Journal of Hazardous Materials 462 (2024) 132685

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Research Paper

Performance evaluation of PM, NOx, and hydrocarbon removal in diesel

engine exhaust by surface discharge-induced plasma
Kohei Kawakami a, Ken Watatani b, Haruhiko Yamasaki a, b, Tomoyuki Kuroki a, b,
Masaaki Okubo a, b, *
a
Department of Mechanical Engineering, Osaka Metropolitan University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Japan
b
Department of Mechanical Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Japan

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• NOx, PM, and HC in exhaust are treated

simultaneously by surface discharge
plasma. Diesel engine
• Removal efficiencies of 70% for NOx,
98% for PM, and 67% for HC are NO, PM, hydrocarbon
achieved. exhaust
• NOx could be reduced by reacting with
HC and CO in the exhaust gas.
• Proposed exhaust gas treatment exhibits
2NO+2CO→N2+2CO2
Surface
higher removal at a lower specific discharge
energy. 4NO+2HC→2N2+2CO2+H2
• A total pollution control system can be plasma
realized using a scrubber and catalyst. NO: 70%
PM: 98%
hydrocarbon: 67%
simultaneous reduction

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

Editor: Zaher Hashisho Diesel engines are characterized by low CO2 emissions and high fuel efficiency. However, their exhausts contain
nitrogen oxides (NOx), particulate matter (PM), and hydrocarbons (HC) that require removal by aftertreatment.
Keywords: A novel low-temperature plasma-based aftertreatment method has been developed for the simultaneous removal
Diesel engine of NOx, PM, and HC. NOx could be reduced by reacting with HC and CO in the exhaust gas. The particle and gas
Surface discharge plasma
concentrations in the exhaust are measured using a scanning mobility particle sizer, a NOx analyzer, and a total
NOx
hydrocarbon analyzer. The treatment performance is evaluated using the resulting measurements. The diesel
PM
Hydrocarbon engine is operated under 0%, 25%, 50%, and 75% loads (maximum output of 2 kW), and the exhaust gas is mixed
with N2 + O2 (13%) gas. The power is adjusted to provide 100, 200, 300, and 400 W input power during the
plasma reactor treatment. The aftertreatment removal of NOx, PM, and HC is evaluated, and the engine exhibits a
removal efficiency of 70% for NOx, 98% for PM, and 67% for HC at 75% engine load and an input power of 100
W.

* Corresponding author at: Department of Mechanical Engineering, Osaka Metropolitan University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Japan.
E-mail address: mokubo@mokubo.com (M. Okubo).

https://doi.org/10.1016/j.jhazmat.2023.132685
Received 15 July 2023; Received in revised form 23 September 2023; Accepted 30 September 2023
Available online 4 October 2023
0304-3894/© 2023 Elsevier B.V. All rights reserved.
K. Kawakami et al. Journal of Hazardous Materials 462 (2024) 132685

1. Introduction waste management issues. The paper [44] evaluates the performance of
waste foundry sand and bauxite residue in reducing NOx emissions from
Diesel engines have long been favored in several segments of the diesel exhaust. The paper [45] introduces a novel system, employing
vehicle industry. One of the core reasons for their popularity is their cascaded plasma-ozone injections, to decrease total hydrocarbon emis­
inherent capability to produce lower CO2 emissions compared to their sions from diesel exhaust. The results were promising and activating
gasoline counterparts. Another compelling feature of diesel engines is inexpensive adsorbents and catalysts with plasma opens the way to
their superior fuel efficiency, allowing them to move longer distances on various industrial applications for environmental cleaning.
a single fuel tank. These advantages make diesel engines a sustainable In a previous study [46], a plasma reactor and high-frequency,
choice for long-haul transport and heavy-duty vehicles. Although every high-voltage power supply, which were the components of a plasma
technology has its challenges, a significant concern is the exhaust gas for aftertreatment system, were installed to conduct new tests with the aim
diesel engines. The exhaust from these engines consists of a mix of ni­ of applying it practically as a PM aftertreatment technology to meet
trogen oxides (NOx), particulate matter (PM), and hydrocarbons (HC). future emission regulations. Evidently, PM oxidation removal by surface
These components, especially NOx and PM, are harmful to both the discharge plasma was confirmed, thus indicating the possibility of the
environment and human health. To curb these emissions, the intro­ simultaneous removal of PM and NOx [27,28,46,47].
duction of aftertreatment technologies becomes indispensable [1–15]. In this study, we treat a plasma filtration technique aimed at
The industry has relied on a few established aftertreatment methods. extracting particulate matter (PM) while it is airborne, achieved by
One of the most commonly employed is the selective catalytic reduction directly subjecting PM-laden gas to plasma. Within this approach, PM
(SCR). Several studies on SCR [13–15] should be explained. The article gets eliminated through chemical reactions and the particle-collecting
[13] predicted the efficiency of the SCR system through modeling. The influences inherent to plasma. This is realized by guiding PM-
article [14] analyzed the treatment of NOx, HC, CO, and other pollutants containing gas through a cylindrical plasma reactor housing surface
in the SCR system in detail through experiments. The article [15] discharge electrodes. Because minimal pressure is lost and performance
identified the issue of urea crystallization in the SCR system. SCR works degradation over extended operation periods is negligible, the process
efficiently in reducing NOx emissions. However, it is not without its remains efficient and uninterrupted, obviating the need for filter reju­
challenges. For SCR to function effectively, a urea water solution is venation or cleansing. Additionally, the reactor exhibits the capability to
needed, necessitating a separate storage tank. Over time, the SCR eliminate nitrogen oxides (NOx = NO + NO2), odors, and gases con­
catalyst degrades and must be replaced periodically. Another limitation taining volatile organic compounds (VOCs). The primary aim of this
is the inability of HC and NOx trap catalysts to be used with heavy oils, current investigation is to explore a plasma system capable of accom­
limiting their application in certain conditions. modating substantial filtration volumes, enhancing the enduring pres­
Beyond the challenge posed by NOx, the removal of particulate ence of radicals, and amplifying the overall decomposition efficiency of
matter (PM), such as PM2.5, is a significant concern, particularly in the the system. Furthermore, to evaluate the treatment performance, the
East Asian region. Upon inhalation, it gets lodged in the lungs and particle and gas concentrations (NO, NOx, CO, CO2, O2, HC, HNO3, and
detrimentally impacts human well-being. Consequently, there has been O3) are measured. Additionally, to compare reactor performance at
global attention directed towards its mitigation. Indoor air cleaners these loads, experiments are conducted with engine loads of 0%, 25%,
containing electrostatic precipitators and high-efficiency particulate air 50%, and 75%. In summary, as the vehicle industry progresses, the
(HEPA) filters prove efficacious in eliminating airborne PM. Employing imperative to find efficient, cost-effective, and sustainable aftertreat­
these air purifiers indoors can lead to a substantial reduction in PM ment solutions grows. While traditional methods like SCR and DPF have
levels [2,3]. Diesel particulate filters (DPF) have emerged as a leading their place, innovations like low-temperature plasma offer a glimpse
solution in this domain. These filters are integrated into most modern into a cleaner future for diesel engines.
diesel automobiles, ensuring they meet stringent annual emissions reg­
ulations [16–18]. However, again, DPFs are not free from complications. 2. Experimental setup and methods
As they trap particulates, they need regular maintenance. Over time, PM
accumulates, leading to a high-pressure drop and clogging of the filter. 2.1. Experimental setup
Thus, passive regeneration, which is done continuously, and active
regeneration, which is periodic high-temperature burn-off, are essential Fig. 1(a) shows a schematic of the experimental setup for the diesel
to maintain the DPF’s efficiency [19–25]. The passive regeneration is engine exhaust treatment system using a surface discharge plasma
made with catalysts while active regeneration is made with electric reactor. The experimental apparatus consists of a diesel engine
heaters or afterburners. (KDE2.0E, Wuxi Kipor Power Co., Ltd.) exhaust flow path and dilution
In the development of the automobile industry, hybrid-powered cylinder flow path, which are mixed and diluted before entering the
vehicles, which combine the power of traditional combustion engines plasma reactor to treat the NOx, PM, and HC in the exhaust gas. In the
and electric motors, are gaining traction. With this evolution, there is a figure, N2 cylinder gas (secondary pressure fixed at 0.2 MPa) and syn­
significant shift in aftertreatment technologies, too. Low-temperature thetic air cylinder gas (N2 = 79%, O2 = 21%, secondary pressure fixed at
plasma, an innovation harnessing electrical energy, stands out as a 0.2 MPa) are used as the dilution gases. The N2 cylinder gas and syn­
promising technology. Unlike traditional methods, it does not rely on thetic air are mixed at an O2 concentration and flow rate of 13% and 2.5
ammonia or catalysts for NOx, PM, and HC removal [26–45]. L/min, respectively, using a set of mass flow controllers (SFC280,
Low-temperature plasma, in essence, leverages high voltage to generate Hitachi Metals, Ltd.), with maximum flow rates of 5 and 10 NL/min (N
a plasma field. Within this field, reactive oxygen species, known for their indicates the standard state of 0 ◦ C, one pressure). Additionally, flow
strong oxidizing power, are produced. These species then interact with meter A (RK1710, KOFLOC Corp.; maximum flow rate = 5 NL/min) is
NOx, PM, and HC, effectively breaking them down. The advantages are used to adjust the flow rate of the dilution gas. Further, to evaluate the
manifold. For instance, this technology can treat low-temperature removal performance of NOx, PM, and HC, the exhaust gas passes
exhaust gases continuously. Additionally, it does not experience the through a plasma reactor. Thus, the O2 concentration in the reactor must
same pressure drop issues as DPFs, making it a viable alternative [42]. be matched with that of the exhaust gas. Therefore, dilution gas with an
Some papers will introduce research on the treatment of hydrocarbons O2 concentration of 13% is prepared as the O2 concentration of diesel
and NOx. The paper [43] investigates the use of a plasma/adsorbent engine exhaust gas is approximately 13%. In this experiment, the diluted
system to treat NOx emissions in diesel exhaust. By using solid industrial gas (flow rate = 2.5 L/min) is mixed with the exhaust gas, and the mixed
wastes as the adsorbent, the authors present a potentially sustainable gas (flow rate = 5 L/min; dilution ratio = 2.0) is prepared and tested.
method for NOx reduction, simultaneously addressing pollution and The reason for dilution is that if the exhaust gas is used without dilution,

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K. Kawakami et al. Journal of Hazardous Materials 462 (2024) 132685

Fig. 1. Experimental setup for diesel exhaust treatment system using a surface discharge plasma reactor. (a) Schematic of experimental equipment. (b) Photograph of
the diesel engine, exhaust piping, apparatus, and flow directions used in the experiment.

3
K. Kawakami et al. Journal of Hazardous Materials 462 (2024) 132685

the PFA tube becomes clogged, and particles become trapped because of and hollow fiber membrane filter (DRY7–1/4, KITZ Corporation). Sub­
the effects of the large amount of soot contained in the exhaust gas and sequently, a set of gas analyzers (PG-235 and PG-240, HORIBA, Ltd.)
water vapor in the exhaust gas adhering to the PFA tube in the flow path, and total hydrocarbon (THC) or total volatile organic fraction (TVOC)
thus rendering difficulty in obtaining accurate experimental data and analyzer (FV-250, HORIBA, Ltd.) are used to measure the gas compo­
conducting the experiment. It is noted that O2 concentration of the raw nents (NO, NOx, O2, CO, and CO2) and THC, respectively. In the other
exhaust gas is almost the same as the diluted gas. Therefore, the dilution flow path, the flow rate is adjusted to 1 L/min, and the gas is sampled
has little effect on the reaction pathways of the plasma reactor. The using flow meter D (RK1650, KOFLOC Corp.; maximum flow rate = 1 L/
mixed gas is pressurized using a pump (APN-110LVX1–2, Iwaki Co., min). The sampled gas is diluted to 1/5 concentration with N2 cylinder
Ltd.; maximum discharge pressure = 0.10 MPa), and the flow rate is gas (secondary pressure fixed at 0.1 MPa) using flow meter B (RK1710,
adjusted to 5 L/min using a flow meter C (RK1710, KOFLOC Corp.; KOFLOC Corp.; maximum flow rate = 5 L/min) and measured using a
maximum flow rate = 5 L/min). Next, the gas mixture is introduced into scanning mobility particle sizer (SMPS). The SMPS is comprised of a
the plasma reactor, where PM and HC are oxidized and removed by the differential mobility analyzer (DMA, Model 3080, measurement range of
surface discharge plasma. The concentrations of HNO3 and O3 in the particle size: 10–414 nm, TSI Inc.) and a condensation particle counter
exhaust gas after the treatment are measured using gas detector tubes (CPC, Model 3787, TSI Inc.). As the particle concentration dN/dlogDp in
(No. 15 L nitric acid, No. 18 M ozone, GASTEC CORPORATION) through the CPC measurement ranges from 0 to 2.5 × 105 (cm–3), dilution with
a gas detector tube sampling port. Note that the treated exhaust gas N2 gas is necessary to avoid exceeding the upper limit of 2.5 × 105
contains the O3 generated in the reactor, which may corrode and dam­ (cm–3). Additionally, the current, voltage, and power waveforms in the
age the measurement equipment. Therefore, a tubular furnace (KPO-14 reactor are measured using an oscilloscope (DLM3054, Yokogawa
K, Isuzu Seisakusho Co., Ltd.) is installed immediately after the reactor Electric Corporation) using a current probe (MODEL 2878, Pearson
to perform pyrolysis at a set temperature of 300 ◦ C. Three-way valves A Electronics, Inc.; 10 A/V) and a high-voltage probe (HV-P60, Iwatsu
and B are installed to prevent the exhaust gas from flowing into the Electric Co., Ltd.; 2 kV/V). The exhaust gas and reactor surface tem­
reactor by changing the flow path when the reactor is turned off. When peratures are measured using thermocouple thermometers (MTCTS,
the exhaust gas flow into the reactor, water vapor and particles accu­ MISUMI Group Inc. and AD-5602, A&D Company, Limited,
mulate and negatively affects the measurement. respectively).
After treatment in the plasma reactor, the gas is divided into two flow Fig. 1(b) shows a photograph of the diesel engine, exhaust piping,
paths. The exhaust gas is adjusted to a flow rate of 4.0 L/min using flow apparatus, and flow directions used in this experiment. The diesel en­
meter E (RK1710, KOFLOC Corp.; maximum flow rate = 5 L/min), and gine exhaust gas obtained from the sampling port has a high tempera­
particles are removed using an air filter (ZFC-EL-4, SMC Corporation) ture and contains water vapor, which is removed and cooled by passing

Fig. 2. Surface discharge plasma reactor. (a) Surface discharge element and cross section of the inner wall of the element. (b) Front view of the surface discharge
element and the high-frequency and high-voltage power supply. (c) Photograph inside the surface discharge plasma reactor when the power is turned off. (d)
Photograph inside the surface discharge plasma reactor when the reactor input power is 400 W.

4
K. Kawakami et al. Journal of Hazardous Materials 462 (2024) 132685

it through a drain pot.

2.2. Plasma treatment system

2.2.1. Overview of plasma reactor equipment

Fig. 2 shows the cylindrical surface discharge element (HCII-OC70,
Masuda Research Inc.) constituting the surface discharge plasma reactor
used in this experiment. Fig. 2(a) shows a schematic of the cylindrical
surface discharge element and cross-section of the inner wall of the
element. The exhaust gas flows in through the sample inlet and flows out
through the sample outlet after being treated with plasma. The equip­
ment consists of a surface discharge tube utilizing the surface discharge
induced plasma chemical process (SPCP discharge tube: OC-70/AC,
Masuda Research Inc.) technology and a high-frequency and high-
voltage power supply (HCII− 70/2, input: voltage = three-phases 200 Fig. 3. Relationship between each composition of the raw exhaust gas com­
Vac, power = 1.5 kVA (50/60 Hz), output: peak-to-peak voltage ponents and the engine load.
= 14 kV (no electrical load), input power = 70 − 860 W, frequency
= 9.9 kHz, Masuda Research Inc.). Fig. 2(b) shows the front view of the
conditions, and the measurements are performed under one condition.
surface discharge element and the high-frequency and high-voltage
The gas concentration before the treatment is the average value of the 1-
power supply. The element is a ceramic tube (outer diameter =
min period immediately before the reactor is turned on. The gas con­
80 mm; length = 300 mm) with a discharge electrode on its surface of
centration after the treatment is the average value at 1 min after the
the ceramic tube and an induction electrode inside the ceramic. A sur­
reactor power stabilized. During the measurement of one condition,
face discharge is extended along the inner walls of the discharge elec­
changes in the exhaust gas components over time are recorded. In this
trode and ceramic tube by applying a high frequency and voltage
experiment, the engine load is changed to 0%, 25%, 50%, and 75%, and
between the two electrodes. Thus, a surface discharge plasma is gener­
the reactor removal performances at each engine load are compared.
ated on the surface of the discharge electrode, thereby producing reac­
When the engine load is 100%, the exhaust gas concentrations fluctuates
tive free radicals (active oxygen (O) and nitrogen (N)) with strong
greatly because it is a critical condition of the engine performance.
oxidation properties. The PM, HC, and NOx in the exhaust gas react with
Therefore, the experiment could not be conducted because it was not
these active oxygen species for their removal. Air cooling of the heat-
possible to dilute the flue gas accurately, and to compare the gas con­
dissipating fins attached to the outer wall of the ceramic tube prevents
centrations before and after the treatment accurately. For all the con­
overheating of the surface discharge elements. Figs. 2(c) and 2(d) show
ditions, the engine and gas analyzer warm-up times are both 60 min.
the internal structure of the reactor, as photographed by the endoscope.
Under each condition, the particle size distribution and gas concentra­
Fig. 2(c) shows the results when the power is turned off, whereas Fig. 2
tion in the engine exhaust are measured using an SMPS, gas analyzer,
(d) shows the results when the reactor input power is 400 W. These
and gas detector tube.
images show that the discharge is generated along the electrodes on the
ceramic surface.
2.2.3. Reactions of PM, HC, and NOx in the plasma reactor
Diesel exhaust particles (DEP) contain dry soot (C), soluble organic
2.2.2. Experimental condition and measurement procedure
compounds (SOF), hydrocarbon compounds (HC), sulfates, and water
Table 1 shows the engine specifications and experimental conditions.
droplets. PM (C, SOF, and HC) is oxidized by active oxygen species, and
Fig. 3 shows the relationship between each composition of the raw
gaseous CO and CO2 are induced. Thus, PM may be treated spatially. The
exhaust gas components and the engine load. Regarding CO2, NO, and
main chemical reactions for PM oxidation and removal are shown in
NOx, the values increase as the load increases. Regarding THC, O2, and
reactions (1)–(11) [16,25,27,28].
CO, the values decrease with increasing load. This graph gives the
exhaust boundary conditions of the experiments. The input power to the O3 → O2 + O (1)
plasma power supply is set to 0, 100, 200, 300, and 400 W, and the
particle-removal efficiency of the reactor, discharge power, and con­ NO + O → NO2 (2)
centration changes in the engine exhaust are measured. The time NO2 → NO + O (3)
required for each power level to stabilize is 10 min. To determine the
particle concentration before removal, the particle concentration is C + 2 O → CO2 (4)
measured using the SMPS when the reactor is turned off. Subsequently,
C + O → CO (5)
the flow path is changed using three-way valves A and B, and the reactor
is turned on and allowed to stabilize for 10 min. After stabilization, CO2 → CO + O2 /2 (6)
measurements are taken using the SMPS and an oscilloscope, and these
are used as the results when the reactor is turned on. The state of the SOF + O → mCO2 (mCO) + nH2O (7)
reactor is alternately repeated three times between off and on 2HC + 5 O → 2 CO2 + H2O (8)

Table 1 2HC + 5NO → 5 N2 /2 + H2O + 2CO2 (9)

Engine specifications and experimental conditions.
2NO2 + 2 C → N2 + 2CO2 (10)
Load, % 0 25 50 75
2NO2 + 4 C → N2 + 4CO (11)
Number of cylinder 1
Diameter of cylinder, mm 70
(m, n: Integers).
Stroke of cylinder, mm 55
Displacement volume, mL 211 In these reactions, according to reactions (4)–(8), C, SOF, and HC are
Rotating speed, rpm 3600 oxidized by oxygen radicals induced by reactions (1)–(3). Simultaneous
Power, kW 0 0.5 1.0 1.5 reduction of NO and HC is induced by reaction (9). Simultaneous
Dry weight of engine, kg 60
reduction of NO2 and dry soot is induced by reactions (10) and (11).

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K. Kawakami et al. Journal of Hazardous Materials 462 (2024) 132685

3. Results and discussion can vary depending on specific conditions and engine design. The
following papers [48–50] provide information about diesel engine
3.1. Particle concentration and removal efficiency exhaust particles. Each paper focuses on the characteristics of particles
under specific engine load conditions. PM is composed primarily of soot
Fig. 4 shows particle concentration before and after plasma treat­ and the soluble organic fraction (SOF), which are carbon components.
ment for engine loads of: (a) 0%, (b) 25%, (c) 50%, and (d) 75%. The Organic components, such as SOF, attach to the surface of agglomerates
particle size distribution of PM in the mixed gas is measured to confirm formed by the aggregation of soot particles and are emitted as PM. As the
the PM treatment performance of the reactor for each engine load engine load increases, soot particle agglomerates tend to form more soot
(sampling flow rate, Q = 5 L/min, and dilution air flow rate, QA= 2.5 L/ particles, SOF, and agglomerates. In addition, the combustion temper­
min). The horizontal and vertical axes represent the particle diameter ature in the engine increases, and small particles are burned. Conse­
(nm) and particle concentration of dN/dlogDp (cm–3), respectively. Each quently, as the number of small particles decreases, the proportion of
symbol indicates the particle concentrations before and after treatment coarse particles increases. These observations suggest that the peak
at 100, 200, 300, and 400 W. Additionally, each symbol represents the concentration of particles before treatment is likely to shift toward
average value of the measurements, and each error bar represents the larger particle diameters.
standard deviation ± σ . The figure shows that the reactor performs well Fig. 5 shows particle removal efficiency for engine loads of: (a) 0%,
in PM removal at each load and input power based on particle concen­ (b) 25%, (c) 50%, and (d) 75%. The horizontal and vertical axes
tration measurements. As the load increased, the peak value of the represent the particle size (nm) and removal efficiency (%), respectively.
particle diameter distribution before treatment transitioned to a larger The symbols indicate the removal efficiencies after treatment with input
particle diameter range. This is speculated to be due to the fact that the powers of 100, 200, 300, and 400 W. When the particle concentration
PM particle diameter is larger, and the percentage of coarse particles before treatment at each particle diameter is less than 2% of the peak
increases as the engine load increases. Generally, there is a tendency for value, it is excluded to ensure measurement accuracy. The figure shows
the diameter of diesel engine exhaust particles to increase as the engine that in the particle size range of 23.8 nm and above, the averaged
load becomes larger. When the engine load increases, the combustion removal efficiency is higher than 96% for all loads and input powers
process becomes more efficient, leading to an increase in particle gen­ except for a plot point protruded from the frame of Fig. 5(c). The plot
eration, which could result in larger particle diameters. However, this point is the removal efficiency of 95% and standard deviation of 3.35 for

Fig. 4. Particle concentration before and after plasma treatment for engine loads of: (a) 0%, (b) 25%, (c) 50%, and (d) 75%. The white symbol indicates particle
concentration before treatment, and the colored symbols indicate the particle concentration after treatment with input power of 100, 200, 300, and 400 W. Each
symbol and error bar represent the average value of the measurements and the standard deviation ± σ , respectively.

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K. Kawakami et al. Journal of Hazardous Materials 462 (2024) 132685

Fig. 5. Particle removal efficiency for engine loads of: (a) 0%, (b) 25%, (c) 50%, and (d) 75%. Symbols indicate the average removal efficiency after treatment with
input power of 100, 200, 300, and 400 W.

the particle size of 20.2 nm at the power of 200 W. However, it is found measured. This process of turning on and off is repeated three times for
that for the particle size range of 10 − 40 nm, the nucleation mode each power level. It is noted that the reason why there is a difference
particle removal efficiency is relatively lower, as shown in Fig. 5(c). This between the first time and the second time is that the first time mea­
indicates that a surface discharge plasma reactor provides high perfor­ surement was affected by the previous experimental conditions. For
mance for PM removal. example, although Fig. 6(b) is a measurement result at P = 100 W, it is
considered that it was affected by the post-treatment gas at 200 W that
was performed previously. It is difficult to completely remove this effect
3.2. Gas concentration over time during engine load change due to experimental time constraints. Repeating these experiments more
consistently will be considered in future work. The figure shows that the
Fig. 6 shows time-dependent gaseous concentrations (input power NO, NOx, and THC concentrations decrease, whereas the CO concen­
P = 100 W) for various engine loads of: (a) 0%, (b) 25%, (c) 50%, and tration increases when the reactor is turned on. The HC is oxidized by
(d) 75%. In the figure, the horizontal axis represents the elapsed time (s); the active oxygen species such as oxygen (•O) and hydroxyl (•OH)
the left vertical axis represents the concentrations of CO, CO2/10, O2/ radicals generated by the discharge plasma [43–45,47].
100 (ppm), and THC × 10 (ppmC); and the right vertical axis represents Fig. 7 shows typical time-dependent gaseous concentrations with an
NO and NOx concentrations (ppm). It is noted that the THC unit of ppmC engine load = 75% and input power = 400 W. Evidently, the THC
means methane (CH4) equivalent concentration. The two-direction ar­ concentration decreases, whereas the NO, NOx, and CO concentrations
rows indicate the periods in which the power is turned on (ON) and off increase owing to the formation of NO and NOx by the active nitrogen
(OFF). The dotted line indicates the time that the flow path is switched generated in the reactor for large power of 400 W. When the plasma is
with the three-way valves A and B to measure the particle concentration, turned off, CO2 concentration is increasing. This could be mainly caused
and the gas concentrations instantaneously change. To determine the by CO2 reduction to CO when the plasma is turned on. Under the con­
particle concentration before removal, the particle concentration is ditions in Fig. 7, a carbon balance is achived before and after treatment
measured during the period when the reactor is turned off. Subse­ within the range of measurement accuracy. A similar trend to that in
quently, the reactor is turned on and maintained for 10 min to stabilize Fig. 7 is observed at loads of 0%, 25%, and 50% loads (input power,
the power. After the stabilization, the particle diameter distribution, 400 W).
reactor discharge power, and O3 and HNO3 concentrations are

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K. Kawakami et al. Journal of Hazardous Materials 462 (2024) 132685

Fig. 6. Time-dependent gaseous concentrations (input power P = 100 W) for various engine loads of: (a) 0%, (b) 25%, (c) 50%, and (d) 75%.

the average values for one minute immediately before turning on and off
of the reactor. Since the value during that time was stable, the stabili­
zation time of 10 min is reasonable.
Fig. 8(a) shows that the NO, NOx, and THC concentrations after
treatment decrease at an input power of 100 W for all engine loads.
Essentially, the simultaneous removal of NOx, PM, and HC is achieved.
As HNO3 is generated at this time, the reduced NO and NOx first react
with active oxygen species such as ozone, oxygen, hydroxyl radicals etc.,
and then with water in the exhaust gas to generate HNO3. The O3 con­
centration decreases, whereas the HNO3 concentration increases with
increasing load. More than 57% HC removal is achieved at all loads and
powers. The highest removal efficiencies of 70%, 98%, and 67% for NOx,
PM, and HC, respectively, are achieved at a 75% engine load because the
amount of water in the exhaust gas increase at higher loads, which en­
hances the conversion of NOx to HNO3.
Fig. 8(b) shows that the NO and NOx concentrations increase after
Fig. 7. Typical time-dependent gaseous concentrations (engine load = 75%; treatment at an input power = 200 W. The amount of HNO3 generated is
input power = 400 W). insignificant. Increased NO and NOx concentrations vary with the load
owing to the influence of exhaust gas components. As the engine load
3.3. Gaseous concentrations before and after treatment for various engine increases, the CO2 concentration increases, whereas the THC and CO
load concentrations before the treatment decrease. This is owing to an in­
crease in the combustion temperature of the engine and the ratio of
Fig. 8 shows the gaseous concentrations before and after the treat­ completely combusts PM to HC in the exhaust gas.
ment for various engine loads, with input powers of: (a) 100 W, (b) Fig. 8(c) and (d) show that the trends at input powers of 300 and
200 W, (c) 300 W, and (d) 400 W. The horizontal axis represents the 400 W are similar to that at 200 W. The results reveal that the system
load (%), the left vertical axis represents the concentrations of CO, CO2/ performs well at an input power of 100 W for NOx, PM, and HC simul­
10 (ppm), and THC × 10 (ppmC), and the right vertical axis represents taneous removal. Combined with a wet scrubber for HNO3 removal and
NO, NOx, HNO3, and O3 (ppm). The solid lines indicate the gas con­ a catalyst bed for O3 removal followed by the plasma reactor, absorp­
centration after treatment, and the dotted lines indicate the gas con­ tion, neutralization, and removal enable the simultaneous removal of
centration before treatment. It is noted that the gas concentration values NOx, PM, HC, HNO3, and O3, and a total pollution control system will be
used in the comparison before and after treatment shown in Fig. 8 are realized. The trend with some hypothesis and reaction kinetics in the

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K. Kawakami et al. Journal of Hazardous Materials 462 (2024) 132685

Fig. 8. Gaseous concentrations before and after treatment for various engine load, with an input power of: (a) 100 W, (b) 200 W, (c) 300 W, and (d) 400 W. The solid
lines indicate the gaseous concentrations after treatment, and the dotted lines indicate the gaseous concentrations before treatment.

plasma discharge zone are discussed in the next section. obtained from the values shown in Fig. 5. NOx and HC removal effi­
ciencies are calculated from the NOx and HC concentrations before and
after treatment, as shown in Fig. 8. Note that a NOx removal of less than
3.4. NOx, PM, and HC removal for various specific energy zero is excluded. Therefore, NOx plots are fewer NOx plots than those for
PM and HC. At an input power of 100 W or SE less than 824 J/L, NOx in
Fig. 9 shows the results of NOx, PM, and HC removal efficiencies for the exhaust gas is reduced and removed by reacting with HC and CO in
various specific energy. The horizontal and vertical axes represent the the exhaust gas through the following reactions.
specific energy (SE) (J/L) and removal efficiency (%), respectively; the
symbols indicate the removal efficiencies of NOx, PM, and HC, respec­ 2NO + 2CO → N2 + 2CO2 (12)
tively. The specific energy is calculated dividing the discharge power by 2NO2 + 2CO → N2 + O2 + 2CO2 (13)
the flow rate of 5 L/min = 0.0833 L/s. The PM removal efficiency is
4NO + 2HC → 2 N2 + 2CO2 + H2 (14)

4NO2 + 2HC → 2 N2 + 2CO2 + H2 + 2 O2 (15)

It is known from the figure that more than 98% removal of PM, 70%
removal of NOx, and 67% removal of HC are achieved at a specific en­
ergy of 634 J/L. Concerning about HC removal, removal efficiency is
almost constant irrespective of SE because the exhaust gas contains a
certain concentration of hydrocarbons which are difficult to be
decomposed by the plasma, such as monocyclic and polycyclic aromatic
hydrocarbons. The decomposition efficiency of each component of the
hydrocarbon have not been measured, and it should be done in future
research. At a power of 200 W or more, the exhaust gas reaches a tem­
perature of about 80 ◦ C, and the plasma produces NOx at a concentration
higher than the NOx can be reduced by HC and CO. Therefore, NOx
removal efficiency becomes negative. This suggests that this exhaust gas
treatment system can achieve a high treatment performance when
operated at low specific energy.

Fig. 9. NOx, PM, and HC removal efficiencies for various specific energy.
Symbols indicate the removal efficiencies of NOx, PM, and HC, respectively.

9
K. Kawakami et al. Journal of Hazardous Materials 462 (2024) 132685

4. Conclusions Data Availability

A performance evaluation of PM, NOx, and HC removal from diesel Data will be made available on request.
engine exhaust by surface-discharge-induced plasma is performed. The
main conclusions are as follows. Acknowledgments

(1) At 100 W input power, NOx, PM, and HC are removed at engine The authors acknowledge the cooperation of Mr. Ryotaro Tamaoki,
loads, with top efficiencies of 70% for NOx, 98% for PM, and 67% an undergraduate student of mechanical engineering at Osaka Prefec­
for HC at 75% load. NOx reduces by interacting with HC and CO. ture University, in conducting this research. This study was partially
Increasing CO concentration leads to PM and HC oxidation from supported by JSPS KAKENHI Grant Number JP20H02374 and
reactive oxygen species such as O in plasma discharge. Further­ JP23H01626.
more, simultaneous reduction of NO and HC, and simultaneous
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