying speeds and volume
concentrations (AlRamadan et al., 2021; Dinesha et al., 2022; Zhang and
Qi, 2021).
Ethanol has superior performance coupled with reduced emissions
when used in a blend with gasoline (Masum et al., 2013). However, it
cannot be used as an independent fuel due to its lower heating value.
Shaktivel et al. observed 75% and 66% lower carbon monoxide (CO) and
hydrocarbon (HC) emissions, respectively, for an E30 blend with rising
emissions of oxides of nitrogen (NOx) as compared to neat gasoline
(Sakthivel et al., 2019). According to Turner et al., substantial re­
ductions in carbon dioxide (CO2) were observed with an E85 blend
(Turner et al., 2013). Lower emissions with a marginal improvement in
SI engine performance was observed when gasoline was added with a
mixture of trioctyl borate, ammonia borane, and ethanol (S Simsek et al.,
2022b). Increasing the additive concentration beyond 0.5% deteriorated
the engine performance and emissions. The use of higher percentages of
ethanol has resulted in lower NOx, CO2, and HC emissions as compared
to neat gasoline, as reported by Mohammed et al. (2021). Celik reported
higher engine power to the tune of 29% and a 10% reduction in CO2 with
an E50 blend in comparison to neat gasoline (Celik, 2008). Higher
exhaust gas temperature (EGT) was observed with ethanol blends by
Bhadrawada and Susastriawan due to higher concentrations of oxygen
in ethanol fuel (Badrawada and Susastriawan, 2019). This has led to
superior engine performance due to higher combustion rates. From the
literature, it can be inferred that lower ethanol blends resulted in
reduced emissions and enhanced engine performance.
Hydrogen peroxide (H2O2), due to its antibacterial, disinfectant, and
antiviral properties, is extensively used in medical applications (Han
et al., 2019; Li et al., 2020). Apart from its medicinal properties, H2O2 is
also used as an oxidizing agent in rocket propulsion systems (Guang
et al., 2022). It is highly sensitive to decomposition and dissociation
processes, which are complex in nature. Decomposition is a slow process
2
Environmental Pollution 310 (2022) 119866
that results in the release of oxygen and water with the simultaneous
liberation of heat. Dissociation leads to the formation of hydroxyl and
hydroperoxyl radicals. These two features favor H2O2 as an ideal addi­
tive in combustion applications. Higher thermal conductivity and spe­
cific heat were observed when H2O2 was used in a fuel blend, leading to
improved combustion of the fuel. The atomization and vaporization
features of the fuel showed an improvement due to micro-explosions of
H2O2 and this was further enhanced with H2O2 concentration (Yeom,
2017; Yoon and Yeom, 2018).
The use of H2O2 as a fuel additive in compression ignition (CI) en­
gines has been demonstrated by several researchers. The present authors
have previously reported that use of H2O2 up to 1.5% (v/v) has resulted
in improved performance and reduced emissions including NOx (Mohan
and Dinesha, 2022a). The performance and emissions were further
improved with the addition of Multiwalled Carbon Nanotubes (Mohan
et al., 2022) and CeO2 nanoparticles (Mohan and Dinesha, 2022b) to the
H2O2 emulsified fuel blends. H2O2 also increases the heat release rate as
the volume concentration increases. Nguyen et al. observed a higher
heat release rate for jatropha biodiesel- H2O2 emulsified blends (Nguyen
et al., 2014). They also reported lower CO and NOx emissions for the
same fuel blends. Similar results have been reported by Sanjeevannavar
et al. for a B30 biodiesel with 10% H2O2 (Sanjeevannavar et al., 2022).
The authors compared the test results with a non-emulsified B40 bio­
diesel. Tingas simulated the effect of H2O2 addition to premixed H2/air
flames and showed an increase in the laminar flame speed with the
addition of H2O2 (Tingas, 2021). Saleh et al. investigated the influence
of H2O2 on a CI engine and assessed the engine performance and exhaust
emission characteristics (Saleh, 2021). The authors prepared biodiesel
from different vegetable oils and emulsified it with H2O2 at 5–20% v/v
concentrations. H2O2 at 5% concentrations has led to minimum change
in brake specific fuel consumption (BSFC) coupled with reduced
emissions.
The literature review on the use of H2O2 on CI engine combustion
and emission characteristics has reported that H2O2 has a positive
impact on fuel combustion and leads to improved engine efficiency with
reduced emissions. There is limited literature available on the use of
H2O2 with biodiesel blends in a CI engine. However, the literature
available relating to the application of H2O2 in SI engine is very limited
and the study of the combined effect of ethanol and H2O2 has not been
reported. In the current study, an effort has been made to investigate the
combined effect of ethanol and H2O2 on the performance and emissions
characteristics of a SI engine.
2. Materials and methods
2.1. Preparation of fuel blends and properties
Hydrogen peroxide (30% Assay) and anhydrous ethanol (99.9%)
used in the study were purchased from a local supplier. This engine
study was conducted by using eight fuel variants, as depicted in
Table S1. The neat gasoline operation is considered as baseline study and
the results of other fuel variants are compared to the baseline results.
The ethanol composition in the fuel blends was limited to 10% (v/v) and
the composition of hydrogen peroxide was varied in proportions of
0.5%, 1%, and 1.5%, respectively. The gasoline along with specific
concentrations of ethanol and H2O2 were mixed in a closed container
and stirred in a magnetic stirrer for 1 h. After ensuring stabilization and
no separation of phase, the blend was transferred to the engine fuel tank.
To avoid complications of vapor lock and drop in injection pressure, the
H2O2 proportion was restricted to 1.5% (Mohan and Dinesha, 2022a,
2022b). The physico-chemical properties of individual fuels are shown
in Table S2.
2.2. Experimental setup
The experiments were performed on a Maruti Suzuki make four
A.B.V. Barboza et al.
Fig. 1. (a) BTE (b) CO emissions (c) HC emissions (d) NOx emissions for varying fuel blends and engine speeds in this work.
stroke three-cylinder MPFI engine having a rated brake power of 15 kW.
Fig. S1 illustrates the schematic of the experimental test rig, and speci­
fication details are shown in Table S3. The engine is equipped with a
water-cooling arrangement and a hydraulic dynamometer for loading.
The load was uniformly maintained at 9 kg throughout the experimen­
tation. The speed was varied in steps of 500 rpm from the baseline value
of 1500 rpm–3000 rpm. The experiments were carried out with the
factory set spark timing for all the trails. A constant equivalent ratio of
1.1 was maintained throughout the study. These features aid in
improving the functioning of the engine and maintaining emissions at a
lower level (Heywood, 2018; Li et al., 2017).
After conducting the experiments with neat gasoline to investigate
baseline results, the experiments were conducted for seven different fuel
variants to assess performance and emissions. The tailpipe emissions
such as CO, NOx, HC, and CO2 were recorded using an AVL 444 DI gas
analyzer. Prior to recording the readings, the steady state condition of
the engine is attained by noting the exhaust gas temperature. Table S4
shows the uncertainty values for the recorded parameters. The analysis
was carried out in a relative manner for all the fuel variants regarding
emissions and performance. The uncertainties of the dependent pa­
rameters such as brake thermal efficiency (BTE) and BSFC were ascer­
tained using the result perturbation method (Holman, 2011).
2.3. ANN-PSO modeling
The experimental trials for the present study were carried out for
neat gasoline and E10 fuel blends with the emulsification of H2O2
varying from 0.5% to 1.5%. Each trial is carried out three times for
consistency in the data. Three variables were thus used in the study –
concentration of ethanol (0 and 10%), concentration of H2O2 (0–1.5%)
and engine speed (1500–3000 rpm). A total set of 32 trials are carried
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Environmental Pollution 310 (2022) 119866
out which is repeated two more times to get a total of three replicates (96
trials). The data on BTE, BSFC, EGT, emissions of CO, CO2, HC, and NOx
were recorded. Artificial neural networks (ANN) is used in this work to
derive relationship between input variables with output responses. For
the ANN model, one input layer with three nodes (ethanol concentra­
tion, H2O2 concentration, and engine speed), one hidden layer with 10
nodes, and one output layer with four nodes (BTE, emissions of CO, HC,
and NOx) are used. 70% of the trials are used for training, 15% for
validation, and 15% for testing the ANN model. The model is trained
using the Levenberg-Marquardt (L-M) algorithm. The model is retrained
until the regression coefficients for training, testing, and validation are
more than 0.90, and the mean square error (MSE) is less than 1e-3. Once
an acceptable model is obtained, the ANN biases and weights are
extracted, and equations for the outputs are established using the
transfer function (tan sigmoid). The transfer function serves as the
objective function for optimization modeling. In this work, optimization
of the output responses was carried out using PSO, which is a meta­
heuristic algorithm. The equations for BTE, emissions of CO, HC, and
NOx act as the objective functions. Here, the BTE is desired to be a
maximum while all the other emissions are required to be minimized.
The optimal set of results are plotted using Pareto plots which shows the
set of optimal operating conditions. The working of PSO optimization
models are discussed in detail by the authors in previously published
articles (Mohan et al., 2021b, 2021a). For the algorithm, a large swarm
size of 200 is used to avoid any false local minima. An inertia weight of
0.5 was used, and a value of 2.0 was assigned for both the cognitive and
social components in the algorithm. The solution iteration was stopped
when the total number of generations reached 30. The PSO analysis was
carried out using MATLAB software R2015a.
A.B.V. Barboza et al.
3. Results and discussion
3.1. Engine performance
BTE indicates the extent of conversion of energy in the fuel to me­
chanical work. Fig. 1 (a) and Fig. S2 shows the plots of BTE and BSFC,
respectively, at varying engine speeds and different fuel blends. For all
the fuel blends, the highest BTE and the lowest BSFC is recorded at an
engine speed of 2000 rpm, except for the gasoline fuel for which the
optimal performance was obtained at 2500 rpm. Increasing the con­
centration of H2O2 increases the BTE and decreases BSFC for all the fuel
blends. Compared to the gasoline blends, E10 blends show better per­
formance. The highest BTE (27.4%) and the lowest BSFC (0.317 kg/
kWh) is seen for E10+H1.5 at 2000 rpm wherein an improvement of
17.6% and 15.9% respectively, is obtained compared to gasoline fuel.
The performance of E10 blends is higher than gasoline blends for all the
concentrations of H2O2. The average increase (%) in BTE for E10 blends
is 6.5% compared to gasoline blends and the average decrease in the
BSFC is 2.7%. When compared to neat gasoline, a 4.8% increase in the
BTE is obtained with E10+H1.5. Ethanol blending with gasoline in­
creases the oxygen content and since H2O2 is an active carrier of oxidant
with •OH radicals, the air to fuel ratio comes to near stoichiometric
condition. This results in improved combustion and increasing the en­
ergy conversion. The enhancement in the combustion is also aided by
the better mixing of fuel and air as H2O2 induces micro explosions of fuel
droplets and better atomization. While ethanol increases the octane
number and latent heat, H2O2 increases the specific heat of the fuel
blend. Ethanol also has higher flame propagation speed, leading to
smaller combustion duration and broadening the flammability limit.
Since the combustion duration is smaller, lesser fuel is burnt leading to
better BTE and lower BSFC.
3.2. Emissions
3.2.1. Emissions of carbon monoxide and carbon dioxide
The emissions of CO and CO2 for varying fuel blends and engine
speeds is shown in Fig. 1 (b) and Fig. S3, respectively. The presence of
CO indicates poor combustion in the engine cylinder, which is a product
of incomplete combustion. As the CO further oxidizes, a decrease in the
CO should coincide with an increase in the emissions of CO2, which is
observed in Fig. S3. Ethanol blended fuels showed a substantial decrease
in the emissions of CO. The lowest CO of 0.9 %vol. is reported at 2000
rpm for the fuel blend E10+H1.5 containing 1.5% H2O2, which is 55.2%
lower than the gasoline blend (2.01 %vol.). The average CO emissions
for all the gasoline blends is 2.33 %vol. while the E10 blends returned
with 1.66 %vol. The increase in the concentration of H2O2 decreases the
CO emissions for both gasoline and E10 blends indicating that both E10
and H2O2 in combination influence the improvement in combustion
quality. Consistent with the CO emission reduction, the CO2 emissions
also show a gradual increase with increasing H2O2 concentration. The
average CO2 emissions for the E10 blends (12.53 %vol.) is 2.6% higher
than the gasoline blends (12.21 %vol.). The addition of ethanol and
H2O2 in the fuel blends provides ample amount of oxidant, which assists
in complete burning of the fuel and oxidizing CO to CO2. The peroxide
content in the fuel acts as an excellent oxidant carrier (Plauck et al.,
2016) with an increase in the •OH radicals (Zhou et al., 2019) in the fuel
blend when emulsified with H2O2. In addition, the lower viscosity of
H2O2 leads to micro explosions (Yoon and Yeom, 2018) and better at­
omization leading to a better mix of the injected fuel and combustion air.
The additional oxidant content tends to widen the lean burn limit
leading to better combustion, thereby reducing the emissions of CO and
converting it into CO2.
3.2.2. Hydrocarbon emissions
Fig. 1 (c) shows the hydrocarbon emissions reported in this study. A
decrease in the HC emissions is observed due to the influence of both
4
Environmental Pollution 310 (2022) 119866
ethanol and H2O2 concentrations. Similar to CO emissions, the HC
emissions are lower for the E10 blends compared to gasoline blends. The
highest HC is seen at 1500 rpm for gasoline fuel (485 ppm) and the
lowest HC is recorded at 2500 rpm for E10+H1.5 blend (198 ppm). The
average decrease in the HC emissions for E10 blends compared to gas­
oline blends is 10.3%. In contrast, the average decrease in the HC
emissions is 27.5% when 1.5% H2O2 is emulsified with the fuels. The
reduction in the HC emissions is attributed to the promotion of better
combustion in the presence of H2O2 and additional oxygen from ethanol
in the fuel blends. H2O2 is an oxidant carrier that releases both the O2
and •OH radicals when decomposed. The higher content of •OH radicals
results in better oxidation of hydrocarbons which leads to lower emis­
sions of HC. In addition, ethanol improves the octane number of the fuel
blend, and at higher engine speeds and concentrations of H2O2, the
availability of •OH radicals also promotes better combustion of the
unburnt hydrocarbons.
3.2.3. Exhaust gas temperature
Fig. S4 shows the exhaust gas temperature of the engine for different
fuel blends and engine speeds. Increasing the speed increases the EGT
due to higher fuel flow into the cylinder leading to more combustion and
increased temperatures. The highest and the lowest EGT is seen for E10
at 3000 rpm (515 ◦ C) and G + H1.5 at 1500 rpm (280 ◦ C), respectively.
Compared to the gasoline blends, E10 blends show an increase in the
EGT. A 3% average increase in the EGT is seen for E10 blends compared
to the gasoline blends. The emulsification of H2O2 to the fuel blends led
to a decrease in the EGT for both the gasoline and E10 blends. The
average decrease in EGT with an emulsification concentration of 1.5%
for gasoline blends and E10 blends were 8.9% and 7.3%, respectively.
The average decrease in EGT for E10 blends is lesser because E10 con­
tributes to an increase in EGT. The additional oxygen present due to
ethanol blending and H2O2 emulsification, rises the temperature of
combustion due to the complete combustion of CO and unburnt HC.
However, a decrease in the EGT is seen due to the absorption of latent
heat by H2O2. Ethanol also has a higher latent heat which not only re­
duces the in-cylinder temperature but also improves volumetric
efficiency.
3.2.4. Emissions of oxides of nitrogen (NOx)
The emissions of NOx are formed inside the engine cylinder mainly
due to the increase in combustion and flame temperature, availability of
oxygen near the reaction zone and residence time of nitrogen. Different
pathways of NOx formation are presented in the literature (Yilmaz and
Atmanli, 2017). The gases are usually formed due to three pathways –
thermal NOx, fuel NOx, and prompt NOx (Atmanli and Yilmaz, 2020).
The nitrogen present in combustion air is responsible for the thermal
NOx formation at higher temperature, the nitrogen from the fuel pro­
motes the formation of fuel NOx at low temperature, and prompt NOx are
formed at the flame front when atmospheric nitrogen reacts with the
combustion radicals (Bazooyar et al., 2016). The additional fuel bound
oxygen in biodiesels usually contributes for a cleaner combustion of HC
and CO leading to a rise in cylinder temperature. Hence NOx is usually
formed via thermal NOx with the additional availability of fuel bound
oxygen. The largest contribution to NOx is thermal formation as repre­
sented in the literature using Zeldovich model (Yilmaz and Atmanli,
2017). The emissions of NOx in the present study are shown in Fig. 1 (d).
The trend of NOx emissions follows that of the EGT, as seen in Fig. S4. An
overall decreasing trend in the NOx emissions is seen mainly because of
H2O2. The average NOx for gasoline blends is 1389 ppm compared to
1437 ppm for E10 blends. Ethanol composition in the blends have raised
the emissions of NOx due to the additional oxygen contribution from the
ethanol. Increasing the engine speed increases the emissions of NOx. The
lowest NOx is seen for G + H1.5 at 1500 rpm (580 ppm) and the highest
value of NOx is obtained for E10 at 2000 rpm (1658 ppm). An overall
average increase of 7.39% in NOx is seen if gasoline is replaced with E10.
However, the emulsification of H2O2 up to 1.5% results in an average
A.B.V. Barboza et al.
Fig. 2. Contour plot of (a) BTE (b) CO emissions (c) HC emissions (d) NOx emissions at 2000 rpm.
decrease of 22.5% in the emissions of NOx irrespective of the baseline
fuel used. Therefore, an overall decrease in the NOx emissions is recor­
ded. For the gasoline fuel, BSFC is higher leading to higher cylinder
temperature and formation of NOx. For the ethanol and H2O2 blended
fuels, the latent heat of ethanol and H2O2 results in the reduction of
in-cylinder temperature and exhaust gas temperature that suppresses
NOx formation.
3.3. Comparison of H2O2 emulsification with ethanol concentration on
the performance and emissions
The reduction in the emissions and improvement in the engine per­
formance is seen due to both the effect of ethanol and H2O2 concen­
trations. To ascertain the combined influence, relationships between the
output responses and the input factors were developed at using an ANN
fitting model. The built model returned an R2 value of more than 0.95
for all the responses. The developed model was then used to generate a
matrix of 30,351 responses by varying the concentrations of ethanol and
H2O2 in steps of 0.05% and 0.01%, respectively. The speed was kept
constant at 2000 rpm as the highest BTE is obtained at this level. The
resulting matrix data was used to generate 2D contour plots. Fig. 2 (a)
shows the contour plot of BTE at 2000 rpm. The highest BTE is obtained
for H2O2 concentration >1% and ethanol concentration between 0 and
4%. Since both the ethanol and H2O2 provides adequate oxidant, the air
to fuel ratio is near to stoichiometric and promotes complete combustion
and energy conversion. The graph clearly indicates the increase in BTE
as the increase in H2O2 concentration in the blend increases. Whereas
the BTE increases to a maximum when the ethanol concentration is
between 2 and 4%, and further increases in the concentration reduce the
BTE. At higher blend compositions of ethanol beyond 6%, the H/C ratio
increases and the heating value of the blend decreases, resulting in lower
5
Environmental Pollution 310 (2022) 119866
energy output and hence lower BTE.
Fig. 2 (b) shows the contour plot of emissions of CO at 2000 rpm. It is
clearly seen that both the concentrations of ethanol and H2O2 influence
the lowering of CO emissions. From the figure for the baseline gasoline
blend, the CO emissions are the highest while the lowest emissions are
obtained for fuel blend with 1.5% H2O2 and ethanol concentration be­
tween 6 and 10%. Increasing the H2O2 concentration and ethanol
blending to gasoline increases the oxidant content and H/C ratio. With
the additional oxidant available, CO emissions are further oxidized to
CO2. The introduction of H2O2 in the fuel decreases the HC emissions as
seen from the contour plot depicted in Fig. 2 (c). A relatively lower
emission reduction is observed when the concentration of ethanol in­
creases in the fuel blends. From the contour plot, the fuel having 1.5%
H2O2 and ethanol concentration between 3 and 7% can yield the lowest
HC emissions. Better combustion of the fuel is promoted due to the
additional oxygen and •OH radicals present in the fuel due to ethanol
and H2O2 blending respectively.
Fig. S5 and Fig. 2 (d) shows the contour plots of EGT and emissions of
NOx respectively. The lowest EGT at 2000 rpm is recorded for H2O2
between 0.5 and 1.5%. Similarly, the lowest NOx is obtained when the
H2O2 in the fuel blend is between 0.75% and 1.25%. Highest EGT is
observed when ethanol is 10% in the fuel blend for which the NOx
emissions is also the highest. Increasing the concentration of ethanol up
to 5% in the fuel decreases the overall NOx and further increasing the
concentration, increases the NOx emissions. Higher concentration of
ethanol results in higher amount of oxygen in the fuel blend leading to
formation of NOx. Similarly blends without ethanol also yields higher
NOx emissions which may be due to higher residence time in the cyl­
inder increasing the duration of combustion resulting in the formation of
NOx emissions. This shows that the concentration of ethanol in
conjunction with H2O2 has specific range of operation within which
A.B.V. Barboza et al. Environmental Pollution 310 (2022) 119866

concentration is reduced. A parameter called composite desirability (DC )

is estimated by considering the desirability of individual response. The
values of individual desirability range from 0 to 100% wherein 100%
indicates a perfect optimal response. The highest value of BTE and the
lowest values of CO, HC, and NOx emissions are considered as optimal
values. For example, the lowest value of CO emission is 0.9 %vol.
(E10+H1.5 blend). The desirability of the values obtained from the PSO
results are calculated against the CO emission at E10+H1.5. At BTE of
24% and 27.7%, the PSO optimal values for CO is 1.05 and 2.7% vol.
respectively. This corresponds to an individual desirability of 94% and
27.7% respectively. Likewise, individual desirability for each parameter
is calculated. Each response is given equal priority to be optimized and
the composite desirability is then calculated by taking the geometric
mean of values of individual desirability as shown in Equation (1).

(1)
1
DC = (D1 × D2 × … × Dn )n
In the equation, n represents the total number of objective functions,
Fig. 3. Pareto plot for BTE (maximized) against the emissions of CO, HC, and DC is the composite desirability of an optimized condition, and D1 , D2 ,
NOx (minimized) obtained from PSO. …, Dn are the values of individual desirability of an output response for
the optimized condition. In the present study, the individual desirability
optimal performance and emission parameters are obtained. of BTE, CO, HC, and NOx are calculated, and composite desirability is
estimated as shown in Table 1. The values of DC increases from 81% to
89.5% if the optimized BTE is increased from 24% to 26%. DC signifi­
3.4. PSO optimization
cantly reduces to 51% at 27.7% BTE as the value of NOx is very high
which has an individual desirability <27%. From the Table, it can be
The contour plots at 2000 rpm as discussed in section 3.3 shows that
inferred that by operating the engine at around 2000 rpm and blending
there are different range of concentrations at which desired output of
gasoline with 1.5% H2O2 and 4–6% ethanol, the highest composite
higher BTE and lower emissions are obtained. To optimize the operating
desirability of 89.5% can be achievable that satisfies all the responses.
conditions, Multi-Objective Particle Swarm Optimization is used in this
work. The different objective functions are BTE (to maximize) and the
4. Conclusions
emissions of CO, HC, and NOx (to minimize). The objective functions are
obtained from the regression equations derived from ANN. All the
In this work, the combined effect of ethanol and hydrogen peroxide
equations derived using the regression weights were checked and vali­
(H2O2) in gasoline fuel is assessed on the performance and emissions of a
dated to ensure the coefficient of determination more than 0.95. All the
spark ignition engine. The emulsification of 1.5% H2O2 along with 10%
equations are simultaneously optimized to get a composite desirability.
ethanol increases the Brake Thermal Efficiency (BTE) up to 21.4% and
The optimized solution set is plotted as a Pareto plot as shown in Fig. 3.
returns with an average reduction of 21%, 28%, and 25% in the emis­
Since only BTE was required to be maximized, it is placed in the abscissa.
sions of CO, HC, and NOx respectively. The contour plots clearly indicate
The optimized solutions for CO and NOx emissions seem to show an
an optimal range for ethanol concentration and further optimizing using
increasing trend if the BTE requirement is maximum. On the contrary,
ANN-PSO model showed that the highest composite desirability of
the optimized emission of HC decreases with the optimized BTE values.
89.5% can be achieved by operating the engine at 2000 rpm using
The emissions find a minimum near 25% BTE beyond which the values
ethanol blending between 4 and 6% and H2O2 emulsification of 1.5%.
further increase. Table 1 shows the optimal operating conditions at
These outcomes could complement the phase-wise blending of gasoline
different range of values of BTE. The concentration of ethanol varies
with ethanol promoted by many governments across the globe. How­
from 3.7% to 6% and increasing the concentration reduces the optimal
ever, the issues of vapor lock in the pump beyond the concentration of
BTE. The emissions of CO and NOx decreases with the increase in the
1.5% of H2O2 reported in this work necessitates adequate studies to
ethanol content. For increasing the BTE with minimal emissions, the
ascertain the suitability of emulsifying gasoline or E10 blends with
engine speed is required to be increased. The maximum BTE of 27.7% is
H2O2.
achievable for an engine speed of 2349 rpm at which the emissions of
CO, HC, and NOx are 2.7 %vol., 220 ppm, and 1976 ppm respectively.
CRediT author statement
From Table 1, it is also seen that at lower optimized values of BTE, the
concentration of H2O2 remains constant at 1.5%. For BTE values more
Augustine B. V. Barboza: Conceptualization, Data curation, Inves­
than 26%, the optimal H2O2 concentration drops down to 0.5%. From
tigation. Sooraj Mohan: Formal Analysis, Software, Writing-original
Figs. 1 (a) and Fig. 2 (a), it is seen that BTE of more than 27% is obtained
draft. P. Dinesha: Conceptualization, Supervision, Writing-review &
at 1.5% concentration. But after implementing PSO optimization, the
editing.
concentration of H2O2 reduces to 0.5% mainly to minimize the emis­
sions of CO, HC, and NOx. At 1.5% concentration, an increase in the
emissions of NOx is observed. To minimize this effect, the optimal H2O2

Table 1
Composite desirability and optimized set of values for different BTE.
BTE (%) Ethanol (%) H2O2 (%) Speed (rpm) CO (% vol.) HC (ppm) NOx (ppm) Composite Desirability (%)

24 6 1.5 1788 1.05 239 387 81.2

25 6.2 1.5 1969 1.27 220 321 85.3
26 5.7 1.5 2066 1.35 207 552 89.5
27 3.9 0.8 2116 1.90 200 826 83.6
27.7 3.7 0.5 2349 2.70 220 1976 51.2

6
A.B.V. Barboza et al. Environmental Pollution 310 (2022) 119866

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The authors declare that they have no known competing financial Mohan, S., Dinesha, P., 2022b. Performance and emissions of biodiesel engine with
interests or personal relationships that could have appeared to influence hydrogen peroxide emulsification and cerium oxide (CeO2) nanoparticle additives.
the work reported in this paper. Fuel 319, 123872. https://doi.org/10.1016/j.fuel.2022.123872.
Mohan, S., Dinesha, P., Aiswarya, V., 2022. Synergetic influence of hydrogen peroxide
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Mohan, S., Dinesha, P., Bekal, S., 2021a. NOx reduction of biodiesel engine using
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