separations

Review
Purification Technologies for NOx Removal from Flue Gas:
A Review
Zihan Zhu 1 and Bin Xu 1,2, *

1 State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and
Engineering, Tongji University, Shanghai 200092, China
2 Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, China
* Correspondence: [email protected]; Tel.: +86-021-6598-1831 (ext. 8016)

Abstract: Nitrogen oxide (NOx) is a major gaseous pollutant in flue gases from power plants,
industrial processes, and waste incineration that can have adverse impacts on the environment
and human health. Many denitrification (de-NOx) technologies have been developed to reduce
NOx emissions in the past several decades. This paper provides a review of the recent literature
on NOx post-combustion purification methods with different reagents. From the perspective of
changes in the valence of nitrogen (N), purification technologies against NOx in flue gas are classified
into three approaches: oxidation, reduction, and adsorption/absorption. The removal processes,
mechanisms, and influencing factors of each method are systematically reviewed. In addition, the
main challenges and potential breakthroughs of each method are discussed in detail and possible
directions for future research activities are proposed. This review provides a fundamental and
systematic understanding of the mechanisms of denitrification from flue gas and can help researchers
select high-performance and cost-effective methods.

Keywords: flue gas purification; NOx removal; oxidation; reduction; absorption; adsorption

Citation: Zhu, Z.; Xu, B. Purification

1. Introduction
Technologies for NOx Removal from
Flue Gas: A Review. Separations 2022,
The pollutants produced by power plants, industrial processes, and municipal solid
9, 307. https://doi.org/10.3390/
waste incineration mainly include particulate matter, sulfur oxides, and nitrogen oxides
separations9100307 (NOx) [1,2]. NOx in flue gas mainly exists in the form of NO (90–95%) and NO2 (5–10%).
NOx emissions can cause a series of health problems, such as eye and throat inflamma-
Academic Editor: Alena Kubatova
tion, chest tightness, nausea, and headaches, as well as environmental problems, such as
Received: 10 August 2022 ozone depletion, acid rain, haze, photochemical smog, and greenhouse gas emissions [3,4].
Accepted: 10 October 2022 Therefore, NOx emissions must be reduced and controlled.
Published: 13 October 2022 In regard to different combustion stages, NOx control methods can be categorized
into pre-combustion, in-combustion, and post-combustion control [5]. For pre-combustion
Publisher’s Note: MDPI stays neutral
control, the focus is on reducing the nitrogen in the fuel, specifically by selecting a fuel with
with regard to jurisdictional claims in
a low nitrogen content or reducing the nitrogen content of the fuel. The in-combustion
published maps and institutional affil-
iations.
control technology, also called low-NOx combustion technology, is mainly used to suppress
NOx generation by adjusting operation parameters, modifying burners, etc. [6]. For pre-
combustion and in-combustion control methods, only low removal efficiencies can be
achieved. Without further countermeasures, most of the exhaust gases from industrial
Copyright: © 2022 by the authors. furnaces cannot meet emission standards. Therefore, a post-combustion approach is usually
Licensee MDPI, Basel, Switzerland. used to achieve a higher NOx reduction [7].
This article is an open access article Substantial research has been conducted in developing post-combustion technologies
distributed under the terms and to meet stricter environmental regulations for NOx. Figure 1 presents the statistics of yearly
conditions of the Creative Commons published papers on the topic of NOx purification from flue gas. Table 1 lists currently
Attribution (CC BY) license (https:// used purification technologies for NOx removal from flue gas after combustion.
creativecommons.org/licenses/by/
4.0/).

Separations 2022, 9, 307. https://doi.org/10.3390/separations9100307 https://www.mdpi.com/journal/separations

Separations
Separations2022,
2022,8,9,x307
FOR PEER REVIEW 2 2ofof29
27

Figure
Figure1.1. Publication
Publicationof ofpapers
papersfrom
fromthe
thelast
lastfour
fourdecades
decadeson onNOx
NOxpurification
purificationfrom
fromflue
fluegas.
gas.The
The
data
data were retrieved
retrievedfrom
fromthethe
WebWeb of Science
of Science database
database with
with the the of
topics topics
“NOx ofremoval”
“NOx removal”
or “DeNOx” or
“DeNOx”
and “flue and
gas”“flue gas”
(totally (totally
2078 2078(a)
papers). papers). (a) represented
represented the publication
the publication trend of
trend of papers papers1981
between be-
tween 1981(b)and
and 2021. 2021. (b) demonstrated
demonstrated the statistical
the statistical results of top 10results of ranked
journals top 10 byjournals ranked
the number by the
of articles.
number of articles.
Table 1. Post-combustion methods for NOx removal.
Table 1. Post-combustion methods for NOx removal.
Method Operation Concept Advantage Disadvantage Ref.
Method Operation Concept Advantage Disadvantage Ref.
HighHigh
costs costs
of catalysts
of catalysts
Use gaseous reductants to
Ammonia slip
Selective catalyticUse gaseous
reduce NOxreductants to reduce High efficiencies
with catalysts Ammonia slip
Selective catalytic Corrosion of equipment [8]
reduction (SCR) NOx with under approximate
catalysts under ap- High efficiencies Limited Corrosion ofcatalyst
equipment [8]
reduction (SCR) life span of
temperature
proximate temperature Limited
Large amounts lifeof
span of catalyst
waste
Large amounts
High consumption of waste
of reactant
Use gaseous reductants to Reliable technology
Selective non-catalytic reduce NOx without NoReliable
catalyst used
High
Ammoniaconsumption
leakage of reactant
technology The formation of N2 O and CO Fly [9]
Selective
reduction (SNCR) Use gaseous reductants
catalysts under high to reduce Less equipment Ammonia leakage
No catalyst used ash and unburned
non-catalytic re- NOx withouttemperature
catalysts under high investment The formation of N2O and CO [9]
carbon increasing
Less equipment invest-
duction (SNCR) temperature Fly ash and unburned carbon
Simultaneous ment
removal
Exposed to liquid of muti-pollutant
increasing
High amount of liquid waste
Absorption absorbents to scrub NOx Simultaneous
Simple operationremoval of Low efficiency [10]
High amount of liquid waste
Exposed to liquid
from absorbents to Stability
gas phase muti-pollutant
against Large multi-stage scrubbers
Absorption inlet gas operation Low efficiency [10]
scrub NOx from gas phase Simple
Large multi-stage scrubbers
NOx can be adsorbed by No liquid against
Stability wastes inlet gas
porous solid materials HighNopurification
liquid wastes High investment cost
Adsorption [11]
NOx canunder
be adsorbed by porous
approximate efficiency Huge equipment
pressure and temperature High purification efficien- High investment cost
Adsorption solid materials under approximate Simple equipment [11]
cy Huge equipment
pressure and temperature
High-energy electrons
Low equipment cost
Simple equipment
excite molecules to High energy cost
Non-thermal No waste
Low equipment cost
generate radicals that can Low efficiency [12]
plasma (NTP) High-energy electrons excite mol- Simple operation High energy cost
Non-thermal oxidize NOx in a very No waste Low operating pressure
ecules to generate
short radicals
time that can Useful by-product Low efficiency [12]
plasma (NTP) Simple operation
oxidize NOx in a very short time Low operating pressure
Useful by-product
In this paper, the existing NOx purification methods are summarized and reviewed. In
regards to the different transformation approaches (methods causing an increase, decrease,
Separations 2022, 9, 307 3 of 27

or no change in the chemical valence of nitrogen), the purification against NOx from
flue gas is classified into three types: oxidation methods (N valence increases), reduction
methods (N valence decreases), and absorption/adsorption methods (no change in N
valence). Furthermore, some innovative methods that are still at laboratory scale, such as
non-thermal plasma, are also discussed. The aim of this paper is to present a comprehensive
overview of post-combustion NOx purification technologies with different physical state
reagents and to help researchers select methods with high performance for NOx removal
in specified situations.

2. Oxidation Methods
Regarding the presence of large amounts of insoluble NO in flue gas, oxidizing NO
to a much more soluble NO2 is a highly necessary step, followed by wet scrubbing or dry
absorption. In regard to the states of oxidants required for NO oxidation, the reactants are
divided into gas oxidants, liquid oxidants, and solid oxidants. The reaction mechanism
and the factors affecting the removal efficiency are reviewed.

2.1. Gas Oxidants

Due to the full and effective contact between reactants, gaseous oxidants are widely
employed to remove NOx from flue gas. Gas oxidants include oxygen (O2 ), ozone (O3 ),
chlorine species, and non-thermal plasma.

2.1.1. Oxygen (O2 ) Oxidants

Oxygen is one of the most common oxidants. Thermodynamically, oxygen can
spontaneously oxidize NO to NO2 and the activation energy for oxidizing NO by O2
is −4.41 kJ/mol in the temperature range of 270–600 K [13]. However, previous studies
have reported that in flue gases from power plants and in industrial processes, such as
sintering and waste incineration, the ratio of NO/NOx is still more than 90%, even though
there is a considerable proportion of oxygen (3–8%) in the flue gas [14–16].
In oxygenated gaseous environments, the reaction of NO with O2 proceeds as a
third-order reaction [17]:
2NO + O2 → 2NO2 (1)
d[NO] d[NO2 ]
− =+ = 2 k· [NO]2 ·[O2 ] (2)
dt dt
where the rate constant k is dependent on temperature. In untreated flue gases of power
plants, the concentration of NOx usually ranges between 200 and 400 ppm [18]. In the tail
gas of cement kilns, the concentration of NOx can reach 500–800 ppm or more, and O2 is
concentrated over 8–10% [19]. Therefore, the oxidation rate of NO by O2 is still low without
a catalyst.
Numerous reaction pathways, including a trimolecular reaction, a pre-equilibrium
mechanism with a dimer of NO ((NO)2 ) as an intermediate, and a pre-equilibrium mech-
anism with NO3 as an intermediate, have been proposed to explain the homogenous
oxidation of NO by O2 [20].
NO2 is produced from NO and O2 at a high pressure and low temperature.
Ting et al. [21] investigated the oxidation of NO to NO2 in the gas phase, absorption
in liquid water, and interactions with water vapor at pressures ranging from ambient to
30 bar. As the conversion rate of NO approached 90% over a longer residence period,
dry gas oxidation performed well in comparison to global reaction kinetics, which are
frequently applied at lower pressures. The study also demonstrated that the NO/NO2 ratio
is mostly unaffected by temperature (25–500 ◦ C).
Although O2 might directly oxidize NO, the oxidation rate is still constrained. Cat-
alysts, including noble metals, metal oxides/complexes, activated carbon materials, etc.,
have been extensively studied in recent years. The introduction of diverse catalysts pro-
vided active sites, enhancing the reaction between nitric oxide and oxygen and improving
the oxidation efficiency. Mn-based catalysts are common catalysts that have recently at-
 Although O2 might directly oxidize NO, the oxidation rate is still constrained. Cat-
alysts, including noble metals, metal oxides/complexes, activated carbon materials, etc.,
have been extensively studied in recent years. The introduction of diverse catalysts pro-
Separations 2022, 9, 307 4 of 27
vided active sites, enhancing the reaction between nitric oxide and oxygen and improv-
ing the oxidation efficiency. Mn-based catalysts are common catalysts that have recently
attracted interest due to their plentiful supply, low cost, easy fabrication technique, and
tracted interest stability
strong thermal due to their
[22]. plentiful
The MnOsupply, low
2 catalysts cost,
with easy fabrication
various technique, have
crystal morphologies and
strong
shownthermal stability
significant [22]. activity.
catalysis The MnOThe 2 catalysts
γ-MnOwith various
2 catalyst crystal morphologies
demonstrated the highesthave
ac-
shown significant catalysis activity. The γ-MnO catalyst demonstrated the
tivity among the four catalysts (α-, β-, γ-, and δ-MnO2) and exhibited 91% NO conversion
2 highest activity
among
at 250 °C the[23].
four catalysts
Gao (α-,proposed
et al. [24] β-, γ-, and δ-MnO
reaction 2 ) and exhibited
pathways 91% NO conversion
for NO oxidation at
by α-, β-, and
250 ◦ C [23]. Gao et al. [24] proposed reaction pathways for NO oxidation by α-, β-, and
γ- MnO2 catalysts, as shown in reactions (3) and (4).
γ- MnO2 catalysts, as shown in reactions (3) and (4).
O2 NO2 (gas)
Mn −◻ −Mn → 2(−MnO) → MnO − NO − OMn
O2 NO2 (gas) (3)
Mn −  − Mn → 2 (− MnO )
(◻ represents oxygen vacancy, same below) → MnO − NO − OMn (3)
( represents oxygen vacancy, same below)
MnO − NO − OMn → Mn − O − Mn + NO2 (4)
MnO − NO − OMn → Mn − O − Mn + NO2 (4)
Lattice oxygens
Lattice oxygens contributed
contributed to
to the
the production
production ofof bridging
bridging nitrates
nitrates on
on the
the -MnO
-MnO2
2
catalyst. The presence of Mn cations, which were quickly oxidized, led to the conversion
catalyst. The presence of Mn cations, which were quickly oxidized, led to the conversion of
of NO
NO andand trans-(N
trans-(N 2O2)2 species [25]. As a result, in addition to reactions (3) and (4)
2 O2 )2 species [25]. As a result, in addition to reactions (3) and (4) above,
above,
the the following
following reactions,
reactions, reactions
reactions (5) and
(5) and (6), also(6), also
exist exist [24]:
[24]:
Mn−O or Mn=O
NO (gas) → Mn−OMnO
or Mn−
=ONO − OMn (5)
NO (gas) → MnO − NO − OMn (5)
1
Mnn+ O 1
− 2Mn2n+
− 2 O2 (6)
NO(gas) → NO(NO
gas)→ → NO
NO2 (gas)
→ NO2 (gas) (6)
Yuan et
Yuan et al.
al. [26]
[26]discovered
discovered that that NO
NO adsorbed
adsorbed atat oxygen
oxygen vacancy
vacancy would
would bebe aa critical
critical
poisoning species and
poisoning and deactivate
deactivateMnO MnO2.2 Possible
. Possiblepathways
pathways of of
NONO oxidation based
oxidation on the
based on
Mars–van
the Mars–vanKrevelen
Krevelen(MvK)
(MvK)mechanism
mechanism were proposed
were proposed(as (as
shown
shownin Figure 2). 2).
in Figure As the
As
favoured
the pathway
favoured pathway showed,
showed,the the
O2 on
O2 oxygen vacancies
on oxygen reacted
vacancies withwith
reacted the the
nearby
nearbyNONO ab-
sorbed onon
absorbed thetheMnMn cations. An An
cations. intermediate (ONOO)
intermediate (ONOO)waswasformed during
formed this this
during step step
and
and
thenthen decomposed
decomposed to NOto2. In
NOthis
2 . In this process,
process, the adsorption
the adsorption of oxygen ofonoxygen
oxygenonvacancies
oxygen
vacancies was considered
was considered as a decisive
as a decisive step. Thisstep. This
result result
was was consistent
consistent with previous
with previous studies
studies [24,27,28].
[24,27,28].

Figure 2. Possible pathways of NO oxidation with the Mars–van Krevelen mechanism occurring
on Mn5c site and lattice O on MnO2 . The red pathway represented the favoured mechanism of NO
oxidation on MnO2 . Modified from [26] with permission from the American Chemical Society.
 Figure 2. Possible pathways of NO oxidation with the Mars–van Krevelen mechanism occurring on
Mn5c site and lattice O on MnO2. The red pathway represented the favoured mechanism of NO
Separations 2022, 9, 307 oxidation on MnO2. Modified from [26] with permission from the American Chemical Society.5 of 27

2.1.2. Ozone (O3) Oxidants

2.1.2.OOzone
3 was extensively
(O3 ) Oxidantsstudied for flue gas purification or emission control due to its
high oxidation
O3 was extensively studied forexcellent
rate and efficiency, oxidation selectivity,
flue gas purification or emission and broaddue
control temperature
to its high
range of use [29].
oxidation rate and efficiency, excellent oxidation selectivity, and broad temperature range
Recently,
of use [29]. an ab initio calculation of quantum chemistry has been used to simulate
the oxidation process of NOx.
Recently, an ab initio Mok etofal.quantum
calculation [30] proposed
chemistrythe has
main
been12-step
usedoxidation
to simulate reac-
the
tion of NOx
oxidation oxidation.
process NO Mok
of NOx. can beet directly oxidized the
al. [30] proposed by O 3 to NO
main 2 (reaction
12-step (7)) reaction
oxidation and the
rate constant
of NOx is measured
oxidation. NO canasbeshown
directlyin oxidized
Equation by(8).OThe main pathways of NOx oxida-
3 to NO2 (reaction (7)) and the rate
tion by Ois
constant 3 are shown as
measured in shown . However,
Figure 3in Equation (8).this The
12-step
mainreaction
pathways mechanism ignores the
of NOx oxidation by
interaction of some intermediate gases (such as N 2 O, H 2 O, HNO 3 , etc.).
O3 are shown in Figure 3. However, this 12-step reaction mechanism ignores the interaction
of some intermediate gases (such as N2 O, H2 O, HNO3 , etc.).
NO + O3 → NO2 + O2 (7)
NO + O3 → NO2 + O2 (7)
k = 1.8 × 10−14 cm3 mol−1 s−1 (8)
k = 1.8 × 10−14 cm3 mol−1 s−1 (8)

Schematic diagram
Figure 3. Schematic
Figure diagram of
of the
the main
main pathways
pathways of NOx oxidation by O33.. Solid
Solid lines
lines represent
represent
reactions occurring and
reactions always occurring anddashed
dashedlines
linesrepresent
represent reactions
reactions occurring
occurring under
under certain
certain condi-
conditions.
tions.
AdaptedAdapted from [31].
from [31].

Several studies
Several studies have
have confirmed
confirmed thatthat the
the molar
molar ratioratio affected
affected the
the mechanism
mechanism of of NO
NO
oxidation by O [31–33]. When the molar ratio was less than
oxidation by O3 [31–33]. When the molar ratio was less than 1, NO was mainly oxidized1, NO was mainly oxidized to
NO
to NO 2 . 2When
. Whenthe themolar
molarratio
ratiowas
wasgreater
greaterthan
than1,1,the theoxidation
oxidationproducts
products were
were NO
NO22,, N N22OO55,,
and HNO
and HNO33. .According
According toto Ref.
Ref. [31],
[31], thethe formation
formation of HNO
of HNO 3 was
3 was due due
to thetopresence
the presence of H2Oof
H O in flue gas. It was also found that the concentrations
in flue gas. It was also found that the concentrations of N2O5 and HNO3 sharply de-
2 of N2 O 5 and HNO 3 sharply
decreased at temperatures ranging from120120°C◦ C to 180 ◦ C. Therefore, a way to control HNO
creased at temperatures ranging from to 180 °C. Therefore, a way to control HNO33
formation when oxidizing NO by
formation when oxidizing NO by O33 could be to O could be to increase
increase thethe reaction
reaction temperature.
temperature. The The
maximum yield of N O was produced at 90 ◦ C when the molar ratio of O /NO was larger
maximum yield of N22O55 was produced at 90 °C when the molar ratio of O33/NO was larger
than 1.
than 1. The
The most
most soluble
soluble nitrogen
nitrogen oxides,
oxides, N N22OO55, ,were
werethe theend
endproduct
productof ofNO
NOoxidation
oxidation by by
O . As Figure 3 depicted, the products besides
O33. As Figure 3 depicted, the products besides N2O25 included N O 5 included NO
NO2, NO , NO , N O
2 3, N32O3, 2HNO , HNO
3 2, and 2,
and HNO
HNO 3 . In particular,
3. In particular, NO3 NO can rapidly
can3rapidly reactreact
withwith NO NO and and decompose
decompose to 2NO
to NO 2 . Finally,
. Finally, all
the NOx species can be transformed into N2O5 by the excess amount of O3. The NOxNOx
all the NOx species can be transformed into N 2 O 5 by the excess amount of O 3 . The re-
removal rate reached 96.5% when the molar ratio of O3 /NO NO was 1.8 [34].
moval rate reached 96.5% when the molar ratio of O3/NO NO was 1.8 [34].
Zhou et al. used ozone oxidation and an alkaline counter-flow packed scrubber to
Zhou et al. used ozone oxidation and an alkaline counter-flow packed scrubber to
investigate ozone decomposition, the oxidation properties of NOx, the removal efficiencies
investigate ozone decomposition, the oxidation properties of NOx, the removal effi-
of NOx and SO2 , and the optimal factors [35]. It was found that as the temperature increased
ciencies of NOx and SO2, and the optimal factors [35]. It was found that as the temper-
and the initial ozone concentration declined, the NOx oxidation efficiency decreased. The
ature increased and the initial ozone concentration declined, the NOx oxidation effi-
NO conversion process was not significantly impacted by SO2 presence. The most effective
ciency decreased. The NO conversion process was not significantly impacted by SO2
additive to lower ozone consumption was CO(NH2 )2 . The ideal conditions for reducing
presence. The most effective additive to lower ozone consumption was CO(NH2)2. The
SO2 and NOx were reached, including a temperature of 150 ◦ C, a stoichiometric ratio (0.6)
ideal conditions for reducing SO2 and NOx were reached, including a temperature of
of ozone and NO, and a pH of approximately 8.
150 °C, a stoichiometric ratio (0.6) of ozone and NO, and a pH of approximately 8.
2.1.3. Chlorine (Cl2 ) and Chlorine Dioxide (ClO2 ) Oxidants
Gaseous chlorine species mainly refer to chlorine (Cl2 ) and chlorine dioxide (ClO2 ).
There is little research on its direct application for NO oxidation. As a high-valence
gaseous form of chlorine, ClO2 is more oxidative compared to Cl2 . At temperatures
Separations 2022, 9, 307 6 of 27

ranging from 220 to 367 K, the oxidation rate constant of NO to NO2 by ClO2 (reaction (9))
was measured and found to be negatively correlated to temperature, with an Arrhenius
expression (Equation (10)) [36]:

OClO + NO → ClO + NO2 (9)

k = (1.04 ± 0.24) × 10−13 exp[(347 ± 58)/T] cm3 mol−1 s−1 (10)

where k represents the reaction constant rate and T represents the temperature of the
reaction, K.
Laboratory-scale experiments were carried out to investigate the conversion of NO to
NO2 [37]. It was found that ClO2 could effectively oxidize NO, and the conversion rate was
up to 100%. Cl2 /ClO2 were often generated on-site using chemical or electrolytic methods
from either sodium chlorite or sodium chlorate solutions (reviewed in Section 2.2.3) owing
to the shipment and storage security requirements [38]. The application of Cl2 /ClO2 for
de-NOx is usually followed by liquid phase scrubbing technology.

2.1.4. Non-Thermal Plasma (NTP)

Plasma is typically an ionized gas made up of several highly energetic electrons, free
radicals, excited species, photons, etc. Electricity-generated plasma is typically divided into
two forms: thermal plasma and non-thermal plasma [39]. Since gaseous pollutants might be
transformed into inert compounds by free radicals (H•, N•, O•, OH•, O3 •, HO2 •, etc.) in
plasma [40], NTP has been expanded to remove NOx in flue gases at atmospheric pressure
with significantly less investment, maintaining cost and energy requirements [12]. De-NO
and de-SO2 in a pulsed corona discharge process (PCDP) reactor have been modeled using
a mechanism and kinetic scheme, and the model has been confirmed by experimental data.
It has been discovered that NO and SO2 react with oxidizing radicals to form oxides with
higher valence states [41]. Table 2 lists the NTP procedures that are currently accessible
for NO oxidation from the perspectives of the NTP reactor, additives, gas composition,
reaction conditions, and removal efficiency.

Table 2. Experimental conditions and removal efficiencies of available NTP processes for
NO oxidation.

Maximum
NTP Reactor Gas Composition Reaction Condition Removal Ref.
Efficiency
Energy density: 90 J/L
Gas residence time: 3.3 s
DBD * Dry Air/NO (206 ppm) 99.5% [42]
Reaction temperature: 25 ◦ C
Gas flow rate: 1 L/min
Energy density: 22 J/L
Coal-fired flue gas, NO Reaction temperature: 75 ◦ C (do*)/90 ◦ C
30%(do)/70%(io) [43]
(200 ppm), SO2 (250 ppm) (io*)
Gas flow rate: 150 m3 /h
Energy density: 570 J/L
N2 /NO (500 ppm) Gas residence time: 0.64 s 80% [44]
Gas flow rate: 10 L/min
Catalyst: TiO2
Pulse frequency: 900 Hz
NO (300 ppm), SO2 (260 ppm), Capacitor-Charging voltage: 12 kV Gas
100% [45]
N2 balance residence time: 1.0 s
Reaction temperature: 25 C
Gas flow rate: 5 L/min
Separations 2022, 9, 307 7 of 27

Table 2. Cont.

Maximum
NTP Reactor Gas Composition Reaction Condition Removal Ref.
Efficiency
Energy density: 7.6 J/L
NO (200 ppm), SO2 (150 ppm),
Gas residence time: 1.68 s
PCD * CO (150 ppm), H2 O (10%), O2 65% [41]
Reaction temperature: 137 ◦ C
(20%)
Gas flow rate: 1 L/min
Energy density: 80 J/L
NO (120 ppm), SO2 (525 ppm),
Gas residence time: 5.0 s
O2 (6%), CO2 (12%), H2 O (3%), 71% [46]
Reaction temperature: 25 ◦ C
N2 balance
Gas flow rate: 6 L/min
Energy density: 45.8 J/L
NO (180 ppm), SO2 (1013 ppm), Gas residence time: 4.4 s
40% [47]
air balance Reaction temperature: 25 ◦ C
Gas flow rate: 72 L/min
Energy density: 48.3 J/L
NO (537 ppm), O2 (22%), H2 O
Reaction temperature: 25 ◦ C 98.3% [48]
(RH = 60%), N2 balance
Gas flow rate: 0.3 m3 /h
Absorbed dose: 20 kGy
NO (200 ppm), NO2 (200 ppm) Reaction ratio: 1:2
EBGP * 94.5% [49]
SO2 (200 ppm), air balance Gas residence time:30–40 s
Gas flow rate: 1 L/min
Wet scrubber: NaClO2
NO (1046 ppm), fuel-combustion Absorbed dose: 10.9 kGy
95.03% [50]
flue gas Gas residence time:11 min
Gas flow rate: 200 mL/h
* DBD represents dielectric barrier discharge; PCD represents pulsed corona discharge; and EBGP represents
electron beam generated plasma.

As shown in Figure 4, there are often three steps to the elimination of NOx via the
collision of electrons with neutral molecules [51]. Within the first nanoseconds, the intense
plasma electrons collide with gaseous molecules (with the main components being H2 O, N2 ,
and O2 ), forming primary radicals (HO•, O•, and N•) and ions. Excited molecules, such
as oxygen, quickly interact with the main gas after it has been quenched to form more O
and HO. Then, the electron–ion and ion–ion reactions continue to produce more secondary
radicals with energies higher than those of gas molecules. Although these radicals have a
short lifetime under atmospheric pressure and ambient temperature settings, they could
convert NOx into HNO3 in a relatively short period of time (usually 10−3 s). These reactions
are intense with no apparent sequential response. Finally, before the NH4 NO3 is collected
and used as a fertilizer, the HNO3 might be neutralized by the ammonia that was generally
used in the pulse corona discharge process.

2.2. Liquid Oxidants

For the removal of NOx, wet scrubbing techniques are comparable with other post-
combustion technologies. They may also be employed to regulate acid gases and particulate
matter simultaneously. As an advanced and stable technology, wet flue gas de-SO2 (WFGD)
contributes to more than 95% of the de-SO2 capacity and is now being implemented
worldwide [52]. However, due to the poor solubility of NO, almost all WFGD technologies
are unable to concurrently remove NOx. As a result, upgrading the WFGD to boost the de-
NOx function has lately drawn increasing interest. The simultaneous removal of SO2 and
NOx by the oxidation-scrubbing approach is possible if the NO is effectively oxidized, since
the solubility of NOx in water increases greatly with its valence. In Table 3, representative
oxidants and their redox potentials for liquid phase oxidation are listed.
 form more O and HO. Then, the electron–ion and ion–ion reactions continue to produce
more secondary radicals with energies higher than those of gas molecules. Although
these radicals have a short lifetime under atmospheric pressure and ambient temperature
settings, they could convert NOx into HNO3 in a relatively short period of time (usually
10−3 s). These reactions are intense with no apparent sequential response. Finally, before
Separations 2022, 9, 307 8 of 27
the NH4NO3 is collected and used as a fertilizer, the HNO3 might be neutralized by the
ammonia that was generally used in the pulse corona discharge process.

Figure 4.
Figure Removal process
4. Removal process of
of NOx
NOx by
by the
the collision
collision of
of electrons
electrons with
with neutral
neutral molecules. Adapted
molecules. Adapted
from [51]
from [51] with
with permission
permission from
from Elsevier,
Elsevier,Copyright
Copyright2021.
2021.

Table 3. Standard oxidation potentials of representative oxidants used in gas–liquid oxidation.

Oxidation Potential
Oxidant Half-Cell Reaction Ref.
(eV)
Fluorine (F2 ) F2 + 2e− + 2H+ → 2HF 3.05 [53]
Hydroxyl radical (HO•) HO• + H + +
e− → H2 O 2.80 [54]
Sulfate radical (SO4 − •) SO4− • + e− → SO24− 2.60 [55]
Ozone (O3 ) O3 + 2H + 2 +
e− → O2 + H2 O 2.07 [53]
Persulfate (S2 O8 2− • )
S2 O28− • + 2e− → 2SO24− 2.01 [53]
Peroxymonosulfate (HSO5 − ) HSO5− +H +
+ 2e− → H2 O + SO24− 1.82 [56]
Hydrogen peroxide (H2 O2 ) H2 O2 + 2H +
+ 2e− → 2H2 O 1.78 [53]
Permanganate (MnO4 −) MnO4− + 4H +
+ 3e− → 2H2 O + MnO2 1.70 [53]
Chloranion (ClO3 - ) 2ClO3− + 12H +
+ 10e− → 2H2 O + Cl2 1.49 [53]
−
Chloine (Cl2 ) Cl2 + 2e− → 2Cl 1.36 [53]
Chromate (Cr2 O7 2− )
Cr2 O27− + 14H +
+ 6e− → 7H2 O + 2Cr 3+ 1.33 [53]
Molecular oxygen (O2 ) O2 + 4H +
+ 4e− → 2H2 O 1.23 [53]

2.2.1. H2 O2 Oxidants
Hydrogen peroxide (H2 O2 ) is an environment-friendly oxidant. However, the reaction
rate of direct NOx oxidation by H2 O2 is still not ideal [57]. Therefore, it has attracted
extensive attention as a precursor of HO• [58]. Transition metal ions (such as Fe2+ , Cu2+ ,
and Cr3+ ), transition metal oxides (such as CrO3 , Al2 O3 ), and physical phenomena are
widely used to catalyze the conversion of H2 O2 to HO• [59].
The oxidation of NO by Fenton reagent can be divided into two main steps: (1) oxygen
radical generation; and (2) the oxidation of NO. The mechanism reactions are summarized
as follows [60,61]:
(1) Oxygen radical generation (Fenton reaction):

Fe2+ + H2 O2 → Fe3+ + OH− + ·OH (11)

·OH + H2 O2 → H2 O + ·O2 H (12)

3+ 2+
Fe + ·O2 H → Fe + O2 + ·OH (13)
Fe2+ + ·OH → Fe3+ + OH− (14)
(2) Oxidation by •OH
NO + ·OH → H+ + NO2− (15)
NO + ·OH → ·H + NO2 (16)
NO2 + ·OH → H + NO3−
+
(17)
NO2− + ·OH → ·H + NO3− (18)
 NO +· OH →· H + NO2 (16)

NO2 +· OH → H + + NO−
3 (17)

Separations 2022, 9, 307 NO− −

2 +· OH →· H + NO3
9(18)
of 27

To increase oxidation efficiency, studies have focused on increasing hydroxyl radical

(•OH) Togeneration and H2Oefficiency,
increase oxidation 2 consumption rates [62]. In a lab-scale bubbling reactor, Guo
studies have focused on increasing hydroxyl radical
et al. [63] investigated the effects
(•OH) generation and H2 O2 consumption of operating
ratesparameters, such as bubbling
[62]. In a lab-scale pH value,reactor,
H2O2 con-
Guo
centration, NO inlet concentration, and reaction temperature, on the
et al. [63] investigated the effects of operating parameters, such as pH value, H2 O2 concen- NO removal effi-
ciency.
tration,ANO significant impact of pH
inlet concentration, andvalue on NO
reaction removal effectiveness
temperature, on the NO removalwas discovered,
efficiency.
and the effectiveness of NO removal decreased as the reaction
A significant impact of pH value on NO removal effectiveness was discovered, temperature rose. and
Haotheet
al. [64] developed
effectiveness of NOanremoval
integrated UV-heat/H
decreased 2O2 oxidation system that removed NO by
as the reaction temperature rose. Hao et al. [64]
96.3%.
developed an integrated UV-heat/H2 O2 oxidation system that removed NO by 96.3%.
Since
Since itit is
is challenging
challenging to to recover
recover thethe homogeneous
homogeneous catalyst
catalyst from
from the
the solution,
solution, the
the
proposed Fenton-like method is a good substitute for the use
proposed Fenton-like method is a good substitute for the use of transition metals of transition metals as cat-as
alysts.
catalysts. By substituting
By substitutingFe2+ Fe
with wet heterogeneous
2+ with wet heterogeneous Fenton (-like)(-like)
Fenton oxidation systems
oxidation (i.e.,
systems
utilizing metalmetal
(i.e., utilizing oxideoxide
catalysts or other
catalysts solid solid
or other materials to catalyze
materials H2O2Hto
to catalyze create OH
2 O2 to create
radicals),
OH radicals), it is suggested that the
it is suggested thatFenton process
the Fenton (homogeneous
process (homogeneouscatalysis) overcame
catalysis) these
overcame
drawbacks
these drawbacks [59,65–67]. FigureFigure
[59,65–67]. 5 illustrates the the
5 illustrates mechanism
mechanism of of NONOremoval
removalinin thethe
Fe O -based Fenton-like system
Fe2 O3 -based Fenton-like system [68].
2 3 [68].

Figure
Figure 5.
5. Mechanism
Mechanism ofof NO removal using Fe Fe22O33-based
-based Fenton-like
Fenton-like oxidation
oxidation system.
system. Modified
Modified
from
from[60]
[60]with
with permission
permission from
from Elsevier,
Elsevier, Copyright
Copyright 2019.
2019.

2.2.2.Peroxydisulfate/Peroxymonosulfate
2.2.2. Peroxydisulfate/Peroxymonosulfate(PS/PMS) (PS/PMS)Oxidants
Oxidants
SO
SO44•• has a larger oxidation potential, more selectivity,
a larger oxidation potential, more selectivity, greater efficiency,
greater and aand
efficiency, widera
range range
wider of pH ofadaptation than HO
pH adaptation •. ItHO•.
than is also
It utilized to oxidize
is also utilized SO2 andSO
to oxidize NOx concurrently.
2 and NOx con-
The two precursors,
currently. peroxydisulfate
The two precursors, (PS) and peroxymonosulfate
peroxydisulfate (PMS), typically
(PS) and peroxymonosulfate (PMS), have
typ-
standard
ically haveredox potentials
standard redoxofpotentials
2.01 V andof1.822.01V,Vrespectively
and 1.82 V,[69]. These two[69].
respectively sulfate radicals
These two
are kinetically sluggish and stable before stimulation but extremely reactive
sulfate radicals are kinetically sluggish and stable before stimulation but extremely reac-after stimula-
tionafter
tive [70].stimulation
The corresponding
[70]. Theformation
correspondingmechanisms of SO
formation 4 •− are shown
mechanisms of SOin reaction (19)
4•− are shown
and (20) [71,72].
in reaction (19) and (20) [71,72].
heat/UV/ultrasound
S2 O28− heat/UV/ultrasound
→ 2SO4•− (19)
2−
S2 O8 → 2SO•−4
(19)
(n)+ (n+1)+
S2 O28− + Me(aq) → SO4•− + SO24− + Me(aq) (20)
(n)+ (n+1)+
S2 O2− •− 2−
8 + Me(aq) → SO4 + SO4 + Me(aq) (20)
There are many factors influencing the oxidation process of SO2 and NOx by SO4 − •,
such as the temperature, pH value of the solution, and catalyst dosage. NO was oxidized
by PS in a bubble column reactor that was run in the semibatch mode [72]. The effects
of Na2 S2 O8 concentration, temperature, and solution pH on NO removal efficiency were
examined. It was found that the presence of SO2 significantly increased the NO gas
absorption and oxidation. The NO conversions in the presence of SO2 varied from 77 to
83% with lower temperatures (23 ◦ C and 30 ◦ C).
In the past years, several studies have focused on developing more effective activation
techniques for PS/PMS. Chen et al. [73] introduced a combined method with PMS and heat-
ing in a rotating packed bed (RPB) pilot reactor. The effectiveness of NO removal exceeded
70%. Liu et al. [74] looked into the variables affecting simultaneous desulfurization and
denitrification by using a NH4 S2 O8 /UV reactor with a heat exchanger. The elimination of
NO with the maximum effectiveness was 96.1%. This might be due to UV light, which sped
up the breakdown of S2 O8 2- into SO4 •, combined with water to create •OH, and had a
severe oxidizing effect on NO in both cases [75–77]. Liu et al. [74] then conducted research
 tion techniques for PS/PMS. Chen et al. [73] introduced a combined method with PMS
and heating in a rotating packed bed (RPB) pilot reactor. The effectiveness of NO removal
exceeded 70%. Liu et al. [74] looked into the variables affecting simultaneous desulfuri-
zation and denitrification by using a NH4S2O8/UV reactor with a heat exchanger. The
Separations 2022, 9, 307 elimination of NO with the maximum effectiveness was 96.1%. This might be due 10 toofUV27
light, which sped up the breakdown of S2O82- into SO4•, combined with water to create
•OH, and had a severe oxidizing effect on NO in both cases [75–77]. Liu et al. [74] then
conducted
on research on
the simultaneous the simultaneous
absorption of SO2 and absorption
NO by theofconcurrent
SO2 and NO by the
thermal concurrent
activation of
(NH4 )2 S2 O8 by an ultrasound and Fe . The suitable addition of Fe in the (NH4 )of
thermal activation of (NH ) S O by an ultrasound and Fe
4 2 2 8 2+ 2+. The suitable
2+ addition Fe2+
2 S2 O8
in the (NH
solution 4)2S2Othe
boosted 8 solution
oxidation boosted the oxidation
and absorption of NOand absorption
to some of NO to
extent because thesome extent
addition of
because
2+ the addition of Fe 2+ might result in the production of free radicals in the
Fe might result in the production of free radicals in the (NH4 )2 S2 O8 solution [78]. Figure 6
(NH4)2S2O8the
illustrated solution
removal[78]. Figure 6 illustrated
mechanism the removal
[79]. However, excessivemechanism
(NH4 )2 S2 O[79]. However, ex-
8 would engage in
cessive (NH4)2S2Oreactions
self-consumptive 8 would withengage freeinradicals
self-consumptive
SO4 • and •reactions
OH, reducingwiththe
freeeffectiveness
radicals SOof 4•

and •OH, reducing the

the NO elimination [69,80]. effectiveness of the NO elimination [69,80].

Figure 6. Removal
Removalmechanism of of
NONO
andand
SO2SO
by2ultrasound/Fe 2+ /heat/(NH
2+/heat/(NH 4)2S2O8 system.
Figure mechanism by ultrasound/Fe 4 )2 S2 O8Adapted
system.
from [79]from
Adapted . [79].

2.2.3. NaClO/ NaClO2 Oxidants

2.2.3. NaClO/ NaClO2 Oxidants
Flue gas contaminants are typically removed using hypochlorite and chlorate due to
Flue gas contaminants are typically removed using hypochlorite and chlorate due to
their high oxidizability. The mechanism of NOx removal was investigated by Liu et al. [81]
their high oxidizability. The mechanism of NOx removal was investigated by Liu et al.
utilizing UV-assisted Ca(ClO)2 and NaClO aqueous solution in a spray reactor. According
[81] utilizing UV-assisted Ca(ClO)2 and NaClO aqueous solution in a spray reactor. Ac-
to reactions (21) to (24), the direct oxidations of hypochlorite were the auxiliary reactions,
cording to reactions (21) to (24), the direct oxidations of hypochlorite were the auxiliary
while the oxidations of NO by a hydroxyl radical were the primary reactions (25)–(27).
reactions, while the oxidations of NO by a hydroxyl radical were the primary reactions
(25)–(27). UV light
HClO → ·OH + ·C (21)
UV light
HClO → ∙ OH +∙ C (21)
NO + ·OH ↔ HNO2 (22)
NO·OH
HNO2 + +∙ OH ↔ HNO
↔ HNO 2 ·H
3+ (22)
(23)
HNO2 + HClO ↔ HNO3 + HCl (24)
HNO2 +∙ OH ↔ HNO3 +∙ H (23)
NO + ClO− ↔ NO2 + Cl− (25)
HNO
3NO +2 O
2 +2H HClO ↔ HNO33++NO
↔ 2HNO HCl (24)
(26)
NO2 + H2 O ↔−HNO3 + HNO 2 (27)
NO + ClO ↔ NO2 + Cl− (25)
The direct removal of NO from flue gas using hypochlorite was not so impressive.
Byoun et al. [82] performed the removal tests of NO, SO2 , and Hg0 in flue gas from an
industrial combustion unit using a spray wet scrubber with NaClO at a concentration of
0.1 L/m3 . At a vaporization temperature of 165 ◦ C and a solution pH range of 4.0–6.0, the
removal efficiencies of NO were only 50%
A series of studies have been conducted on the factors influencing the removal of NO
from flue gas by chlorates. Zhao’s [50] research on the removal of NO from diesel engine
exhaust using an electron beam and a wet scrubber revealed that the performance of NO
oxidation removal went NaClO2 > NaClO3 > NaClO, from high to low. The elimination
rate for NOx increased to 95% when CaO2 was introduced to a NaClO2 solution for
oxidation [83]. Hao et al. [84] made a NaClO2 /Na2 S2 O8 compound oxidant to study the
oxidation of NO. The maximum NO elimination effectiveness could reach 82.7% under
optimal conditions. The effectiveness of NO removal rose with the compound oxidant flow
rate, solution pH, and vaporization temperature, but declined with the flue gas flow.
Recently, numerous processes have been studied to improve removal efficiency.
Hao et al. [85] proposed a three-region NO oxidation elimination technique with a NO
removal effectiveness of 94.5%. Furthermore, it was shown that ClO2 was quite selective in
the oxidation of NO. ClO2 is more likely to oxidize NO when various contaminants coexist
Separations 2022, 9, 307 11 of 27

in the flue gas. The results agreed with Hao’s [86] findings after oxidizing NO and Hg0
with UV/NaClO2 , UV/NaClO, UV/Na2 S2 O8 , UV/KHSO5 , and UV/H2 O2 . In comparison
to the others (•OH and SO4 •), the free radicals formed by UV/NaClO2 and UV/NaClO
showed higher activity, selectivity, and a better tolerance to the high concentration of
SO2 . As a result, chlorate had a high rate of oxidation and was simple to obtain, offering
considerable potential for the combined removal of contaminants from flue gases.

3. Reduction Methods
Numerous reductants, including gaseous reductants, liquid reductants, and solid
reductants, can convert NO in flue gas to N2 . The reduction process, catalysts, mechanism,
and key factors impacting the removal efficiency are reviewed. Table 4 summarizes the
typical reductants used for NOx purification from flue gas based on the physical states of
these reductants.

Table 4. Typical reductants used for technologies of NOx removal.

Physical
Reductants Technologies Reaction Scheme Key Factors Ref.
State
4NH3 + 4NO + O2 → 4N2 + 6H2 O
4NH3 + 6NO → 5N2 + 6H2 O Temperature window, NH3 /NOx
Gas Ammonia (NH3 ) SCR ratio, oxygen concentration, catalyst [87]
4NH3 + 2NO + 2NO2 → 4N2 + 6H2 O
8NH3 + 6NO2 → 7N2 + 12H2 O loading and the type of catalyst
Hydrogen (H2 ) SCR 2NO + 4H2 + O2 → N2 + 4H2 O support used [88]
temperature, reagent/flue gas
2CO(NH2 )2 + 4NO + O2 → 4N2 + 2CO2 +
Urea (CO(NH2 )2 ) SNCR mixing, reagent/NOx ratio and [89]
2H2 O
reaction time
Gas–liquid ratio, solution
Sodium sulfide concentration, oxidants
Liquid Wet Scrubbing 2NO2 + Na2 S → N2 + Na2 SO4 [30]
(Na2 S) concentration, temperature, pH
Urea solution Wet scrubbing 2HNO2 + NH2 –CO–NH2 → 2N2 + CO2 + 3H2 O value, reaction time [90]

3.1. Gas Reductants

The gas phase reduction of NO often involves the use of NH3 /urea, CO, H2 , and HC.

3.1.1. NH3 and Urea(CO(NH2 )2 ) Reductants

The current gas phase NOx treatment methods are mainly selective catalytic reduction
(SCR) and selective non-catalytic reduction (SNCR).
Selective catalytic reduction (SCR) of NOx using ammonia (NH3 ) has been extensively
investigated. Due to the great efficiency (>90%) and good stability of this technology,
post-combustion NOx removal has been applied in numerous industrial applications [91].
It is well known that the main reactions of SCR with NH3 are as below [92,93]:

4NH3 + 4NO + O2 → 4N2 + 6H2 O (28)

4NH3 + 6NO → 5N2 + 6H2 O (29)

4NH3 + 2NO + 2NO2 → 4N2 + 6H2 O (30)
8NH3 + 6NO2 → 7N2 + 12H2 O (31)
Regarding the side reactions, the most frequently employed catalysts have a tendency
to produce nitrous oxide (N2 O) at high temperatures (>400 ◦ C). As demonstrated in
reactions (32) and (33), which depict the oxidation of NH3 to NO, the unfavorable oxidizing
characteristics of the SCR catalysts became more prominent at temperatures greater than
500◦ C, hence restricting the maximal NOx conversion [94]. Ammonium nitrate (NH4 NO3 )
would be generated at lower temperatures below 200 ◦ C in accordance with reaction
(34) [87].
4NH3 + 4NO + 3O2 → 4N2 O + 6H2 O (32)
Separations 2022, 9, 307 12 of 27

4NH3 + 5O2 → NO + 6H2 O (33)

2NH3 + 2NO2 → NH4 NO3 + N2 + H2 O (34)
Catalysts are one of the most important factors influencing the removal efficiency
of SCR, which can directly determine other factors, such as the temperature, residence
time, and ratio of NH3 /NOx. Catalysts should possess the following characteristics when
selecting appropriate SCR catalysts: a high mechanical strength, high de-NOx activity,
operating temperature range, and excellent anti-poisoning. Catalysts of several varieties,
including supported noble metals (Pt, Pd, Ag, Au), supported noble/transition metals
(Pt/Al2 O3 , Pd/Al2 O3 , Rh/Al2 O3 , Rh/ZSM-5, etc.), supported transition metal oxides (NiO,
CO3 O4 , V2 O5 , Fe3O4 , MnO2 , etc.), and transition metals (Cu, Fe, Cr, V, Mn, etc.) have been
studied [91,95,96].
Mn-based catalysts have been the most widely explored among all transition metals
because of their high NOx removal potential at low temperatures [97]. The primary
variables that determine the catalytic activity of MnOx are crystallinity, specific surface
area, shape, and the oxidation state of Mn [98]. The fact that Mn is a multivalent transition
metal allows it to create a variety of stable oxides. MnO2 > Mn5 O8 > Mn2 O3 > Mn3 O4 >
MnO is the order of the MnOx catalysts’ activities [99]. The efficiency of NOx removal was
improved by increasing the amount of oxygen vacancies on the surface of the catalysts.
However, deactivation is a problem for Mn-based catalysts as well. Chemical poisoning,
sulfur poisoning, hydrocarbon poisoning, and hydrothermal deactivation are the principal
deactivation processes of Mn-based catalysts [100–106]. The performance of Mn-based
catalysts against SO2 poisoning and their high-temperature hydrothermal stability are still
subpar, and there are few current studies in this area. Future study could concentrate
on enhancing the catalyst’s functional elements and creating novel support materials to
extend the catalyst’s useful life, increase its dependability, and lessen the deactivation of
Mn-based catalysts.
Similar to SCR, SNCR also has a broad use, regardless of the cost of its catalysts. With
NH3 acting as the reductant, the reaction temperature window for SNCR typically ranges
from 850 to 1100◦ C. The operating circumstances have an impact on the reduction efficiency.
The normal removal efficiency in actual applications is less than 50%. Urea is a preferred
agent as an alternative to NH3 because of its nontoxicity, durability, high performance in a
wide temperature range, and low NH3 slip [9]. The decomposition mechanism of urea is
described as follows [93]:

NH2 –CO–NH2 (aqueous) → NH2 –CO–NH2 (molten) (35)

NH2 –CO–NH2 (molten) → NH3 (gas) + HNCO (gas) ∆H298 = +186 kJ/mol (36)
298
HNCO (gas) + H2 O (gas) → NH3 (gas) + CO2 (gas) ∆H = −96 kJ/mol (37)
The overall urea breakdown is depicted in reaction (38).

NH2 –CO–NH2 +H2 O → 2NH3 +CO2 (38)

Recently, research on urea-SCR-based catalysts has also been conducted. The NO

conversion mechanism on the binary Cu0.5 Mn0.5 /NUAC catalyst was presented and exten-
sively studied after a number of binary catalysts were created [107].
Concerns about handling large amounts of NH3 include: (I) safety issues, high toxicity,
and corrosion; (II) the outlet discharge of unreacted NH3 to the environment; (III) the
formation of ammonium sulfate, a corrosive and sticky liquid that is harmful to combustion
and downstream equipment; and (IV) high operating costs [5].

3.1.2. H2 Reductants
Hydrogen is regarded as a clean fuel and an environmentally favorable substance.
As a result, the favored NOx removal technique for catalysts is a low-temperature and
Separations 2022, 9, 307 13 of 27

selective catalytic reduction using H2 . H2 offers a viable solution to meet the criterion of
raising emission limits without introducing secondary pollutants [88]. Under conditions
of excess oxygen, H2 has been studied as an effective reducing agent for SCR. Due to its
high efficiency, ability to reduce NOx at lower temperatures (<200 ◦ C), high N2 selectivity,
and ability to only produce water, this technology is considered to be environmentally
friendly [108].
H2 -SCR technology is particularly useful in industrial settings with access to H2 gas,
such as petrochemical factories and oil refineries. The reactions of NO removal by H2 -SCR
in the presence of O2 are shown as follows [88]:
 
2NO + 4H2 + O2 → N2 + 4H2 O ∆H298 = −574.0 kJ/mol NO (39)
 
2NO + 3H2 + O2 → N2 O + 3H2 O ∆H298 = −412.0 kJ/mol NO (40)
 
O2 + 2H2 → 2H2 O ∆H298 = −241.8 kJ/mol H2 (41)
 
2NO + H2 → N2 O + H2 O ∆H298 = −170.2 kJ/mol NO (42)

Catalysts are still the key factor in H2 -SCR. The two primary components of H2 -SCR
catalysts are active components and supports. The active components, such as noble
metals, bimetallic complexes, and non-noble metals (like Ce and Zr), have been extensively
studied [109,110].
In H2 -SCR, noble metals are frequently utilized as catalysts. Noble metals have the
ability to degrade H2 . Then the degraded H2 converts NO into N2 effectively. Platinum
is one of the most frequently utilized noble metals for H2 -SCR (Pt). According to Resi-
toglu [111], the reaction over the Pt/Al2 O3 catalyst began at about 90 ◦ C. However, Pt
catalysts have a limited selectivity for N2 and an excellent selectivity for N2 O, despite
having significant activity at low temperatures. The type of supports had a significant
impact on the catalytic activity of the Pt catalyst (such as Al2 O3 , SiO2 , ZSM5, etc.) [110].
The catalyst activity could be impacted by the acidity and alkalinity of the catalyst. The
Pt/SiO2 catalyst performed better in terms of activity at low temperatures when Al2 O3 and
SiO2 were compared as supports.
Noble metal catalysts, on the other hand, were poorly resistant to sulfur dioxide, which
caused sulfates and sulfites to develop on the catalysts’ active sites. Such species eventually
caused the SCR to stop working and decrease NO removal at low temperatures [112]. The
fundamental drawback of H2 -SCR is the prevalence of expensive supported noble metal
catalysts as its active catalysts.

3.1.3. HC Reductants
The SCR of NOx with hydrocarbons(HC) as reducing agents has attracted a great deal
of attention [113]. HC-SCR appeared to be a promising technique for the removal of NOx
from flue gas [114]. However, the reducibility of CH4 was significantly lower than that of
H2 and CO, because it was a non-polar, high-bond-energy tetrahedron molecule [115].
The oxidation of NO to surface nitrates and the concurrent oxidation of HC to surface
oxygenates are the initial steps in the HC-SCR reaction of NOx. The ensuing reaction
between the surface intermediates results in the formation of CN and NCO species. After
then, the hydrolysis or oxidation of N2 -containing molecules triggers the production of N2
and CO2 .
Studies have shown that the surface acidity of catalysts, the oxidation activity of metal
ions, and the degree of metal dispersion were crucial variables impacting catalytic activities,
even though some aspects of these reaction processes were conflicting. Below are the SCR
reactions for NOx emissions utilizing HCs as the reductant [116]:

N2 + O2 → NO2 (43)
Separations 2022, 9, 307 14 of 27

Cx Hy Oz + NO2 → N2 + CO2 + H2 O (44)

The small temperature window of HC-SCR in comparison to other de-NOx systems is
one of its drawbacks (NSR and urea-SCR). These traits are largely related to hydrocarbons’
low selectivity for NOx [117]. Therefore, a range of active catalysts was used in the
HC-SCR process to improve the catalytic performance and widen the active temperature
window [118,119].

3.1.4. CO Reductants
Carbon monoxide (CO) is recognized as an efficient reagent for NOx reduction due to
its cheap cost. Since CO is also created during combustion and coexists in flue gas, CO-SCR
technology reduces NOx and CO concurrently, and it is anticipated that using CO as the
reducing agent would result in a far more affordable and straightforward feeding system
for the NOx abatement process [120].
The following two reactions might take place on the surface of a catalyst based on
the catalytic process of the L-H mechanism for supported metal oxide catalysts (M: low-
valence-state metal oxide, MO: high-valence-state metal oxide) [121]:

MO + CO(g) → M + CO2 (g) (45)

M + NO(g) → MO + N2 (g) (46)

Other two reactions also take place in the presence of oxygen:

M + NO(g) + O2 (g) → MO + N2 (g) (47)

M + O2 (g) → MO (48)
In addition, the subsequent four reactions (Mx(SO4 )y: metal sulfate) would also take
place in the presence of O2 , SO2 , and H2 O [122]:

M + H2 O(g) + SO2 (g) → Mx (SO4 )y + H2 (g) (49)

MO + H2 O(g) + SO2 (g) → Mx (SO4 )y + H2 (g) (50)

M + O2 (g) + SO2 (g) → Mx (SO4 )y (51)

MO + O2 (g) + SO2 (g) → Mx (SO4 )y (52)

Mx (SO4 )y + CO(g) → M + COS(g) + CO2 (g) (53)

Mx (SO4 )y + CO(g) → MO + COS(g) + CO2 (g) (54)

When oxygen, sulfur dioxide, and water vapor are present, reactions (49), (50), (51)
and (52) lead to the poisoning and deactivation of the catalyst. It is clear from (53) and (54)
that employing CO as a reductant could prevent sulfur dioxide from poisoning catalysts,
which would help extend the catalyst’s life.
CO might be an advantageous reducing agent for NOx removal utilizing the SCR
method due to its poisonous nature [123]. The newly created class of internal combustion
engines, such as HCCI (homogeneous charge compression ignition) engines, released rela-
tively large levels of CO, which could be employed to reduce NO [124]. Since it could be
produced onsite due to the utilization of coal or natural gas at stationary sources, the expen-
sive steps of purchasing, transporting, and storing the reductant could be eliminated [125].

3.2. Liquid Reductants

Using substances, such as ammonia, urea, sodium sulfide (Na2 S), and others, in
aqueous solutions to reduce NOx from flue gas is another de-NOx technique. For instance,
the elimination of NOx could be accomplished via an absorption method with the addition
of Na2 S as a reductant. Mechanism related is shown in reaction (55) [30]. The majority
Separations 2022, 9, 307 15 of 27

of liquid reductants, such as aqueous urea or ammonium salts, often involve the direct
reduction of NOx. In real-world applications, liquid reductants are frequently employed as
absorbents to take acidic gases from flue gas and fix them with more reductants or oxidants.
More detailed relevant trials are required to offer a trustworthy method and development
because some outcomes have been disagreed upon or need further validation.

2NO2 + Na2 S → N2 + Na2 SO4 (55)

Studies also put attention on techniques combining NOx oxidation and reduction
methods in aqueous solutions. Kim et al. designed and tested a wet packed-bed scrubber
with a DBD plasma oxidation process using the reducing agents Na2 SO3 and Na2 S [126].
With a lower chemical consumption and liquid-to-gas ratio, the results indicated that the
Na2 S solution was more suitable than Na2 SO3 .

3.3. Solid Reductants

Polyoxometalates (POMs) have sparked a significant amount of interest from both
academic and industrial groups, due to their Bronsted acidity, vast molecule volume,
abundant active “lattice oxygen,” and pseudo-liquid-phase characteristic [127]. Among the
POMs, H3 PW12 O40 (HPW) stood out among the group thanks to its stronger affinity for the
polar NO and NO2 molecules. The published literature claimed that, in addition to nitrate,
the adsorbed NOx also exists in the bulk structure as NOH+ and N2 O3 [128]. Yang [129]
and Belanger [128,130] completed a series of pioneering works on the adsorption and
denitrification performance of HPW. Yang developed a two-step process using H3 PW12 O40
as a solid catalyst to efficiently reduce NO to N2 in flue gas without the use of any reducing
gas. A total of 70% of the NO in a simulated flue gas was absorbed in the fixed bed at
150 ◦ C at a space velocity of 5000 h−1 . A total of 68.3% of the absorbed NO was converted
into N2 at 450 ◦ C. The absorption of NO required the presence of O2 and H2 O, whereas
SO2 and CO2 had no impact on either absorption or decomposition. These results were
confirmed by McCormick [131] and Zhang [132].
Keggin-type polytungstic acid is one of the most significant POMs and might produce
a variety of lacunary structures when the pH of its solution rises. With more internal
oxygen atoms exposed, these lacunary POMs could interact with different metals to gener-
ate substituted-type saturation structures, which would enhance the surface properties of
POMs. Germanium POMs were used as adsorbents and catalysts in a two-step procedure
described by Wang et al. [127]. W, Mo, and V derivatives of the Keggin structure were cre-
ated. A maximum adsorption efficiency of 80% (16.2 mgNO2 /g) and an optimal adsorption
temperature of around 230 ◦ C were found for germanium-based POMs.
There are three basic challenges in NO reduction by solid reductants: (1) the efficient
NO adsorption on the solid surface; (2) quick NO breakdown and desorption; and (3) the
cyclic renewal of the solid reducing agent.

4. Absorption/Adsorption Methods
Along with oxidation and reduction techniques, various liquids and solids could
absorb or adsorb NO from flue gas without altering their chemical valence. NO is then
desorbed and collected by adjusting pressure, temperature, pH of solution, etc. As a result,
the absorption/adsorption process produces pure gas compounds or beneficial by-products.
Both liquid phase absorption and solid phase adsorption processes have been thoroughly
studied.

4.1. Liquid Absorbents

4.1.1. Alkaline Solution
Alkaline solution absorption was effective for treating exhaust gases that contained
more than 50% NO2 . Due to the low solubility of NOx, NOx in alkaline solutions could
be transformed into nitrite salts that have a tendency to disintegrate at low pHs and high
temperatures [133]. Based on these characteristics, high-valence NOx was often absorbed
 -
NO(g) + NO2 (g) ⇔ N2 O3 (g)
Separations 2022, 9, 307 16 of 27
NO(g) + NO2 (g) + H2 O(g) ⇔ HNO2 (g) -
w
as-liquid 2NO2 (g)using⇔the2H +
alkali +
−
NO2absorption
solution + NO3method−
following oxidation. While 102
2.44the× absorption
w
effectiveness and the ratio−
of NO2 /NO− were relatively low, this technology might 1recycle
+ 3.56 × 10
N2 O4 (g)
NOx into2H
⇔ + NO
chemicals + NO3 and sulfate, which are commercially
such2as nitrite/nitrate viable.
w
The mechanism of NOx absorption -5 into
in alkaline solutions can be mainly divided
N2 Ogas-phase
3 (g) ⇔ equilibrium, 2NO2 −equilibrium, and liquid-phase equilibrium.
2H + +gas–liquid 6.14 × 10 The main
w summarized in Table 5 [133].
reactions are
N2 O5 (g) ⇔ 2H + + 2NO3 − 4.25 × 1017
Table 5. Reactionswof NOx absorption from gas phase to liquid phase [133].
NO2 (g) + NO2 − ⇔ NO3 − + NO(g) 7.43 × 106
Reaction Phase w
Equilibrium Equilibrium Constant Value Units
Gas HNO2NO
2 (g) ⇔ HNO (l)
2 (g) ⇔ N2 O4 (g) 2 - --
w
3HNO2 (l)NO⇔ g) ⇔ N2 O−
H +2 (+
(g) + NO
NO3 3 (g+ )
2NO(g) -
3.01 × -101
NO(g) + NO2 (g) +w 2H O ( g ) ⇔ HNO 2 (g) - -
+ − −4
Liquid Gas-liquid HNO
2NO2 (2g(l)
w ⇔
) ⇔ 2H + +HNO2 −+ + NO
NO3 −2 2.44 × 102 4.60 × 10
(kmol/m3 )4 /atm2

ww + 3 )4−4
+ NO2 − +−
3HNO2 (l) ⇔ Hw+ + 3.56 × 101 1.12
−
N2 O4 (g) ⇔ 2H
NO3 NO+ 3
2NO(l) × 10
(kmol/m /atm

N2 O3 (g) ⇔w 2H+ + 2NO2 − 6.14 × 10−5 (kmol/m3 )4 /atm

5
−
2H + + 3NON2 O5 (2
⇔ NO3 −3 −+ 2NO(l)
w
g) ⇔ 2H+ + 2NO 4.25 × 1017
8.46 × 10
3 4
(kmol/m ) /atm
w represents
w reactions occurring in
NO2 (g) + NO2 − ⇔ NO3 − + NO(g) 7.43presence
× 106 of water. -
w
HNO2 (g) ⇔ HNO2 (l) - -

For the
3HNO2 (l) ⇔
w
+ NOabove
H+ 3 + 2NO(greactions,
− ) some
3.01 × 10are dominant. The absorp
1 atm2 /(kmol/m3 )
w
Liquid
water l) ⇔ H+the
HNO2 (and −
+ NONaOH
2 solution × 10−4depicted in
4.60was kmol/m3
Figure 7 [13
w
3HNO2 (l) ⇔ H+ + NO3 − + 2NO(l) 1.12 × 10−4 kmol/m3
NOx
+
absorption
− w −
in water and the alkaline
5
solution 3are
−2
summa
2H + 3NO2 ⇔ NO3 + 2NO(l) 8.46 × 10 (kmol/m )

3NO2 + H2 O → 2HNO3 + NO ↑
w represents reactions occurring in presence of water.
(W
For the above reactions, some are dominant. The absorption mechanism of NOx in
water and the NaOH solution was depicted in Figure 7 [134]. The overall reactions of NOx
− − in reactions
− (56)–(58):
2NO + 2OH → NO + NO + H O
absorption in water and the alkaline
2 solution are summarized
3 2 2 (Alka
3NO2 + H2 O → 2HNO3 + NO ↑ (Water) (56)

NO + NO + 2OH − → 2NO− + H2 O
2NO2 + 2OH− → NO3− + NO −
2 2 + H2 O (Alkaline solution
2 ) (Alkal
(57)
NO + NO2 + 2OH− → 2NO2− + H2 O (Alkaline solution) (58)

Figure 7. Scheme of NOx absorption into water and NaOH solution.

Figure 7. Scheme of NOx absorption into water and NaOH solution.

More attention should be given to reducing physical mas

Separations 2022, 9, 307 17 of 27

More attention should be given to reducing physical mass transfer limitations. High
mass-transfer rate absorbers need to be developed to alleviate the footprint problems
associated with tandem processes [135].

4.1.2. Complex Absorbents

A variety of chelating agents were added to the solution to form a complex in order
to increase the removal effectiveness of NO [136]. The solubility of NO in a solution
could be greatly improved by adding metal complexation agents (often ferrous and cobalt
chelating agents) to the wet scrubbing process, which helps to improve the effectiveness of
de-NOx [137].
Chelating substances, such as Fe2+ -EDTA (ethylenediaminetetraacetic acid, or EDTA),
could improve the solubility of NO by creating stable ferrous-nitrosyl complexes as shown
in reactions (59)–(62) [138]. Because Fe2+ -EDTA was quickly oxidized to Fe3+ -EDTA by
O2 , NO, and NO2 in flue gas (reactions (78) and (79)), the concentration of the active
Fe2+ -EDTA in the scrubbing solution diminished quickly. The removal effectiveness of NO
declined dramatically.
NO(g) → NO(aq) (59)
h i 2− h i 2−
NO(aq) + Fe2+ − EDTA → Fe2+ − EDTA(NO) (60)
h i2− h i−
4 Fe2+ − EDTA + O2 + 4H+ → 4 Fe3+ − EDTA + 2H2 O (61)
h i2− h i−
2NO + Fe2+ − EDTA + 2H+ → N2 O + Fe3+ − EDTA + H2 O (62)

The crucial stage in de-NOx by the Fe2+ -EDTA solution was the regeneration of
Fe2+ -EDTA, which involved changing Fe3+ -EDTA and Fe2+ -EDTA(NO) to Fe2+ -EDTA in or-
der to maintain a high NO removal efficiency. Therefore, to effectively reduce Fe3+ -EDTA at
room temperature, a variety of materials have been used, including activated carbon [139],
metal (Se, Zn, Fe, and Al) powders and compounds [140–142], thiosulfates [143], sul-
fites [144], and bisulfates [145,146]. Reaction (63) shows how iron(0) is used to regenerate
Fe3+ -EDTA:
h i 2− h i 2−
5Fe + 2 Fe2+ − EDTA(NO) + 12H+ → 2 Fe2+ − EDTA + 5Fe2+ + 2NH4 + + 2H2 O (63)

It was found that in the presence of sulfite (SO3 2 ) and hydrosulfite (HSO3 − ) ions, Fe3+ was
gradually reduced back to Fe2+ , which meant that a specific SO2 level in the flue gas could
promote NO absorption [147]. However, when the SO2 concentration was excessive, SO2
might compete with NO for the limited complexant (Fe2+ -EDTA) in the solution, thereby
reducing the efficiency of de-NOx.
The pH of the solution is another important factor affecting the efficiency of NOx
removal. In comparison to both low and high pH values, an intermediate pH often
resulted in a higher elimination efficiency [148,149]. It could be concluded that at a pH of
around 6.0, the complex formation constant of Fe2+ -EDTA was at its highest value. The
complex formation constant decreases significantly as the solution becomes more acidic or
more alkaline.

4.2. Solid Adsorbents

NOx could also be removed from flue gas directly through adsorption using porous
solid adsorbents. The removal efficiency, activation techniques, and factors influencing the
efficiency (such as coexisting gases and humidity) were reviewed. In addition to activated
carbons and zeolites, metal-organic frameworks (MOFs) have recently been applied.
Separations 2022, 9, 307 18 of 27

4.2.1. Activated Carbons (AC)

Due to its high porosity, large surface area, and varied surface chemical properties,
activated carbon (AC) is widely utilized industrially as an adsorbent for the control of
NOx. Table 6 summarizes the adsorption of NOx with activated carbons from different
carbon sources.

Table 6. Adsorption of NOx with activated carbons from different carbon sources.

Activation BET
Carbon Source Reaction Condition Performance Ref.
Condition Surface (m2 /g)
Temperature 120 ◦ C, gas flow
rate 0.420 Nm3/h, composition
Commercial Steam activation Removal efficiency:
218 of gases: 82.8% N2 , 6.0% O2 , [150]
activated coke (800 ◦ C) 30.4%
11.0% H2 O, 1000 ppm NO and
1000 ppm NH3 .
Temperature: 200 ◦ C, space
velocity: 6500 L/(kg·h), SO2
Steam activation (1500 ppm), NO (500 ppm),
Commercial Removal efficiency:
(850 ◦ C), V - NH3 (500 ppm), O2 (3.4%), H2 O [151]
activated carbon 70%
impregnation (2.5%), N2 balance, gas flow
rate: 7.00 L/min, contact time:
150 min
Temperature: 200 ◦ C, SO2 (200
Commercial 1 M HNO3 ± 10 ppm), NO (60 ± 3 ppm),
Removal efficiency:
activated carbon impregnation for 1498 air balance, gas flowrate: 0.06 [152]
60%
fibers 48 h L/min, contact time:
20 min
Sorbent: 3.00 g, temperature: 25
Ionic liquid and ◦ C, SO (5 ppm), NO (5 ppm),
2 2
Breakthrough time:
Coconut shell KOH 1114 RH (50%), air balance, gas flow [153]
41 min
impregnation rate: 30.00 L/min, contact time:
1200 min
Temperature: 150 ◦ C, SO2 (2000
CO2 activation
ppm), NO (500 ppm), O2 (10%), Adsorption
Palm shell (1100 ◦ C), Ce - [154]
N2 balance, gas flow rate: 0.15 capacity: 3.5 mg/g
impregnation
L/min, contact time: 300 min

Because of the limited physisorption of pollutants on the micropores or surface of

AC, the absorbed gas escapes frequently when the temperature or air pressure changes.
To enhance catalytic performance, AC must be treated with pre-activation or covering
components. The porosity, surface area, and pore size of ACs could be improved via both
physical activations (steam and CO2 activation) and chemical activations (metal oxides,
alkaline metals, and acids) [155]. Gao et al. [156] investigated the NO adsorption process
using NiO-modified AC/KOH at room temperature. A 5.26 mg/g adsorption capacity and
a 95.6% adsorption efficiency were attained. The results showed that a rise in lattice oxygen
(O2 - in Ni-O) and OH-/Ox species was responsible for the high removal efficiency of NO.
Flue gas typically contains O2 and water vapor, which improve NO removal. The
adsorbed NO on the surface of AC could be easily oxidized by O2 , then NO2 could
be captured by H2 O to form nitrate acids or salts. The Langmuir–Hinshelwood and
Eley–Rideal models provide excellent illustrations of the oxidation pathways of NO over
AC [157].
However, the coexistence of SO2 restricted the NO adsorption, with little NO adsorbed
when the SO2 concentration was more than 700 ppm and the NO adsorption capacity
decreased as the SO2 /NO ratio increased [158]. Due to the creation of sulfates and the
sulfating of the AC surface, additional downsides have also been documented, including
deactivation at low temperatures and poisoning in the presence of SO2 [159].
Separations 2022, 9, 307 19 of 27

The disadvantages mentioned above could be alleviated by impregnating AC with

metal oxides (V2 O5 , CuO, Fe2 O3 , MnO2 , Cr2 O3 , and CeO2 ), which act as initiators to
oxidize NO or reduce it to N2 . For instance, while palm shell activated carbon (PSAC)
could remove SO2 , it might remove SO2 and NO concurrently when it is impregnated with
metal oxides, especially when it is impregnated with 10% the weight of CeO2 [160,161].
The regeneration process played a crucial role in the adsorption technology of NOx.
An effective regeneration of the adsorbents ensures the cost-effectiveness and sustainability
of the integrated process for the removal of NOx from flue gas. Studies have obtained high
regeneration efficiencies (94.2% over five cycles [162] and 94.8% over two cycles [163]) of
activated carbon monoliths synthesized with cobalt oxide (ACM-Co3 O4 ). Furthermore,
Li et al. [164] found that the SCR activity of AC significantly improved after several
desulfurization and regeneration cycles, which indicated that the presence of SO2 could
enhance the performance of AC adsorbence after regeneration.

4.2.2. Zeolites
Zeolites have been widely employed as an adsorbent for SOx and NOx removal be-
cause of their low cost, nontoxicity, special surface features, and well-defined pore structure.
The mechanism of NOx adsorption removal on the zeolites was studied.
Zheng et al. [165] prepared Pd/zeolite as a passive NOx adsorber (PNA) material. It
was found that NOx trapping and release were not simple chemisorption and desorp-
tion events but involved rather complex chemical reactions. Fundamentally, NO might
either physically adsorb by permanently attaching to the surface and forming nitrosyl
complexes, or it could reversibly bind to the surface through the binding of nitrogen with
the framework cations. Pressure swing adsorption (PSA) allowed the removal of physically
adsorbed NO with a minor reduction in pressure, while chemically adsorbed NO could not
be removed as readily, even at extremely low pressures [11].
The adsorption performance of zeolites could be effectively improved by surface
impregnation. To improve the purification performance of NaX zeolite, ion exchange
experiments were conducted with cation K+ , Ca2+ , Mn2+ , and Co2+ by Deng et al. [166].
The result showed that a massive amount of purified NO was degenerated in a reductive
way and mainly converted to N2 . Chiu et al. [167] found that CuCl2 impregnation on the
zeolite MCM-41 (MCM) increased the NO removal from 62.8% to up to 73%.
Several studies have focused on combined technologies to improve the effectiveness of
NO adsorption and remove NOx at the same time. Wang et al. [168] observed NOx storage
and reduction with CH4 over HZSM-5. With this method, a 95% elimination effectiveness
of NOx could be attained at room temperature. The effectiveness of NOx removal was
kept at over 90% in a cyclic operation. The NOx storage and reduction over HZSM-5 in
conjunction with non-thermal plasma in the presence of water were also explored by Wang
et al. Due to the competing adsorption of H2 O and NOx on the surface of HZSM-5, the
NOx adsorption capacity might be reduced when H2 O is present [169].

4.2.3. Metal-Organic Frameworks (MOFs)

More than 20,000 different MOFs have been created in the last decade. Since their
microstructure and constituents are flexible, their shape, size, and functionality can be
modified [170]. As for chemisorption, several primary adsorption pathways between
SO2 /NOx and the active sites of MOFs were proposed [171,172]. Acid–base interactions,
complexation, and hydrogen bonds all played significant roles in the chemisorption among
various host–guest interactions. Figure 8 summarizes these important mechanisms of
adsorption between NOx and MOFs.
When exposed to industrial exhaust flue gas, very few MOFs have been observed
to be stable [173]. Large-scale MOF production has not yet been commercialized. More
attention has been dedicated to improving the stability and selective adsorption capability
of MOFs in recent years.
Separations 2022, 8, x FOR PEER REVIEW 21 of 29
Separations 2022, 9, 307 20 of 27

Figure 8. Main mechanisms between NOx and active sites of MOFs. Modified from [171] with
Figure 8. Main
permission mechanisms
from between2013.
Elesvier, Copyright NOx(a) and active sites
Adsorption on of MOFs. Modified
coordinatively from [171]
unsaturated with
sites (CUS);
permission from Elesvier, Copyright 2013. (a) Adsorption on coordinatively unsaturated
(b) Acid base interaction; (c) Electrostatic interaction; (d) Hydrogen bonding; (e) п-complex formation;sites
(CUS); (b) Acid base
(f) Breathing effect. interaction; (c) Electrostatic interaction; (d) Hydrogen bonding; (e) п-complex
formation; (f) Breathing effect.
5. Conclusions and Perspectives
When
In this exposed
paper, to theindustrial exhaust flue
recent literature wasgas, very few
reviewed onMOFs have been observed
the purification technologies to
beforstable
NOx[173].removalLarge-scale
from flue MOFgas.production has not yet been
A novel classification methodcommercialized.
was proposedMore from at-the
tention has been
perspective dedicated
of changes to improving
in the valence of the stability
nitrogen (N).and selectiveto
According adsorption capability
different transforma-
oftion
MOFs in recent (methods
approaches years. causing an increase, decrease, or no change in the chemical
valence of nitrogen), the purification against NOx from flue gas was classified into three
5.types:
Conclusions
oxidation and Perspectives
methods (N valence increased), reduction methods (N valence decreased)
andIn absorption/adsorption methods was
this paper, the recent literature (no change
reviewed in on
N valence). The removal
the purification processes,
technologies for
mechanisms,
NOx removal and frominfluencing
flue gas. Afactors
novel of each method
classification were reviewed
method according
was proposed fromtothe
different
per-
physicalofstate
spective reagents.
changes in the valence of nitrogen (N). According to different transformation
Oxidation
approaches (methods methods utilize
causing gas oxidants
an increase, (including
decrease, oxygenin(Othe
or no change 2 ), chemical
ozone (Ovalence
3 ), Chlo-
rine (Cl
of nitrogen),2 )/Chlorine dioxide (ClO
the purification against ) and non-thermal plasma (NTP)), and
2 NOx from flue gas was classified into three types: liquid oxidants
(including
oxidation H2 O2 , peroxydisulfate/peroxymonosulfate
methods (N valence increased), reduction methods (PS/PMS), and NaClO/NaClO
(N valence decreased) and2 ).
Among these reagents, methods
absorption/adsorption gas oxidants(nohave attracted
change in Na large amount
valence). Theof removal
attention due to their
processes,
full and effective contact with NOx. However, the high energy
mechanisms, and influencing factors of each method were reviewed according to dif- consumption of oxidants’
generation
ferent physicalrestricted their large-scale use. Methods utilizing liquid oxidants possessed
state reagents.
many advantages, such
Oxidation methods utilize as available and inexpensive
gas oxidants (includingreagents,
oxygen (O simple operations, and the
2), ozone (O3), Chlorine
simultaneous removal of multi-pollutants. Nevertheless,
(Cl2)/Chlorine dioxide (ClO2) and non-thermal plasma (NTP)), and liquid high oxidation performance
oxidants (in- still
required homogeneous and heterogeneous catalysts to
cluding H2O2, peroxydisulfate/peroxymonosulfate (PS/PMS), and NaClO/NaClO2). participate in the reaction. Solid
catalysts
Among showed
these their promise
reagents, in liquid
gas oxidants haveoxidation
attractedduea to the amount
large uncomplicated recovery
of attention duefrom
to
aqueous
their solutions.
full and effective contact with NOx. However, the high energy consumption of ox-
idants’Reduction
generationmethods
restrictedwere
theirwidely applicable
large-scale in mostutilizing
use. Methods industrial
liquidsituations.
oxidants Muchpos-
research has been focused on the design and development of more efficient, more durable
sessed many advantages, such as available and inexpensive reagents, simple operations,
catalysts that is more resistant to H2 O and SO2 . Liquid reductants were generally utilized
and the simultaneous removal of multi-pollutants. Nevertheless, high oxidation perfor-
after the oxidation of NOx into NO2 to ensure a high reduction efficiency. Recently, solid
mance still required homogeneous and heterogeneous catalysts to participate in the re-
reductants have attracted interest from both academic and industrial groups. For instance,
action. Solid catalysts showed their promise in liquid oxidation due to the uncomplicated
H3 PW12 O40 (HPW) was reported to reduce NO without any reducing gas.
recovery from aqueous solutions.
Absorption/adsorption methods provided an effective way to transfer NOx from the
Reduction methods were widely applicable in most industrial situations. Much re-
gas phase to the liquid/solid phases. However, due to the extremely low solubility of NO
search has been focused on the design and development of more efficient, more durable
in aqueous solutions, pre-oxidation is necessary to make the ratio of NO2 /NOx exceed 50%
catalysts that is more resistant to H2O and SO2. Liquid reductants were generally utilized
beyond alkaline absorption. Regarding solid adsorption methods, porous materials, such
after the oxidation of NOx into NO2 to ensure a high reduction efficiency. Recently, solid
as activated carbon, zeolites, and metal–organic frameworks (MOFs) were widely studied.
reductants have attracted interest from both academic and industrial groups. For in-
According to the proposed mechanisms, increasing the acidity or alkalinity of the adsorbent
stance, H 3PW12O40 (HPW) was reported to reduce NO without any reducing gas.
surface and covering it with metal oxides can dramatically improve the performance of NO
Absorption/adsorption
adsorption. methods provided
Therefore, the development an effective
of adsorbent way to transfer
modification methods NOxwithfrom the
a higher
gas phase to the
performance and liquid/solid
more detailedphases. However,
mechanisms ofdue
the to the extremely
behavior betweenlow NOx solubility of NO
and adsorbents
inneeds
aqueous solutions, pre-oxidation
to be further studied. is necessary to make the ratio of NO 2/NOx exceed 50%

beyond alkaline absorption. Regarding solid adsorption methods, porous materials, such
as activated carbon, zeolites, and metal–organic frameworks (MOFs) were widely stud-
Separations 2022, 9, 307 21 of 27

Author Contributions: Conceptualization, Z.Z. and B.X.; methodology, Z.Z.; investigation, Z.Z.; data
curation, Z.Z.; writing—original draft preparation, Z.Z.; writing—review and editing, Z.Z. and B.X.;
visualization, Z.Z.; supervision, B.X.; funding acquisition, B.X. All authors have read and agreed to
the published version of the manuscript.
Funding: This research was funded by National Key R&D Program of China (No. 2019YFC1904001)
and the Natural Science Foundation of Shanghai (21ZR1468000).
Data Availability Statement: Not applicable.
Acknowledgments: This study was partially sponsored the Foundation of State Key Laboratory of
Pollution Control and Resource Reuse (Tongji University), China, (No. PCRRE), and the Shanghai
Institute of Pollution Control and Ecological Security.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Li, H.-M.; Zhang, N.; Guo, X.; Dou, M.-Y.; Feng, Q.; Zou, S.; Huang, F.-C. Summary of Flue Gas Purification and Treatment
Technology for Domestic Waste Incineration. IOP Conf. Ser. Earth Environ. Sci. 2020, 508, 012016. [CrossRef]
2. Lin, F.; Wang, Z.; Zhang, Z.; He, Y.; Zhu, Y.; Shao, J.; Yuan, D.; Chen, G.; Cen, K. Flue gas treatment with ozone oxidation: An
overview on NOx , organic pollutants, and mercury. Chem. Eng. J. 2020, 382, 123030. [CrossRef]
3. Shan, W.; Yu, Y.; Zhang, Y.; He, G.; Peng, Y.; Li, J.; He, H. Theory and practice of metal oxide catalyst design for the selective
catalytic reduction of NOx with NH3 . Catal. Today 2021, 376, 292–301. [CrossRef]
4. Yuan, B.; Mao, X.Z.; Wang, Z.; Hao, R.L.; Zhao, Y. Radical-induced oxidation removal of multi-air-pollutant: A critical review.
J. Hazard. Mater. 2020, 383, 121162. [CrossRef] [PubMed]
5. Gholami, F.; Tomas, M.; Gholami, Z.; Vakili, M. Technologies for the nitrogen oxides reduction from flue gas: A review. Sci. Total
Environ. 2020, 714, 136712. [CrossRef] [PubMed]
6. Jing, W.; Changjian, L.; Haibo, W.; Ping, J.; Zhiyu, L.; Fanfei, M. Research progress of low-NOx combustion technology for boilers.
Clean Coal Technol. 2022, 28, 99–114. [CrossRef]
7. Skalska, K.; Miller, J.S.; Ledakowicz, S. Trends in NOx abatement: A review. Sci. Total Environ. 2010, 408, 3976–3989. [CrossRef]
[PubMed]
8. Sun, Y.; Zwolińska, E.; Chmielewski, A.G. Abatement technologies for high concentrations of NOx and SO2 removal from exhaust
gases: A review. Crit. Rev. Environ. Sci. Technol. 2016, 46, 119–142. [CrossRef]
9. Javed, M.T.; Irfan, N.; Gibbs, B.M. Control of combustion-generated nitrogen oxides by selective non-catalytic reduction. J. Environ.
Manag. 2007, 83, 251–289. [CrossRef]
10. Guo, R.-T.; Hao, J.-K.; Pan, W.-G.; Yu, Y.-L. Liquid Phase Oxidation and Absorption of NO from Flue Gas: A Review. Sep. Sci.
Technol. 2015, 50, 310–321. [CrossRef]
11. Rezaei, F.; Rownaghi, A.A.; Monjezi, S.; Lively, R.P.; Jones, C.W. SOx /NOx Removal from Flue Gas Streams by Solid Adsorbents:
A Review of Current Challenges and Future Directions. Energy Fuels 2015, 29, 5467–5486. [CrossRef]
12. Ma, S.; Zhao, Y.; Yang, J.; Zhang, S.; Zhang, J.; Zheng, C. Research progress of pollutants removal from coal-fired flue gas using
non-thermal plasma. Renew. Sustain. Energy Rev. 2017, 67, 791–810. [CrossRef]
13. Atkinson, R.; Baulch, D.L.; Cox, R.A.; Crowley, J.N.; Hampson, R.F.; Hynes, R.G.; Jenkin, M.E.; Rossi, M.J.; Troe, J. Evaluated
kinetic and photochemical data for atmospheric chemistry: Volume I—gas phase reactions of Ox , HOx , NOx and SOx species.
Atmos. Chem. Phys. 2004, 4, 1461–1738. [CrossRef]
14. Shugen, L.; Binh, N.; Ting, L. Production and Control of NOx in Sintering or Pelletizing Process. Sichuan Environ. 2016, 35, 17–22.
[CrossRef]
15. Zhao, B.; Su, Y. Process effect of microalgal-carbon dioxide fixation and biomass production: A review. Renew. Sustain. Energy Rev.
2014, 31, 121–132. [CrossRef]
16. Fang, P.; Tang, Z.; Xiao, X.; Huang, J.; Chen, X.; Zhong, P.; Tang, Z.; Cen, C. Using sewage sludge as a flue gas denitration agent
for the cement industry: Factor assessment and feasibility. J. Clean. Prod. 2019, 224, 292–303. [CrossRef]
17. Gershinowitz, H.; Eyring, H. The Theory of Trimolecular Reactions1. J. Am. Chem. Soc. 1935, 57, 985–991. [CrossRef]
18. Liang, J.; Lu, L.; Liu, L. Study on Pollutant Quantity of Low Calorific-value Gas Power Plant. Sci. Technol. Eng. 2013, 13,
9587–9591.
19. Cai, S. Exploring technical ways to reduce NOx emissions from cement kilns in China. In Proceedings of the Second Summit
Forum on Energy Saving, Emission Reduction and Cleaner Production Control Technology in Cement Industry—Special Session
on Denitrification and Dust Removal Technology in Cement Industry, Jinan, China, 16–18 April 2013; pp. 36–39.
20. Tsukahara, H.; Ishida, T.; Mayumi, M. Gas-Phase Oxidation of Nitric Oxide: Chemical Kinetics and Rate Constant. Nitric Oxide
1999, 3, 191–198. [CrossRef]
21. Ting, T.; Stanger, R.; Wall, T. Laboratory investigation of high pressure NO oxidation to NO2 and capture with liquid and gaseous
water under oxy-fuel CO2 compression conditions. Int. J. Greenh. Gas Control 2013, 18, 15–22. [CrossRef]
Separations 2022, 9, 307 22 of 27

22. Chen, H.; Wang, Y.; Lyu, Y.-K. High catalytic activity of Mn-based catalyst in NO oxidation at low temperature and over a wide
temperature span. Mol. Catal. 2018, 454, 21–29. [CrossRef]
23. Chen, H.; Wang, Y.; Lv, Y.-K. Catalytic oxidation of NO over MnO2 with different crystal structures. RSC Adv. 2016, 6, 54032–54040.
[CrossRef]
24. Gao, F.; Tang, X.; Yi, H.; Chu, C.; Li, N.; Li, J.; Zhao, S. In-situ DRIFTS for the mechanistic studies of NO oxidation over α-MnO2 ,
β-MnO2 and γ-MnO2 catalysts. Chem. Eng. J. 2017, 322, 525–537. [CrossRef]
25. Hadjiivanov, K.; Knozinger, H. Species formed after NO adsorption and NO+O-2 co-adsorption on TiO2 : An FTIR spectroscopic
study. Phys. Chem. Chem. Phys. 2000, 2, 2803–2806. [CrossRef]
26. Yuan, H.; Chen, J.; Guo, Y.; Wang, H.; Hu, P. Insight into the Superior Catalytic Activity of MnO2 for Low-Content NO Oxidation
at Room Temperature. J. Phys. Chem. C 2018, 122, 25365–25373. [CrossRef]
27. Bhatia, D.; McCabe, R.W.; Harold, M.P.; Balakotaiah, V. Experimental and kinetic study of NO oxidation on model Pt catalysts.
J. Catal. 2009, 266, 106–119. [CrossRef]
28. Tang, N.; Liu, Y.; Wang, H.; Wu, Z. Mechanism Study of NO Catalytic Oxidation over MnOx /TiO2 Catalysts. J. Phys. Chem. C
2011, 115, 8214–8220. [CrossRef]
29. Sun, W.-y.; Wang, Q.-y.; Ding, S.-l.; Su, S.-j. Simultaneous absorption of SO2 and NOx with pyrolusite slurry combined with
gas-phase oxidation of NO using ozone: Effect of molar ratio of O2 /(SO2 +0.5NOx ) in flue gas. Chem. Eng. J. 2013, 228, 700–707.
[CrossRef]
30. Mok, Y.S.; Lee, H.-J. Removal of sulfur dioxide and nitrogen oxides by using ozone injection and absorption–reduction technique.
Fuel Processing Technol. 2006, 87, 591–597. [CrossRef]
31. Sun, C.; Zhao, N.; Zhuang, Z.; Wang, H.; Liu, Y.; Weng, X.; Wu, Z. Mechanisms and reaction pathways for simultaneous oxidation
of NOx and SO2 by ozone determined by in situ IR measurements. J. Hazard. Mater. 2014, 274, 376–383. [CrossRef]
32. Li, B.; Zhao, J.; Lu, J. Numerical Study of the Simultaneous Oxidation of NO and SO2 by Ozone. Int. J. Environ. Res. Public Health
2015, 12, 1595–1611. [CrossRef] [PubMed]
33. Wang, H.; Zhuang, Z.; Sun, C.; Zhao, N.; Liu, Y.; Wu, Z. Numerical evaluation of the effectiveness of NO2 and N2 O5 generation
during the NO ozonation process. J. Environ. Sci. 2016, 41, 51–58. [CrossRef] [PubMed]
34. Zou, Y.; Liu, X.; Zhu, T.; Tian, M.; Cai, M.; Zhao, Z.; Wu, H. Simultaneous Removal of NOx and SO2 by MgO Combined with O-3
Oxidation: The Influencing Factors and O-3 Consumption Distributions. ACS Omega 2019, 4, 21091–21099. [CrossRef]
35. Zhou, S.; Zhou, J.; Feng, Y.; Zhu, Y. Marine Emission Pollution Abatement Using Ozone Oxidation by a Wet Scrubbing Method.
Ind. Eng. Chem. Res. 2016, 55, 5825–5831. [CrossRef]
36. Li, Z.; Wuebbles, R.D.; Pylawka, N.J. Rate constant measurement for the reaction of OClO with NO at 220–367 K. Chem. Phys. Lett.
2002, 354, 491–497. [CrossRef]
37. Johansson, J.; Heijnesson Hultén, A.; Ajdari, S.; Nilsson, P.; Samuelsson, M.; Normann, F.; Andersson, K. Gas-Phase Chemistry of
the NO–SO2 –ClO2 System Applied to Flue Gas Cleaning. Ind. Eng. Chem. Res. 2018, 57, 14347–14354. [CrossRef]
38. Jin, D.-S.; Deshwal, B.-R.; Park, Y.-S.; Lee, H.-K. Simultaneous removal of SO2 and NO by wet scrubbing using aqueous chlorine
dioxide solution. J. Hazard. Mater. 2006, 135, 412–417. [CrossRef]
39. Zhang, H.; Ma, D.; Qiu, R.; Tang, Y.; Du, C. Non-thermal plasma technology for organic contaminated soil remediation: A review.
Chem. Eng. J. 2017, 313, 157–170. [CrossRef]
40. Feng, X.; Liu, H.; He, C.; Shen, Z.; Wang, T. Synergistic effects and mechanism of a non-thermal plasma catalysis system in volatile
organic compound removal: A review. Catal. Sci. Technol. 2018, 8, 936–954. [CrossRef]
41. Hong, L.; Chen, D.; Yang, M.; Yin, L.; Wang, D.; Wang, L. Interaction between NO and SO2 removal processes in a pulsed corona
discharge plasma (PCDP) reactor and the mechanism. Chem. Eng. J. 2019, 359, 1130–1138. [CrossRef]
42. Yamamoto, T.; Okubo, M.; Hayakawa, K.; Kitaura, K. Towards ideal NOx control technology using a plasma-chemical hybrid
process. IEEE Trans. Ind. Appl. 2001, 37, 1492–1498. [CrossRef]
43. Obradović, B.M.; Sretenović, G.B.; Kuraica, M.M. A dual-use of DBD plasma for simultaneous NOx and SO2 removal from
coal-combustion flue gas. J. Hazard. Mater. 2011, 185, 1280–1286. [CrossRef] [PubMed]
44. Wang, T.; Sun, B.M.; Xiao, H.P.; Zeng, J.Y.; Duan, E.P.; Xin, J.; Li, C. Effect of Reactor Structure in DBD for Nonthermal Plasma
Processing of NO in N-2 at Ambient Temperature. Plasma Chem. Plasma Process. 2012, 32, 1189–1201. [CrossRef]
45. Pham, H.-C.; Kim, K.-S. Effect of TiO2 Thin Film Thickness on NO and SO2 Removals by Dielectric Barrier Discharge-Photocatalyst
Hybrid Process. Ind. Eng. Chem. Res. 2013, 52, 5296–5301. [CrossRef]
46. Wang, M.; Sun, Y.; Zhu, T. Removal of NOx , SO2 , and Hg From Simulated Flue Gas by Plasma—Absorption Hybrid System. IEEE
Trans. Plasma Sci. 2013, 41, 312–318. [CrossRef]
47. Huang, L.; Dang, Y. Removal of SO2 and NOx by Pulsed Corona Combined with in situ Ca(OH)2 Absorption. Chin. J. Chem. Eng.
2011, 19, 518–522. [CrossRef]
48. Zhao, L.; Luo, Z.; Jiang, J.; Zhou, D.; Gao, X.; Cen, K. Energy Consumption Analysis and OH Radical Detection of NO Conversion
Process From Flue Gas Using Pulsed Corona Discharge. IEEE Trans. Plasma Sci. 2014, 42, 105–113. [CrossRef]
49. Seo, S.H.; Jo, S.H.; Son, Y.S.; Kim, T.H.; Kim, T.H.; Yu, S. A preliminary study on effect of additive in the removal of NOx and SO2
by electron beam irradiation. Chem. Eng. J. 2020, 387, 124083. [CrossRef]
50. Zhao, L.; Sun, Y.X.; Chmielewski, A.G.; Pawelec, A.; Bulka, S. NO Oxidation with NaClO, NaClO2 , and NaClO3 Solution Using
Electron Beam and a One Stage Absorption System. Plasma Chem. Plasma Process. 2020, 40, 433–447. [CrossRef]
Separations 2022, 9, 307 23 of 27

51. Chen, R.; Zhang, T.; Guo, Y.; Wang, J.; Wei, J.; Yu, Q. Recent advances in simultaneous removal of SO2 and NOx from exhaust
gases: Removal process, mechanism and kinetics. Chem. Eng. J. 2021, 420, 127588. [CrossRef]
52. Zhao, S.; Pudasainee, D.; Duan, Y.; Gupta, R.; Liu, M.; Lu, J. A review on mercury in coal combustion process: Content and
occurrence forms in coal, transformation, sampling methods, emission and control technologies. Prog. Energy Combust. Sci. 2019,
73, 26–64. [CrossRef]
53. Standard Electrode Potential (Data Page). Wikipedia Encyclopedia. Available online: https://encyclopedia.thefreedictionary.
com/Standard+electrode+potential+(data+page) (accessed on 12 September 2022).
54. Yi, S.; Liliang, Y.; Haobing, H.; Jiawei, Y.; Shao’an, C. Research trend and practical development of advanced oxdation process on
degradation of recalcitrant organic wastewater. CIESC J. 2017, 68, 1743–1756.
55. Oh, S.-Y.; Kang, S.-G.; Chiu, P.C. Degradation of 2,4-dinitrotoluene by persulfate activated with zero-valent iron. Sci. Total Environ.
2010, 408, 3464–3468. [CrossRef] [PubMed]
56. Wang, J.; Wang, S. Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging
contaminants. Chem. Eng. J. 2018, 334, 1502–1517. [CrossRef]
57. Collins, M.M.; Cooper, C.D.; Dietz, J.D.; Clausen, C.A.; Tazi, L.M. Pilot-scale evaluation of H2 O2 injection to control to NOx
emissions. J. Environ. Eng. ASCE 2001, 127, 329–336. [CrossRef]
58. Martinez, N.S.; Fernandez, J.F.; Segura, X.F.; Ferrer, A.S. Pre-oxidation of an extremely polluted industrial wastewater by the
Fenton’s reagent. J. Hazard. Mater. 2003, 101, 315–322. [CrossRef]
59. Zhu, Y.; Zhu, R.; Xi, Y.; Zhu, J.; Zhu, G.; He, H. Strategies for enhancing the heterogeneous Fenton catalytic reactivity: A review.
Appl. Catal. B Environ. 2019, 255, 117739. [CrossRef]
60. Lopez-Cueto, G.; Ostra, M.; Ubide, C.; Zuriarrain, J. Fenton’s reagent for kinetic determinations. Anal. Chim. Acta 2004, 515,
109–116. [CrossRef]
61. Liu, Y.; Zhang, J.; Sheng, C.; Zhang, Y.; Zhao, L. Simultaneous removal of NO and SO2 from coal-fired flue gas by UV/H2 O2
advanced oxidation process. Chem. Eng. J. 2010, 162, 1006–1011. [CrossRef]
62. Liu, Y.; Pan, J.; Wang, Q. Removal of Hg-0 from containing-SO2 /NO flue gas by ultraviolet/H2 O2 process in a novel photochemical
reactor. Aiche J. 2014, 60, 2275–2285. [CrossRef]
63. Guo, R.-T.; Pan, W.-G.; Zhang, X.-B.; Ren, J.-X.; Jin, Q.; Xu, H.-J.; Wu, J. Removal of NO by using Fenton reagent solution in a
lab-scale bubbling reactor. Fuel 2011, 90, 3295–3298. [CrossRef]
64. Hao, R.; Mao, Y.; Mao, X.; Wang, Z.; Gong, Y.; Zhang, Z.; Zhao, Y. Cooperative removal of SO2 and NO by using a method of
UV-heat/H2 O2 oxidation combined with NH4OH-(NH4)2SO3 dual-area absorption. Chem. Eng. J. 2019, 365, 282–290. [CrossRef]
65. Thomas, N.; Dionysiou, D.D.; Pillai, S.C. Heterogeneous Fenton catalysts: A review of recent advances. J. Hazard. Mater. 2021,
404, 124082. [CrossRef] [PubMed]
66. Li, Y.; Zhang, X.; Lin, H.; Yu, F.; Chen, Z.; Li, C.; Liu, Z.; Yu, J.; Gao, S. The simultaneous removal of SO2 and NO from flue gas
over activated coke in a multi-stage fluidized bed at low temperature. Fuel 2020, 275, 117862. [CrossRef]
67. Li, J.; Ninh Pham, A.; Dai, R.; Wang, Z.; Waite, T.D. Recent advances in Cu-Fenton systems for the treatment of industrial
wastewaters: Role of Cu complexes and Cu composites. J. Hazard. Mater. 2020, 392, R713–R715. [CrossRef]
68. Wu, B.; Zhang, S.; He, S.; Xiong, Y. Follow-up mechanism study on NO oxidation with vaporized H2 O2 catalyzed by Fe2 O3 in a
fixed-bed reactor. Chem. Eng. J. 2019, 356, 662–672. [CrossRef]
69. Matzek, L.W.; Carter, K.E. Activated persulfate for organic chemical degradation: A review. Chemosphere 2016, 151, 178–188.
[CrossRef] [PubMed]
70. Deng, Y.; Ezyske, C.M. Sulfate radical-advanced oxidation process (SR-AOP) for simultaneous removal of refractory organic
contaminants and ammonia in landfill leachate. Water Res. 2011, 45, 6189–6194. [CrossRef] [PubMed]
71. Adewuyi, Y.G.; Khan, M.A.; Sakyi, N.Y. Kinetics and Modeling of the Removal of Nitric Oxide by Aqueous Sodium Persulfate
Simultaneously Activated by Temperature and Fe2+ . Ind. Eng. Chem. Res. 2014, 53, 828–839. [CrossRef]
72. Adewuyi, Y.G.; Sakyi, N.Y. Simultaneous Absorption and Oxidation of Nitric Oxide and Sulfur Dioxide by Aqueous Solutions of
Sodium Persulfate Activated by Temperature. Ind. Eng. Chem. Res. 2013, 52, 11702–11711. [CrossRef]
73. Chen, X.; Hu, X. Removal of NOx and SO2 from the Coal-Fired Flue Gas Using a Rotating Packed Bed Pilot Reactor with
Peroxymonosulfate Activated by Fe(II) and Heating. Energy Fuels 2019, 33, 6707–6716. [CrossRef]
74. Liu, Y.; Liu, Z.; Wang, Y.; Yin, Y.; Pan, J.; Zhang, J.; Wang, Q. Simultaneous absorption of SO2 and NO from flue gas using
ultrasound/Fe2+ /heat coactivated persulfate system. J. Hazard. Mater. 2018, 342, 326–334. [CrossRef] [PubMed]
75. Antoniou, M.G.; Andersen, H.R. Comparison of UVC/S2 O8 2- with UVC/H2 O2 in terms of efficiency and cost for the removal of
micropollutants from groundwater. Chemosphere 2015, 119, S81–S88. [CrossRef] [PubMed]
76. Xu, Y.; Lin, Z.; Zhang, H. Mineralization of sucralose by UV-based advanced oxidation processes: UV/PDS versus UV/H2 O2 .
Chem. Eng. J. 2016, 285, 392–401. [CrossRef]
77. Kwon, M.; Kim, S.; Yoon, Y.; Jung, Y.; Hwang, T.-M.; Lee, J.; Kang, J.-W. Comparative evaluation of ibuprofen removal by
UV/H2 O2 and UV/S2 O8 2− processes for wastewater treatment. Chem. Eng. J. 2015, 269, 379–390. [CrossRef]
78. Wei, Z.; Villamena, F.A.; Weavers, L.K. Kinetics and Mechanism of Ultrasonic Activation of Persulfate: An in Situ EPR Spin
Trapping Study. Environ. Sci. Technol. 2017, 51, 3410–3417. [CrossRef]
79. Si, M.; Shen, B.; Adwek, G.; Xiong, L.; Liu, L.; Yuan, P.; Gao, H.; Liang, C.; Guo, Q. Review on the NO removal from flue gas by
oxidation methods. J. Environ. Sci. 2021, 101, 49–71. [CrossRef] [PubMed]
Separations 2022, 9, 307 24 of 27

80. Adewuyi, Y.G.; Sakyi, N.Y. Removal of Nitric Oxide by Aqueous Sodium Persulfate Simultaneously Activated by Temperature
and Fe2+ in a Lab-scale Bubble Reactor. Ind. Eng. Chem. Res. 2013, 52, 14687–14697. [CrossRef]
81. Liu, Y.; Wang, Y.; Liu, Z.; Wang, Q. Oxidation Removal of Nitric Oxide from Flue Gas Using UV Photolysis of Aqueous
Hypochlorite. Environ. Sci. Technol. 2017, 51, 11950–11959. [CrossRef] [PubMed]
82. Byoun, S.; Shin, D.N.; Moon, I.-S.; Byun, Y. Quick vaporization of sprayed sodium hypochlorite (NaClO(aq)) for simultaneous
removal of nitrogen oxides (NOx ), sulfur dioxide (SO2 ), and mercury (Hg0). J. Air Waste Manag. Assoc. 2019, 69, 857–866.
[CrossRef] [PubMed]
83. Wang, Z.; Lun, L.; Tan, Z.; Zhang, Y.; Li, Q. Simultaneous wet desulfurization and denitration by an oxidant absorbent of
NaClO2 /CaO2 . Environ. Sci. Pollut. Res. 2019, 26, 29032–29040. [CrossRef] [PubMed]
84. Hao, R.; Yang, S.; Yuan, B.; Zhao, Y. Simultaneous desulfurization and denitrification through an integrative process utilizing
NaClO2 /Na2 S2 O8 . Fuel Processing Technol. 2017, 159, 145–152. [CrossRef]
85. Hao, R.; Song, Y.; Tian, Z.; Li, Y.; Zhao, Y.; Wang, Z.; Gong, Y.; Ma, Z.; Qian, Z. Cooperative removal of SO2 and NO using a
cost-efficient triple-area control method. Chem. Eng. J. 2020, 383, 123164. [CrossRef]
86. Hao, R.; Ma, Z.; Qian, Z.; Gong, Y.; Wang, Z.; Luo, Y.; Yuan, B.; Zhao, Y. New insight into the behavior and cost-effectiveness of
different radicals in the removal of NO and Hg0. Chem. Eng. J. 2020, 385, 123885. [CrossRef]
87. Madia, G.; Koebel, M.; Elsener, M.; Wokaun, A. Side reactions in the selective catalytic reduction of NOx with various NO2
fractions. Ind. Eng. Chem. Res. 2002, 41, 4008–4015. [CrossRef]
88. Hu, Z.; Yang, R.T. 110th Anniversary: Recent Progress and Future Challenges in Selective Catalytic Reduction of NO by H2 in the
Presence of O2 . Ind. Eng. Chem. Res. 2019, 58, 10140–10153. [CrossRef]
89. Mahmoudi, S.; Baeyens, J.; Seville, J.P.K. NOx formation and selective non-catalytic reduction (SNCR) in a fluidized bed combustor
of biomass. Biomass Bioenergy 2010, 34, 1393–1409. [CrossRef]
90. Li, G.; Wang, B.; Xu, W.Q.; Li, Y.; Han, Y.; Sun, Q. Simultaneous removal of SO2 and NOx from flue gas by wet scrubbing using a
urea solution. Environ. Technol. 2019, 40, 2620–2632. [CrossRef] [PubMed]
91. Gao, F.; Tang, X.; Yi, H.; Zhao, S.; Li, C.; Li, J.; Shi, Y.; Meng, X. A Review on Selective Catalytic Reduction of NOx by NH3
over Mn–Based Catalysts at Low Temperatures: Catalysts, Mechanisms, Kinetics and DFT Calculations. Catalysts 2017, 7, 199.
[CrossRef]
92. Liu, Y.; Zhao, J.; Lee, J.M. Conventional and New Materials for Selective Catalytic Reduction (SCR) of NOx . Chemcatchem 2018, 10,
1499–1511. [CrossRef]
93. Guan, B.; Zhan, R.; Lin, H.; Huang, Z. Review of state of the art technologies of selective catalytic reduction of NOx from diesel
engine exhaust. Appl. Therm. Eng. 2014, 66, 395–414. [CrossRef]
94. Yun, B.K.; Kim, M.Y. Modeling the selective catalytic reduction of NOx by ammonia over a Vanadia-based catalyst from heavy
duty diesel exhaust gases. Appl. Therm. Eng. 2013, 50, 152–158. [CrossRef]
95. Wang, F.; Ma, J.; He, G.; Chen, M.; Zhang, C.; He, H. Nanosize Effect of Al2 O3 in Ag/Al2 O3 Catalyst for the Selective Catalytic
Oxidation of Ammonia. ACS Catal. 2018, 8, 2670–2682. [CrossRef]
96. Zhou, J.; Guo, R.-t.; Zhang, X.-f.; Liu, Y.-z.; Duan, C.-p.; Wu, G.-l.; Pan, W.-g. Cerium Oxide-Based Catalysts for Low-Temperature
Selective Catalytic Reduction of NOx with NH3 : A Review. Energy Fuels 2021, 35, 2981–2998. [CrossRef]
97. Pena, D.A.; Uphade, B.S.; Smirniotis, P.G. TiO2 -supported metal oxide catalysts for low-temperature selective catalytic reduction
of NO with NH3 I. Evaluation and characterization of first row transition metals. J. Catal. 2004, 221, 421–431. [CrossRef]
98. Zhang, Z.; Li, J.; Tian, J.; Zhong, Y.; Zou, Z.; Dong, R.; Gao, S.; Xu, W.; Tan, D. The effects of Mn-based catalysts on the selective
catalytic reduction of NOx with NH3 at low temperature: A review. Fuel Processing Technol. 2022, 230, 107213. [CrossRef]
99. Kapteijn, F.; Singoredjo, L.; Andreini, A.; Moulijn, J.A. Activity and selectivity of pure manganese oxides in the selective catalytic
reduction of nitric oxide with ammonia. Appl. Catal. B: Environ. 1994, 3, 173–189. [CrossRef]
100. Han, L.; Cai, S.; Gao, M.; Hasegawa, J.-y.; Wang, P.; Zhang, J.; Shi, L.; Zhang, D. Selective Catalytic Reduction of NOx with NH3
by Using Novel Catalysts: State of the Art and Future Prospects. Chem. Rev. 2019, 119, 10916–10976. [CrossRef] [PubMed]
101. Xiong, S.; Liao, Y.; Xiao, X.; Dang, H.; Yang, S. The mechanism of the effect of H2 O on the low temperature selective catalytic
reduction of NO with NH3 over Mn-Fe spinel. Catal. Sci. Technol. 2015, 5, 2132–2140. [CrossRef]
102. Mohan, S.; Dinesha, P.; Kumar, S. NOx reduction behaviour in copper zeolite catalysts for ammonia SCR systems: A review. Chem.
Eng. J. 2020, 384, 123253. [CrossRef]
103. Liu, S.-M.; Guo, R.-T.; Sun, P.; Hu, C.-X.; Wang, S.-X.; Pan, W.-G.; Li, M.-Y.; Liu, S.-W.; Sun, X.; Liu, J. Mechanistic investigation of
the different poisoning mechanisms of Cl and P on Mn/TiO2 catalyst for selective catalytic reduction of NOx with NH3 . J. Taiwan
Inst. Chem. Eng. 2017, 80, 314–325. [CrossRef]
104. Cai, S.; Hu, H.; Li, H.; Shi, L.; Zhang, D. Design of multi-shell Fe2 O3 @MnOx @CNTs for the selective catalytic reduction of NO
with NH3 :improvement of catalytic activity and SO2 tolerance. Nanoscale 2016, 8, 3588–3598. [CrossRef] [PubMed]
105. Zhou, A.; Yu, D.; Yang, L.; Sheng, Z. Combined effects Na and SO2 in flue gas on Mn-Ce/TiO2 catalyst for low temperature
selective catalytic reduction of NO by NH3 simulated by Na2 SO4 doping. Appl. Surf. Sci. 2016, 378, 167–173. [CrossRef]
106. Watling, T.C.; Lopez, Y.; Pless, J.D.; Sukumar, B.; Klink, W.; Markatou, P. Removal of Hydrocarbons and Particulate Matter Using
a Vanadia Selective Catalytic Reduction Catalyst: An Experimental and Modeling Study. SAE Int. J. Engines 2013, 6, 882–897.
[CrossRef]
Separations 2022, 9, 307 25 of 27

107. Liu, K.J.; Yu, Q.B.; Wang, B.L.; San, J.B.; Duan, W.J.; Qin, Q. Binary copper-manganese based catalysts with urea for low-
temperature selective catalytic reduction of NO: Performance, characterization and mechanism. Appl. Surf. Sci. 2020, 508, 144755.
[CrossRef]
108. Tu, B.-S.; Sun, W.; Xue, Y.-J.; Zaman, W.Q.; Cao, L.-M.; Yang, J. Facile Synthesis of PtxNiy Catalyst Supported on Carbon for Low
Temperature H2 –SCR. ACS Sustain. Chem. Eng. 2017, 5, 5200–5207. [CrossRef]
109. Liu, Y.; Tursun, M.; Yu, H.; Wang, X. Surface property and activity of Pt/Nb2O5 -ZrO2 for selective catalytic reduction of NO by
H-2. Mol. Catal. 2019, 464, 22–28. [CrossRef]
110. Wang, X.; Wang, X.; Yu, H.; Wang, X. The functions of Pt located at different positions of HZSM-5 in H-2-SCR. Chem. Eng. J. 2019,
355, 470–477. [CrossRef]
111. Resitoglu, I.A.; Keskin, A. Hydrogen applications in selective catalytic reduction of NOx emissions from diesel engines. Int. J.
Hydrog. Energy 2017, 42, 23389–23394. [CrossRef]
112. Cai, X.; Sun, W.; Zaman, W.Q.; Cao, L.; Yang, J. Limited Ce doped Ni–Co as a highly efficient catalyst for H2 -SCR of NO with
good resistance to SO2 and H2 O at low temperature. RSC Adv. 2016, 6, 91930–91939. [CrossRef]
113. Mrad, R.; Aissat, A.; Cousin, R.; Courcot, D.; Siffert, S. Catalysts for NOx selective catalytic reduction by hydrocarbons (HC-SCR).
Appl. Catal. A-Gen. 2015, 504, 542–548. [CrossRef]
114. Fu, M.; Li, C.; Lu, P.; Qu, L.; Zhang, M.; Zhou, Y.; Yu, M.; Fang, Y. A review on selective catalytic reduction of NOx by supported
catalysts at 100-300 degrees C-catalysts, mechanism, kinetics. Catal. Sci. Technol. 2014, 4, 14–25. [CrossRef]
115. Feng, T.; Huo, M.; Zhao, X.; Wang, T.; Xia, X.; Ma, C. Reduction of SO2 to elemental sulfur with H-2 and mixed H-2/CO gas in an
activated carbon bed. Chem. Eng. Res. Des. 2017, 121, 191–199. [CrossRef]
116. Resitoglu, I.A.; Keskin, A.; Özarslan, H.; Bulut, H. Selective catalytic reduction of NOx emissions by hydrocarbons over
Ag–Pt/Al2 O3 catalyst in diesel engine. Int. J. Environ. Sci. Technol. 2019, 16, 6959–6966. [CrossRef]
117. Cheng, X.; Bi, X.T. A review of recent advances in selective catalytic NOx reduction reactor technologies. Particuology 2014, 16,
1–18. [CrossRef]
118. Pan, H.; Guo, Y.; Jian, Y.; He, C. Synergistic Effect of Non-thermal Plasma on NOx Reduction by CH4 over an In/H-BEA Catalyst
at Low Temperatures. Energy Fuels 2015, 29, 5282–5289. [CrossRef]
119. Pekridis, G.; Kaklidis, N.; Komvokis, V.; Athanasiou, C.; Konsolakis, M.; Yentekakis, I.V.; Marnellos, G.E. Surface and Catalytic
Elucidation of Rh/γ-Al2 O3 Catalysts during NO Reduction by C3H8 in the Presence of Excess O2 , H2 O, and SO2 . J. Phys. Chem.
A 2010, 114, 3969–3980. [CrossRef]
120. Gholami, Z.; Luo, G. Low-Temperature Selective Catalytic Reduction of NO by CO in the Presence of O2 over Cu:Ce Catalysts
Supported by Multiwalled Carbon Nanotubes. Ind. Eng. Chem. Res. 2018, 57, 8871–8883. [CrossRef]
121. Liu, Z.; Wu, J.; Hardacre, C. Research Progress in the Selective Catalytic Reduction of NOx by H2 in the Presence of O2 . Catal.
Surv. Asia 2018, 22, 146–155. [CrossRef]
122. Liu, K.; Yu, Q.; Qin, Q.; Wang, C. Selective catalytic reduction of nitric oxide with carbon monoxide over alumina-pellet-supported
catalysts in the presence of excess oxygen. Environ. Technol. 2018, 39, 1878–1885. [CrossRef]
123. Tarjomannejad, A.; Farzi, A.; Niaei, A.; Salari, D. NO reduction by CO over LaB0.5B’O-0.5(3) (B = Fe, Mn, B’=Fe, Mn, Co, Cu)
perovskite catalysts, an experimental and kinetic study. J. Taiwan Inst. Chem. Eng. 2017, 78, 200–211. [CrossRef]
124. Hamada, H.; Haneda, M. A review of selective catalytic reduction of nitrogen oxides with hydrogen and carbon monoxide. Appl.
Catal. A-Gen. 2012, 421, 1–13. [CrossRef]
125. Sreekanth, P.M.; Smirniotis, P.G. Selective Reduction of NO with CO Over Titania Supported Transition Metal Oxide Catalysts.
Catal. Lett. 2008, 122, 37–42. [CrossRef]
126. Kim, H.; Han, B.; Woo, C.G.; Kim, Y. NOx Removal Performance of a Wet Reduction Scrubber Combined with Oxidation by an
Indirect DBD Plasma for Semiconductor Manufacturing Industries. IEEE Trans. Ind. Appl. 2018, 54, 6401–6407. [CrossRef]
127. Wang, R.; Zhang, X.; Ren, Z. Germanium-based polyoxometalates for the adsorption-decomposition of NOx . J. Hazard. Mater.
2021, 402, 123494. [CrossRef] [PubMed]
128. Bélanger, R.; Moffat, J.B. A self-contained catalyst for the reduction of NO2 . Appl. Catal. B Environ. 1997, 13, 167–173. [CrossRef]
129. Yang, R.T.; Chen, N. A New Approach to Decomposition of Nitric-Oxide Using Sorbent Catalyst Without Reducing Gas—Use of
Heteropoly Compounds. Ind. Eng. Chem. Res. 1994, 33, 825–831. [CrossRef]
130. Belanger, R.; Moffat, J.B. A Comparative-Study of the Adsorption and Reaction Of Nitrogen-Oxides on 12-Tungstophosphoric,
12-Tungstosilicic, and 12-Molybdophosphoric Acids. J. Catal. 1995, 152, 179–188. [CrossRef]
131. McCormick, R.L.; Boonrueng, S.K.; Herring, A.M. In situ IR and temperature programmed desorption mass spectrometry study
of NO absorption and decomposition by silica supported 12-tungstophosphoric acid. Catal. Today 1998, 42, 145–157. [CrossRef]
132. Zhang, Z.L.; Zhu, L.L.; Ma, J.; Ren, S.L.; Yang, X.Y. Temperature programmed desorption-mass spectrometry study of NO
desorption and decomposition by titania supported 12-tungstophosphoric acid. React. Kinet. Catal. Lett. 2002, 76, 93–101.
[CrossRef]
133. Joshi, J.B.; Mahajani, V.V.; Juvekar, V.A. Absorption Of NOx Gases. Chem. Eng. Commun. 1985, 33, 1–92. [CrossRef]
134. Thomas, D.; Vanderschuren, J. Nitrogen oxides scrubbing with alkaline solutions. Chem. Eng. Technol. 2000, 23, 449–455.
[CrossRef]
135. Valluri, S.; Kawatra, S.K. Simultaneous removal of CO2 , NOx and SOx using single stage absorption column. J. Environ. Sci. 2021,
103, 279–287. [CrossRef] [PubMed]
Separations 2022, 9, 307 26 of 27

136. Yih, S.M.; Lii, C.W. Simultaneous Absorption of Nitric-Oxide and Sulfur-Dioxide in Fe2 —Edta Solutions in a Packed Absorber-
Stripper Unit. Chem. Eng. J. Biochem. Eng. J. 1989, 42, 145–152.
137. Harriott, P.; Smith, K.; Benson, L.B. Simultaneous removal of NO and SO2 in packed scrubbers or spray towers. Environ. Prog.
1993, 12, 110–113. [CrossRef]
138. Yih, S.-M.; Lii, C.-W. Absorption of no and SO2 in Fe(II)-edta solutions I. absorption in a double stirred vessel. Chem. Eng.
Commun. 1988, 73, 43–53. [CrossRef]
139. Yang, L.; Chou, X.-w.; Li, C.; Long, X.-l.; Yuan, W.-k. Reduction of [Fe(III)EDTA]− catalyzed by activated carbon modified with
KOH solution. J. Ind. Eng. Chem. 2013, 19, 784–790. [CrossRef]
140. He, F.; Deng, X.; Chen, M. Evaluation of Fe(II)EDTA-NO reduction by zinc powder in wet flue gas denitrification technology with
Fe(II)EDTA. Fuel 2017, 199, 523–531. [CrossRef]
141. He, F.; Deng, X.; Chen, M. Mechanism and kinetics of Fe(II)EDTANO reduction by iron powder under anaerobic condition. Fuel
2016, 186, 605–612. [CrossRef]
142. Suchecki, T.T.; Mathews, B.; Augustyniak, A.W.; Kumazawa, H. Applied Kinetics Aspects of Ferric EDTA Complex Reduction
with Metal Powder. Ind. Eng. Chem. Res. 2014, 53, 14234–14240. [CrossRef]
143. He, F.; Qian, Y.; Xu, J. Performance, Mechanism, and Kinetics of Fe(III)EDTA Reduction by Thiourea Dioxide. Energy Fuels 2019,
33, 3331–3338. [CrossRef]
144. Suchecki, T.T.; Sada, E.; Kumazawa, H. Reduction of (ethylenediaminetetraacetato)iron(III) by sulfite at the boiling temperature.
Ind. Eng. Chem. Res. 1991, 30, 2201–2204. [CrossRef]
145. Suchecki, T.T.; Mathews, B.; Kumazawa, H. Kinetic Study of Ambient-Temperature Reduction of FeIIIedta by Na2 S2 O4 . Ind. Eng.
Chem. Res. 2005, 44, 4249–4253. [CrossRef]
146. Liang, C.; Liang, C.-P.; Chen, C.-C. pH dependence of persulfate activation by EDTA/Fe(III) for degradation of trichloroethylene.
J. Contam. Hydrol. 2009, 106, 173–182. [CrossRef] [PubMed]
147. Guo, Q.; He, Y.; Sun, T.; Wang, Y.; Jia, J. Simultaneous removal of NOx and SO2 from flue gas using combined Na2 SO3 assisted
electrochemical reduction and direct electrochemical reduction. J. Hazard. Mater. 2014, 276, 371–376. [CrossRef]
148. Adewuyi, Y.G.; Khan, M.A. Nitric oxide removal by combined persulfate and ferrous–EDTA reaction systems. Chem. Eng. J. 2015,
281, 575–587. [CrossRef]
149. Adewuyi, Y.G.; Khan, M.A. Nitric oxide removal from flue gas by combined persulfate and ferrous–EDTA solutions: Effects of
persulfate and EDTA concentrations, temperature, pH and SO2 . Chem. Eng. J. 2016, 304, 793–807. [CrossRef]
˛ K. Properties of activated cokes used for flue gas treatment in industrial waste incineration plants. Fuel Process. Technol.
150. Jastrzab,
2012, 101, 16–22. [CrossRef]
151. Liu, Q.; Liu, Z. Carbon supported vanadia for multi-pollutants removal from flue gas. Fuel 2013, 108, 149–158. [CrossRef]
152. Liu, Z.-S. Adsorption of SO2 and NO from incineration flue gas onto activated carbon fibers. Waste Manag. 2008, 28, 2329–2335.
[CrossRef] [PubMed]
153. Severa, G.; Head, J.; Bethune, K.; Higgins, S.; Fujise, A. Comparative studies of low concentration SO2 and NO2 sorption by
activated carbon supported [C2mim] [Ac] and KOH sorbents. J. Environ. Chem. Eng. 2018, 6, 718–727. [CrossRef]
154. Sumathi, S.; Bhatia, S.; Lee, K.T.; Mohamed, A.R. Cerium impregnated palm shell activated carbon (Ce/PSAC) sorbent for
simultaneous removal of SO2 and NO—Process study. Chem. Eng. J. 2010, 162, 51–57. [CrossRef]
155. Zhang, Z.; Chen, L.; Wang, J.; Yao, J.; Li, J. Biochar preparation from Solidago canadensis and its alleviation of the inhibition of
tomato seed germination by allelochemicals. RSC Adv. 2018, 8, 22370–22375. [CrossRef]
156. Gao, F.; Tang, X.; Yi, H.; Zhang, B.; Zhao, S.; Wang, J.; Gu, T.; Wang, Y. NiO-Modified Coconut Shell Based Activated Carbon
Pretreated with KOH for the High-Efficiency Adsorption of NO at Ambient Temperature. Ind. Eng. Chem. Res. 2018, 57,
16593–16603. [CrossRef]
157. Shen, Y.F.; Ge, X.L.; Chen, M.D. Catalytic oxidation of nitric oxide (NO) with carbonaceous materials. Rsc Adv. 2016, 6, 8469–8482.
[CrossRef]
158. Guo, Y.; Li, Y.; Zhu, T.; Ye, M. Effects of Concentration and Adsorption Product on the Adsorption of SO2 and NO on Activated
Carbon. Energy Fuels 2013, 27, 360–366. [CrossRef]
159. Xiong, Y.; Tang, C.; Yao, X.; Zhang, L.; Li, L.; Wang, X.; Deng, Y.; Gao, F.; Dong, L. Effect of metal ions doping (M=Ti4+ , Sn4+ ) on
the catalytic performance of MnOx /CeO2 catalyst for low temperature selective catalytic reduction of NO with NH3 . Appl. Catal.
A: Gen. 2015, 495, 206–216. [CrossRef]
160. Sumathi, S.; Bhatia, S.; Lee, K.T.; Mohamed, A.R. Selection of best impregnated palm shell activated carbon (PSAC) for
simultaneous removal of SO2 and NOx . J. Hazard. Mater. 2010, 176, 1093–1096. [CrossRef] [PubMed]
161. Sumathi, S.; Bhatia, S.; Lee, K.T.; Mohamed, A.R. SO2 and NO Simultaneous Removal from Simulated Flue Gas over Cerium-
Supported Palm Shell Activated at Lower Temperatures−Role of Cerium on NO Removal. Energy Fuels 2010, 24, 427–431.
[CrossRef]
162. Silas, K.; Ghani, W.A.W.A.K.; Choong, T.S.Y.; Rashid, U.; Soltani, S. Regeneration/Optimization of Activated Carbon Monolith in
Simultaneous SO2 /NOx Removal from Flue Gas. Chem. Eng. Technol. 2019, 42, 1928–1940. [CrossRef]
163. Silas, K.; Ghani, W.A.W.A.K.; Choong, T.S.Y.; Rashid, U. Breakthrough studies of CO3 O4 supported activated carbon monolith for
simultaneous SO2 /NOx removal from flue gas. Fuel Process. Technol. 2018, 180, 155–165. [CrossRef]
Separations 2022, 9, 307 27 of 27

164. Li, Q.; Hou, Y.; Han, X.; Wang, J.; Liu, Y.; Xiang, N.; Huang, Z. Promotional effect of cyclic desulfurization and regeneration for
selective catalytic reduction of NO by NH3 over activated carbon. J. Clean. Prod. 2020, 249, 119392. [CrossRef]
165. Zheng, Y.; Kovarik, L.; Engelhard, M.H.; Wang, Y.; Wang, Y.; Gao, F.; Szanyi, J. Low-Temperature Pd/Zeolite Passive NOx
Adsorbers: Structure, Performance, and Adsorption Chemistry. J. Phys. Chem. C 2017, 121, 15793–15803. [CrossRef]
166. Deng, H.; Yi, H.; Tang, X.; Liu, H.; Zhou, X. Interactive Effect for Simultaneous Removal of SO2 , NO, and CO2 in Flue Gas on Ion
Exchanged Zeolites. Ind. Eng. Chem. Res. 2013, 52, 6778–6784. [CrossRef]
167. Chiu, C.-H.; Hsi, H.-C.; Lin, C.-C. Control of mercury emissions from coal-combustion flue gases using CuCl2 -modified zeolite
and evaluating the cobenefit effects on SO2 and NO removal. Fuel Process. Technol. 2014, 126, 138–144. [CrossRef]
168. Wang, H.; Yu, Q.; Liu, T.; Xiao, L.; Zheng, X. NOx storage and reduction with methane by plasma at ambient temperature. RSC
Adv. 2012, 2, 5094–5097. [CrossRef]
169. Wang, H.; Li, X.; Chen, P.; Chen, M.; Zheng, X. An enhanced plasma-catalytic method for DeNOx in simulated flue gas at room
temperature. Chem. Commun. 2013, 49, 9353–9355. [CrossRef]
170. Vikrant, K.; Kumar, V.; Kim, K.-H.; Kukkar, D. Metal–organic frameworks (MOFs): Potential and challenges for capture and
abatement of ammonia. J. Mater. Chem. A 2017, 5, 22877–22896. [CrossRef]
171. Khan, N.A.; Hasan, Z.; Jhung, S.H. Adsorptive removal of hazardous materials using metal-organic frameworks (MOFs): A
review. J. Hazard. Mater. 2013, 244–245, 444–456. [CrossRef]
172. Murdock, C.R.; Hughes, B.C.; Lu, Z.; Jenkins, D.M. Approaches for synthesizing breathing MOFs by exploiting dimensional
rigidity. Coord. Chem. Rev. 2014, 258–259, 119–136. [CrossRef]
173. Xiao, T.; Liu, D. The most advanced synthesis and a wide range of applications of MOF-74 and its derivatives. Microporous
Mesoporous Mater. 2019, 283, 88–103. [CrossRef]