Chemical Engineering Journal 420 (2021) 127588

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Review

Recent advances in simultaneous removal of SO2 and NOx from exhaust

gases: Removal process, mechanism and kinetics
Rong Chen a, Tongsheng Zhang a, b, *, Yiqun Guo a, Jiawei Wang c, Jiangxiong Wei a, b,
Qijun Yu a, b, *
a
School of Materials Science and Engineering, South China University of Technology, 510640 Guangzhou, China
b
Guangdong Low Carbon Technologies Engineering Center for Building Materials, 510640 Guangzhou, China
c
Energy and Bioproducts Research Institute (EBRI), Aston University, Aston Triangle, B4 7ET Birmingham, UK

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

Keywords: SO2 and NOx, major gaseous pollutants in exhaust gas, can exert adverse effects on human health and envi­
Simultaneous SO2 and NOx removal ronmental disaster. Therefore, numerous desulfurization (de-SO2) and denitrification (de-NOx) technologies have
Catalytic oxidation been designed to reduce SO2 and NOx emissions. Compared to traditional multi-step removal processes, simul­
Catalytic reduction
taneous removal of SO2 and NOx has been attracting significant attention recently. This paper timely reviewed
Absorption or adsorption
Microbial desulfurization and denitrification
available literature focused on simultaneous de-SO2 and de-NOx methods, which are classified into four pathways
as oxidation, reduction, adsorption/absorption and microbial purification. The removal process, basic mecha­
nism and kinetics of each pathway are systematically reviewed in consideration of reactants, catalyzers, tem­
peratures and atmosphere. Moreover, the main challenges and potential breakthroughs in developing novel
simultaneous de-SO2 and de-NOx methods are critically discussed to provide a roadmap for prospective research
activities. Therefore, this review provides a deeper insight in understanding the mechanisms of de-SO2 and de-
NOx, and then helps to develop innovative simultaneous removal methods or improve the efficiency of available
abatement methods.

1. Introduction pollution in China and India. For instance, SO2 and NOx emissions of
China are mainly originated from coal-fired power plants, smelters,
1.1. SO2 and NOx emissions cement plants and transportation as shown in Fig. 1c, which are all
closely related to the combustion of fossil fuel [5].
Sulfur dioxide (SO2) and nitrogen oxides (NOx) are considered as the
primary pollutants in exhaust gases since they are responsible for such
environmental problems like acid rain, photochemical smog, tropo­ 1.2. Generation of NOx and SO2
spheric ozone and regional haze [1]. Additionally, numerous researches
show the associations between exposure to air pollutants and adverse SO2 emissions are assigned to the oxidation of sulfur-containing
health outcomes, such as increased hospital admissions for respiratory minerals during heating and combustion, particularly when coal is
and cardiovascular diseases, congestive heart failure, increases in used as dominant fuel, especially in China and India. Sulfur in coal,
asthma attacks and acute bronchitis, and altered lung function [2,3]. varying from 0.2 to 11 wt% (normally < 4%) depending on coal-forming
With the increasing environmental awareness of government and conditions, is bounded mostly in the forms of sulfides, organic sulfur
society, many efforts have been given to reduce SO2 and NOx emissions, compounds, traces amounts of sulfates and elemental sulfur. Most of
resulting in a significant downward trend in recent decades, particularly organic sulfur compounds and sulfides are volatilized and then oxidized
for SO2 (Fig. 1a). SO2 and NOx emissions of European and North to SO2 in the range of 400–600 ◦ C during combustion (Eqs. (1)–(3)),
American have reduced up to 50–70% since 1990, while those of Asia respectively [8]. In contract, sulfates are decomposed and release SO2 at
have shown a steady upward trend (Fig. 1b) [4], leading to serious air relatively higher temperature (generally > 1200 ◦ C) (Eqs. (4) and (5)).
And a portion of sulfates remain undecomposed in the ash especially for

* Corresponding authors at: School of Materials Science and Engineering, South China University of Technology, 510640 Guangzhou, China.
E-mail addresses: mstszhang@[Link] (T. Zhang), concyuq@[Link] (Q. Yu).

[Link]
Received 9 August 2020; Received in revised form 7 October 2020; Accepted 28 October 2020
Available online 28 November 2020
1385-8947/© 2020 Elsevier B.V. All rights reserved.
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

low-temperature combustion. In fact, there will be an inevitable further that the fuel-NOx mechanism includes a rapid (not rate limiting) con­
oxidation of SO2 to form SO3, depending on the concentrations of SO2 version of fuel nitrogen compounds into intermediate nitrogen com­
and O2 and temperature [9]. Whereas the amount of SO3 is relatively pounds (mainly in terms of HCN, CN, NH2, NH, N), which can either be
small and can be captured by alkali compounds in the ash, leading to a converted to NO by attack of oxygen containing species or be converted
much lower concentration of SO3. Thus, only SO2 is detected in the to N2 by reaction with NO itself (Eqs. (11)–(18)) [13].
exhaust gas under typical flame. In addition, other raw materials (such
Thermal − NOx : O + N2 ⇌ NO + N (6)
as. iron ore and limestone) generally contain sulfides and sulfates,
resulting in high SO2 emissions of cement and smelting industries [10].
N + OH ⇌ NO + H (7)
Elemental sulfur : S + O2 →SO2 (1)
N + O2 ⇌ NO + O (8)
Organic sulfur : R − S + O2 → SO2 + CO2 + H2 O(R : alkyl) (2)
Prompt − NOx : CH + N2 ⇌ HCN + N (9)
Sulfides : 2FeSx + (1.5 + 2x)O2 → Fe2 O3 + 2xSO2 (3)
CH2 + N2 ⇌ HCN + NH (10)
Sulfates : CaSO4 → CaO + SO2 + 0.5O2 (4)
Fuel − NOx : HCN + O = NCO + H (11)
CaSO4 + CO → CaO + SO2 + CO2 (5)
HCN + HO = NCO + H2 (12)
Theoretically, NOx can exist in the form of N2O, NO, NO2, N2O3,
N2O4, NO3 and N2O5. However, NOx in exhaust gas normally consists of CN + O2 = NCO + O (13)
>95% NO and <5% NO2, which might be variable slightly depending on
the temperature and atmosphere (particularly for the concentrations of NCO + O = NO + CO (14)
O2 and CO) [11]. NOx during fuel combustion can be classified into
thermal-NOx, prompt-NOx and fuel-NOx are classified according to their CN + O = N + CO (15)
formation mechanisms. Thermal-NOx is formed through the oxidation of
the N2 in the gas flow under high temperature conditions (>1450 ◦ C). NH + O = N + OH (16)
Thus, the formation of thermal NOx is highly temperature-dependent
and is in proportional to gas residence time in the high temperature NH + O = NO + H (17)
zone and O2 concentration, and Eq. (6) is the reaction controlling step
NH2 + O = NH + OH (18)
due to its higher activation energy as described by the Zeldovich
mechanism (Eqs. (6)–(8)) [12]. Prompt-NOx is produced owing to the For exhaust gases from industrial furnaces or boilers, fuel-NOx is the
reaction between N2 with hydrocarbon radicals (such as CH, C2H and predominant source of NOx emissions of low temperature combustion
CH2) in the fuel rich zone (Eqs. (9) and (10)). Fuel-NOx is produced due process [14], while both thermal-NOx and fuel-NOx contribute to the
to the oxidation of nitrogen-containing species (char-nitrogen and NOx emissions of high temperature combustion process, as the amount
volatile-nitrogen, mainly HCN and NH3) in fuel. It is generally accepted of thermal-NOx increase exponentially with temperature. Prompt-NOx,

Fig. 1. The emissions of SO2 and NOx: (a) global SO2 emissions from 1990 to 2015. Modified from [4]; (b) mean annual rate of change in simulated total inorganic
nitrogen deposition between 1984 and 2016. Modified from [6]; (c) sources of SO2 and NOx emissions by sector in China, in 2017 [7].

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R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

only accounts for <5% of the total NOx emissions, which can be ignored Available flue gas de-SO2 processes, in terms of wet scrubbers, spray
during nearly all combustion processes. Therefore, serves countermea­ dry scrubbers, sorbents injection, etc. are listed and compared in
sures have been taken to mainly reduce the thermal-NOx and fuel-NOx in Table 1. Wet scrubbers, with a maximum removal efficiency as high as
the flue gas. 99%, are the most widely used technologies for SO2 control throughout
the world [20]. Calcium-sodium based sorbents, mainly limestone
1.3. SO2 and NOx abatement methods (CaCO3), lime (CaO), or magnesium-enhanced lime, have been used in a
slurry mixture, which are injected into a specially designed vessel to
With the increasing concern of environmental impacts of industry, react with the SO2 in the flue gas. Sludge byproducts are precipitated
more and more attention has been paid to find effective ways to reduce due to their low solubility and then removed. Dual alkali and aqueous
SO2 and NOx emissions particularly when fossil fuels are used. In the ammonia methods follow the similar processes and produce a disposal
case of incineration processes, three approaches to abatement of SO2 or byproduct [21].
NOx emissions are known as: pre-combustion, control-combustion and Spray dry scrubbers, also referred as semi-dry process, introduce
post-combustion methods. lime suspension slurry to capture SO2, meanwhile the reaction products
are dried by the waste heat of flue gas, and then collected by an efficient
1.3.1. Pre-combustion methods particulate separation device (electrostatic precipitator (ESP) or fabric
Pre-combustion methods, also known as the first-end control tech­ filter). Since dry byproducts can be easily treated or recycled, spray dry
nology, can be simplified described as selecting fuel and raw materials scrubbers are also suggested de-SO2 technologies due to their avail­
with low nitrogen/sulfur contents or reducing the amount of nitrogen/ ability, easier operation and relatively low cost.
sulfur contents in fuel and raw materials. For instance, the most effective Sorbents injection systems are structured in furnace sorbents injec­
measure to reduce SO2 emission is to burn low-sulfur coal. Another way tion, economizer sorbents injection, duct sorbents injection and hybrid
is to wash coal before combustion in coal-fired power plant if high-sulfur sorbents injection. For furnace sorbents injection, dry sorbents, such as
coal must be used in coal-fired power plant, which can reduce 40% of hydrated lime or sometimes limestone, are injected directly into furnace
inorganic sulfur. However, this method is too demanding on coal, which section with temperature range of 950–1000 ◦ C. As hydrated lime or
is very restrictive for areas where natural resources are increasingly limestone decomposes to porous lime with high surface area, which can
scarce. In addition, this method can only slightly reduce the SO2 and capture SO2 in flue gas to form CaSO4. Finally, both CaSO4 and
NOx emissions, as only about 20% of SO2 in flue gas can be removed, and unreacted sorbents are collected with fly ash in the dust collector. In
nearly no effect on NOx reduction has reported [15]. economizer sorbents injection, lime is injected into the connective pass
of a coal-fired utility boiler to react directly with SO2 to form CaSO3 and
1.3.2. Control-combustion methods CaSO4 at an optimum temperature range of 500–570 ◦ C. For duct sor­
Control-combustion methods, also known as clean combustion bents injection, finely dispersed dry sorbents (mostly hydrated lime,
technology, aim to reduce SO2 and NOx emissions from the view point of sometimes sodium bicarbonate) are injected into the flue gas down­
optimizing the combustion processes and improving fuel utilization ef­ stream between the air preheater and particulate collector, to react with
ficiency. The SO2 reduction can be achieved by feeding briquettes with and remove acidic components such as SO2, SO3 and HCl. The advan­
sulfur-fixing additives, or injecting calcium-based absorbents (such as tages of this method are low investment and installation area, easy
limestone, CaO and Ca(OH)2) during combustion process [16], as a large retrofitting on old boilers and maintenance with no slurry handling.
proportion of SO2 can be captured by alkaline absorbents. However, low removal efficiency of SO2 (<50%) and low sorbents uti­
In the late 1950 s, control-combustion were first performed to reduce lization ratio are generally reported.
NOx emissions [17], which could be divided into nitrogen-free com­ (2) Flue gas denitrification methods
bustion and low-NOx combustion. Nitrogen-free combustion controls the Selective catalytic reduction (SCR) and selective non-catalytic
generation of NOx from the source by regulating the substances entering reduction (SNCR) and are major post-combustion NOx abatement tech­
the combustion process [18]. For example, chemical chain combustion nologies for post-combustion treatment of NOx in the flue gas from the
is a flameless combustion process, in which the fuel is not directly stationary sources. For SCR process, reductants (NH3, hydrocarbons
burned in contact with air. Instead, the combustion process is realized by (CxHy), CO and H2) are injected into the flue gas, and then reacts with
cyclically alternating reactions of two oxygen carriers, such as Fe and Ni. NOx over catalyst surface to form N2 and H2O at a temperature of
Fuel-NOx cannot generate in this process and thermal NOx can also be nominally 260–455 ◦ C [22]. In commercial applications, ammonia
controlled, as the flame-free gas–solid reaction temperature is much (NH3) is generally used as a reductant for the SCR process, major
lower than the conventional combustion temperature. In contrast, low- chemical reactions are shown as Eqs. (19)–(21). Catalysts most often
NOx combustion reduces the formation of NOx by restricting the peak used in NH3-SCR process are monolith with vanadium as an active
temperature of combustion flame, limiting the oxygen concentration component and titanium as a support with the addition of tungsten oxide
and residence time in the flame peak (reaction zone). Due to low initial or molybdenum oxide to increase its service life by decreasing the
investment, no running cost, simple maintenance and easy operation, harmful influence of sulfur oxides. The temperature window of these
various low-NOx combustion technologies have been developed and catalysts is broad in comparison to Pt-containing catalysts, but the op­
widely applied. Such as applying low-NOx burners, rearranging the timum operation temperature is 300–400 ◦ C [23]. However, the toxicity
burner design, staging the air/fuel, and introducing over fire air (OFA) of vanadia species and the catalyst poisoning caused by alkali and
[19], which can achieve maximum removal efficiency of 30–50%. oxidation of SO2, erosion and plugging of catalyst due to high dust
concentration remain unavoidable problems that have not been solved
1.3.3. Post-combustion methods yet. Additionally, it is still a challenge to develop cost-effective catalysts
Since both pre-combustion and combustion control methods have for low-temperature SCR process, particularly for temperature
been applied, only a low removal efficiency can be achieved, resulting in under < 200 ◦ C [24]. SNCR process involves injection of ammonia (NH3)
that most of exhaust gas from industrial furnaces cannot meet the or urea (NH2CONH2, release NH3 according to reaction (22)) solutions
emission standards if no further countermeasures are taken. Therefore, without any catalyst and typically at 850–1100 ◦ C. At this temperature
post-combustion methods are implemented to achieve higher NOx/SO2 range, NH3 reacts with NOx, to give harmless N2 and H2O as reaction
reduction. Flue gas de-SO2 and de-NOx were initially carried out in (23). However, the NH3 tends to oxidize to form NOx rather than
separate devices, and then gradually evolved to simultaneous de-SO2 reducing NOx at a higher temperature (>1100 ◦ C). Therefore, SNCR
and de-NOx in one device. process is not as discriminatory towards reduction of NOx as the SCR
(1) Flue gas desulfurization methods process, and then the molar ratio (MR) of NH3 to NOx should be above

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Table 1
Available de-SO2 and de-NOx methods for industrial flue gases.
Gas Method Process Reactant Product Advantages Disadvantages Max removal Ref.
efficiency
(%)

SO2 Wet scrubbers

—Limestone- The SO2 in flue gas is scrubbed Lime or limestone Gypsum 1. Reliable 1. High operation and 95–99% [27]
gypsum by lime or lime stone slurry. technology 2. High maintaining cost 2.
scrubbing removal efficiency Clogging and erosion of
3. Recyclable by- pipes
products
—Wet lime A modified lime process by Magnesia, lime Gypsum 1. Reliable 1. High operation cost 2. 95–99% [28]
scrubbing and involving 3–8% MgO in to lime technology 2. Clogging and erosion
Magnesium- slurry. Regenerable of pipes 3. Large wastewater
enhanced lime MgO discharging
scrubbing
—Dual Alkali The SO2 is scrubbed by NaOH Lime, NaOH Gypsum 1. High removal 1. The oxidation of NaSO3 95–99% [29]
scrubbing solution, and lime is efficiency 2. to NaSO4 2. Gypsum with
introduced to regenerate Regenerable of high sulfates
NaOH. NaOH
—Aqueous The SO2 in flue gas is scrubbed Ammonia Ammonia 1. Reliable 1. High investment cost 2 >90% [30]
ammonia by dilute ammonia. sulfite, technology 2. Ammonia leakage and
scrubbing ammonia Recyclable by- NH3 escaping
bisulfite products
—Seawater The SO2 is scrubbed by the Seawater, limestone Waste 1. Operational 1. Geographical 90–95% [31]
scrubbing natural alkalinity of seawater, seawater simplicity 2. Less restrictions 2. Impacts to
then air is inlet to reduce its equipment marine species 3. Limited
chemical oxygen demand and investment alkalinity of seawater
acidity before discharged back
to the sea.
—Wellman-Lord The SO2 is scrubbed by NaSO3 Sodium sulfite SO2 1. Fast absorption 1. Low recovery ratio 2. >90% [32]
scrubbing solution, then desorbed and speed 2. High High investment costs
collected in the regeneration removal efficiency
unit.
—Cansolv The SO2 is scrubbed by lean Amine SO2 1. High removal 1. High energy >99% [33]
scrubbing amine solution in a efficiency 2. consumption 2. Large
countercurrent scrubbing Regenerable of space occupation
tower, then the amine solution absorbent
is regenerated by indirect
steam stripping and pure SO2
released is collected.
Dry scrubbers The SO2 is scrubbed by dry Limestone or Gypsum, 1. Operational 1. Low removal efficiency 50–60% [29]
sorbents during calcination or dolomite calcium simplicity 2. Less 2. High absorbent
discharging, then byproducts sulfite, equipment consumption
are dried and removed by a flying ash investment
dust precipitator.
Sorbent injection The SO2 is scrubbed by finely Hydrated lime or Gypsum, 1. Operational 1. Low removal efficiency 50–80% [34]
process dispersed dry sorbents injected even limestone, calcium simplicity 2. Less 2. High absorbent
into the downstream of flue sometimes sodium sulfite, equipment consumption
gas. bicarbonate flying ash investment
Circulating The SO2 is scrubbed by dry Lime or limestone Gypsum, 1. Less equipment 1. Low removal efficiency 53–97% (Ca/ [35]
fluidized bed sorbents during combustion. calcium investment 2. Fast 2. Utilization of solid S = 1.2–1.5)
(CFB) sulfite, absorption speed waste
flying ash 3. No waste water
NOx SCR The NOx is reduced to N2 over NH3, CxHy, CO, H2, N2 1. Reliable 1. High operation and 80–95% [36]
the surface of catalysts at low etc. technology 2. High maintaining cost 2.
temperature (typically removal efficiency Catalyst deactivation 3.
200–450 ◦ C). Ammonia leakage 4.
Equipment corrosion
SNCR The NOx is reduced to N2 Ammonia or urea N2 1. Reliable 1. High consumption of 30–70% [25]
without catalyst at high technology 2. No reactant 2. Ammonia
temperature (800–1100 ◦ C). catalyst used 3. leakage 3. The formation
Less equipment of N2O and CO 4. Fly ash
investment and unburned carbon
increasing
Electron beam The NOx reacts with fast – Nitrates 1. Less space 1. High energy 70–90% [37]
irradiation electrons (300–800 keV) occupation 2. consumption 2.
generated under electron beam Operational Generating radiation 3.
irradiation to form nitric acids. simplicity 3. Less High investment cost
secondary
pollution
Alkali absorption The NOx is oxidized and then NaOH, Ca(OH)2, Nitrates 1. Regenerable of 1. Low removal efficiency 10–50% [38]
absorbed to form nitrate NH4OH, etc. adsorbents 2. 2. High consumption of
during passing through Operational adsorbents 3. Large space
alkaline solution. simplicity occupation
Complex The NOx is absorbed by metal Fe2+-EDTA, Co Nitrates 1. Mild reaction 1. Low removal efficiency 10–60% [39]
absorption complex solutions to form (NH3)2+
6 , etc. conditions 2. 2. Difficulty in recycling
(continued on next page)

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Table 1 (continued )
Gas Method Process Reactant Product Advantages Disadvantages Max removal Ref.
efficiency
(%)

metal-nitrosyl complexes Operational of chelates 3. High

rapidly. simplicity 3. Less operational cost
space occupation
Catalytic The NOx is oxidized to nitrate H2O2, KMnO4, Nitrates 1. High utilization 1. Catalyst poisoning 2. 70–95% [40]
oxidation during passing through NaClO2, etc. of oxidant 2. Fast Narrow temperature
absorption solutions containing oxidants oxidation speed 3. window
in the presence of catalyst. High removal
efficiency
Bioprocesses The NOx in the flue gas is Microorganisms NO−3 /NO−2 1. Less secondary 1. Instability of removal 40–90% [41]
converted into organic (denitrifying fungi, or N2 pollution 2. Low efficiency 2. Short life-
nitrogen compounds or N2 the nitrifying archaea, energy span of microorganisms
presence of microorganisms. etc.) consumption

unity. Reduction efficiency tends to maximal value (30–70%), only particularly in developing countries to solve their serious air pollution.
when the MR of NH3 to NOx lies in the range of 1.5–2.5 [25]. In contrast, Such as solid-phase adsorption regeneration, complex absorption, urea
SCR has a much higher reduction efficiency of 80–95%, and optimal MR scrubbing, enhanced wet scrubbing with transition metal ion catalyzer,
of NH3 to NOx equals to 0.9–1.0 [26]. However, NH3 injected cannot absorption agent spray methods, photocatalysis removal, electron beam
react with NOx completely for both SCR and SNCR processes due to irradiation and pulsed corona plasma [42]. Original or modified acti­
insufficient mixing, inappropriate temperature and concentration pro­ vated carbon, activated coke and activated carbon fibers are frequently
files, the NH3 discharged with flue gas not only leads to duct erosion by used for pollutants removal in carbon-based materials adsorption tech­
ammonia bisulfate, but also results in accumulation particulate matter nologies due to their porous structure and strong adsorption ability. For
to form primary and secondary aerosols and then to local smog and haze. wet scrubbing technologies, oxidants (NaClO2, KMnO4/NaOH, urea,
H2O2, etc.) are ultilized to convert water insoluble NO into soluble NO2,
4NO + 4NH3 + O2 → 4N2 + 6H2 O (19)
which could be then removed by chemical solutions. In addition, SO2
and NOx in the flue gas can be reduced simultaneously to sellable
6NO2 + 8NH3 →7N2 + 6H2 O (20)
commercial states without pollution by employing non-thermal plasma
2NO2 + 4NH3 + O2 → 3N3 + 6H2 O (21) (NTP), without chemical additives, lower investment and operating cost
and no secondary pollution. Until now, most of simultaneous DDTs are
NH2 CONH2 + H2 O → 2NH3 + CO2 (22) still being examined in bench-scale or pilot test facilities, only few of
them have been industrialized. However, simultaneous SO2/NOx
4NO + 4NH3 + O2 → 4N2 + 6H2 O (23) removal processes allow simple and reliable cleanup for large volume
exhaust flue gas at a competitive cost, and result in the production of
Numerous methods are also employed to reduce NOx emissions, as
valuable by-products (e.g., fertilizer (such as (NH4)2SO4), gypsum,
set out in Table 1. For instance, electron beam (EB) irradiation process is
elementary S) and especially eliminate solid or liquid the waste mate­
a prosperous method investigated extensively. In this process, NOx is
rials generated in several scrubbing or adsorbing processes. Therefore,
oxidized to nitrate by oxidants (HO•, O, O3) generated under irradia­
simultaneous SO2/NOx removal technologies will be the promising
tion, or reduced to N2 directly by N•. Additionally, NOx can also be
technologies to remove multi-pollutants from industrial flue gas.
captured by liquid absorption, which can be subdivided into oxidation,
According to their removal mechanisms as shown in Fig. 2, simul­
reduction and complex absorption based on removal mechanisms.
taneous SO2/NOx removal processes can be classified into four path­
However, de-NOx efficiency of liquid absorption is not high enough due
ways: oxidation, reduction, adsorption/absorption and microbial
low solubility of NOx, even if oxidants, reductants or complexants are
purification, where catalyzers are often employed to increase the effi­
added to increase their removal efficiency.
ciency. For catalytic oxidation path, SO2 and NOx in flue gas are oxidized

1.4. Desulfurization and denitrification technologies

The de-SO2 and de-NOx technologies (DDTs) can be divided into two
categories. One is multi-step DDTs, in terms of the traditional step-by-
step removal process, in which de-SO2 and de-NOx devices are con­
nected in series. This kind of multi-step removing process is not only
complex in the system but also occupying a large space, which lead to
the extremely high investment and operating costs and then limit the
large-scale application of it. The other is combined DDTs, which com­
bines the de-SO2 and de-NOx processes into one device. According to the
removal mechanism, it can be sub-divided into integrated and simulta­
neous DDTs. Actually, the removal process of SO2 and NOx in the former
is two different processes, in which NH3 is added as reductant, thus the
NOx is removed by SCR reaction while the SO2 is removed by adsorption
and oxidation. However, the simultaneous DDTs can be realized in the
same process with only one chemical reagent.
Considering the difficulty in coupling discrete SO2 and NOx removal
approaches, >70 simultaneous SO2/NOx removal technologies have
been developed since the 1980s, and numerous fundamental researches
on simultaneous de-SO2 and de-NOx are increasingly carried out, Fig. 2. The pathways of de-SO2 and de-NOx.

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to high-valence oxides, and then absorbed due to their highly solubility. control due to its high oxidation rate and efficiency, non-pollution of
The removal processes can be further divided into gas–gas oxidation, decomposition products, excellent oxidation selectivity, broadly appli­
gas–liquid oxidation, gas–solid oxidation and photocatalytic oxidation cable temperature range, and so on [43].
over semiconductors according to the physical state of oxidants. In Since it is difficult to carry out a precise analysis of the mechanisms
catalytic reduction path, SO2 and NOx in flue gas are simultaneously by which O3 oxidizes NO and SO2, the reactions between O3 and various
reduced to a simple state by reductants (mainly CO, H2, CxHy, carbon, pollutants in flue gas are still rarely reported. Recently, ab initio
sodium sulfide and sodium sulfite solutions), which can also be defined calculation of quantum chemistry is employed to simulate the oxidation
as gas–gas reduction, gas–liquid reduction and gas–solid reduction, processes of SO2 and NOx by O3 injection. Mok et al. [44] proposed the
respectively. In addition to oxidation and reduction pathways, SO2 and main 12-step oxidation reaction for NOx oxidization, the dominant
NOx in flue gas can be adsorbed by solid porous materials (activated pathway is that NO is oxidized directly by O3 to produce NO2 (Eq. (24)),
carbon, MOF, zeolite, etc.) and absorbed by liquid solutions (mainly and the rate constants of the corresponding reactions were also given.
alkaline solution and complex solutions), and then desorpted/released The observation indicated that O3 directly oxidizing NO is a dominant
by heating, distillation, etc. followed by collection for recycling purpose. pathway that producing NO2. However, this 12-step reaction mecha­
In recent years, biological purification has been also explored by use of nism ignores the interaction of certain gases (such as N2O, H2O, HNO3,
microorganisms to remove SO2 and NOx from flue gas. etc.) that do exist in the flue gas. Therefore, Wang et al. [45] developed a
In this paper, the available simultaneous de-SO2 and de-NOx methods new 65-step detailed reaction mechanism with 20-species, and the ki­
were summarized according to the physical state of reactants during netic simulation agrees well with the experimental results. By Chemkin’s
their removal pathways. Available reviews mainly focus on removal sensitive analysis (SENKIN module), the main O3 oxidation pathway is
efficiency and influencing factors, the present review, however, aimed at also determined as NO mainly converts to NO2 at 443 K and 2.93 s, with
providing a cutting-edge critical assessment of timely research outputs initial NO concentration of 280 ppm. Further oxidation of NO2 also
on simultaneous SO2 and NOx removal from flue gas. Specifically, occurred, but the amount of N2O5 can be ignored, and NO3 appeared
removal processes, basic mechanisms and reaction kinetics were elab­ only when [O3]/[NO] MR > 0.9. Since>40 kinds of gaseous substances
orately reviewed in consideration of reactants, catalyzers, temperature are contained in the flue gas emitted from actual industrial furnaces
and atmosphere. Newly developed and innovative methods, such as non- [46], a concept of O3 detachment is proposed by Wang et al. [47], and
thermal plasma (NTP), photocatalytic oxidation (PCO) and microbial reaction mechanism consisting of 121 steps and 40 substances are then
purification, were also introduced either. The main challenges and po­ constructed by involving NOx, SO2, Hg, HF, HCl, Cl2, H2S, HCl, CO, and
tential breakthroughs in developing novel simultaneous de-SO2 and de- so on. According to numerical simulation, O3 can be inferred to mainly
NOx methods have been critically reviewed to provide a roadmap for react with NO but rarely with NO2 when no excessive O3 is provided.
prospective research activities carried out this far and establishment of a Generally, major oxidation pathways of NO are illustrated in Fig. 3, the
blue print for future researches. Therefore, this paper provides a deeper arrow thickness describes the reaction intensity of the branch-chain
insight in understanding the mechanisms of simultaneous de-SO2 and reaction. Definitely, NO3 and N2O5 are the senior status of NO oxida­
de-NOx, and then helps to develop novel simultaneous removal methods tion, which are generated via a step-by-step oxidation of NO and only
or improve the efficiency of existing abatement technologies. appear when O3 is excessive [48,49]. Additionally, the reaction between
NO and HO2• can generate HNO and then convert to N2O. Compared
2. Oxidation approach with SO3, the concentration of SO2 in flue gas is much higher due to its
lower dissolvability and reactivity. Generally, the SO2 absorption in a
Compared with SO2 and NO, SO3 and N2O3/N2O5 have much higher humid washer can be accelerated by injection of O3, but the oxidization
reactivity and solubility, thus SO2 and NOx removal process can be rate of SO2 exposure to O3 is not particularly high because of the high
significantly accelerated by oxidizing SO2 and NO to SO3 and N2O3/ energy barrier of reaction (25) [50].
N2O5, respectively, and consequently increases the removal efficiency
NO + O3 → NO2 + O2 k = 1.8 × 10− 14
cm3 mol− 1 s− 1
(24)
particularly for high velocity gas flow. Obviously, the controlling or the
key step is to oxidize low valence nitrogen and sulfur oxides to higher-
SO2 + O3 → SO3 + O2 k = 1.8 × 10− 24
cm3 mol− 1 s− 1
(25)
valence nitrogen and sulfur oxides, and the oxidation rates of SO2 and
NOx largely depends on the reactivity and concentration of oxidants, Numerous literature has shown that the MR of [O3]/[NO] has a great
temperature and catalyzers. According to the state of oxidants used, influence on NO oxidation [50]. Specifically, when MR = 1.25–1.75, NO
catalytic oxidation processes were divided into gas–gas oxidation, is mainly oxidized to NO2, and now begins to be oxidized to high-valent
gas–liquid oxidation and gas–solid oxidation. Then the removal process,
basic mechanism, reaction dynamics and principal factors influencing
the removal efficiency were reviewed.

2.1. Gas-gas oxidation

Gas-gas oxidation allows a fully effective contact between the re­

actants, and the activation energy of the homogeneous gas phase is
relatively low, which makes the reaction easy to proceed. The gaseous
oxidants mainly refer to oxygen (O2), ozone (O3) and chlorine (Cl2) or
chlorine dioxide (ClO2). In addition, non-thermal plasma method ionizes
O2 and H2O to active free radical (O•, HO•, etc.), which can also be
regarded as gaseous oxidant for SO2 and NOx remove from exhaust gas.

2.1.1. Ozone (O3) oxidant

Simultaneous SO2 and NOx removal process can be enhanced by
injection of O3, such that it is able to oxidize the insoluble NO and SO2
into high-soluble nitrogen oxides (such as NO2, NO3, N2O5, etc.) and
SO3, respectively, which are then removed by normal de-SO2 facilities. Fig. 3. Schematic diagram of the main pathways of NOx and SO2 oxidation by
Therefore, O3 is widely studied in flue gas purification or emission O3. Modified from [49].

6
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

nitrogen oxides (such as NO3 and N2O5) only when MR > 1.75. Although Preequilibrium mechanism with NO3 as an intermediate:
high-valent nitrogen oxides have a higher solubility and reactivity,
NO + O2 → NO3 (29)
excessive O3 is rare used practical applications due to the higher prep­
aration cost of O3. Similarly, O3 can also react with SO2 to form highly
NO + NO3 → 2NO2 (30)
soluble SO3, which promotes the absorption of SO2. However, the use of
O3 to simultaneously oxidize SO2 and NO often fails to achieve the Since the above mechanisms are difficult to identify conclusively due
purpose of sufficiently oxidizing SO2. The activation energy for to wide variation of conditions and inaccuracy in experimental data.
oxidizing SO2 with O3 is 20 times as that of NO (58.17 kJ/mol and Thus, quantum chemical and experimental investigations have been
2.58 kJ/mol respectively) [51], suggesting that the reaction between NO performed on NO-O2 system and other related (NO/O−2 ) systems. A
and O3 is much easier to carry out. As a result, NO is preferential significant step forward in understanding the oxidization reactions has
oxidized by O3, and the reaction rate of SO2 and O3 is very low and does made by introducing an ab initio study of the surface potential energy of
not compete with NO. That’s why the MR of [O3]/[NO] had limited N2O4 [57], in which the peroxide ONOONO is a key intermediate
influence on the oxidation of SO2 [52], while the oxidation efficiency of (different from the transition state in the former mechanism). While
NO can be improved sharply by increasing the MR of [O3]/[NO]. Gadzhiev et al. [58] predicted the transition states were not optimized
Temperature is likewise a key factor influencing the removal rate and uniformly, then the reaction between O2 and two NO (II) molecules were
efficacy of NO and SO2. Although both oxidization rate and absorption studied by employing high-level ab initio wave function methods,
rate increase with the temperature of flue gas, the solubility of gaseous including geometry optimizations with coupled cluster (CCSD(T,full)/
molecules to decrease sharply according to the principles of physical cc-pCVTZ) and complete active space with second order perturbation
absorption. Meanwhile, higher temperature results in a higher equilib­ theory levels (CASPT2/cc-pVDZ). The reactions, which take place
rium pressure, which narrows the driving force. In another aspect, lower entirely on the singlet state potential surface, consist of two steps as
temperature benefits both oxidization and absorption processes, as all predicted in Fig. 4. The initial step is to form the CC intermediate with
the reactions are exothermic. And O3 is not stable in air or water at the saddle point TS1 and an activation barrier of 13.98 kJ/mol, then the
relatively high temperature and tends to decomposed to O2 which second step with the saddle point TS2 corresponds to the homolysis of
leading to significant oxidizability loss. Thus, the temperature of flue gas CC, in which elementary reaction of CC → TS2 is the rate-determining
has double impacts on the removal of SO2 and NOx [53], and 60–100 ◦ C step (RDS). However, Olson et al. [59] suggested that the RDS is very
is suggested for industrial application to achieve high de-SO2 and de- likely the addition of NO to either OONO or O2•NO, since ONOONO has
NOx efficiency without excessive consumption of O3. a significantly more facile pathway for rearrangement to lower-energy
species. In this process, various N2O4 isomers (cyclic, cis-cis-, cis–trans-
2.1.2. Oxygen (O2) oxidant , trans–trans-ONOONO, cis- and trans-ONONO2, O2NNO2) should be
Theoretically, O2 can also oxidize SO2 and NO, and the activation taken into consideration, as well as weakly bound molecular clusters
energy for oxidizing NO by O2 is − 4.41[± 3.33] kJ/mol in the tem­ preceding the formation of O2NNO2, and Coupe-type quasi-aromatic
perature range of 0–300 ◦ C [54]. However, the redox potential of O2 hexagonal ring intermediate NO2•O2N [60]. Owing to the differences
(0.401 V) is much lower than that of O3 (1.24 V). As a result, it’s much between the algorithms and their optimization, there are still some is­
harder to apply O2 to de-SO2 and de-NOx without catalysts. Therefore, sues about the oxidation mechanism of NO by O2.
catalysts, including precious metals, metal oxides/complexes, activated The oxidation kinetic of NO has been well established using a third-
carbon materials, etc., have been extensively studied in recent years, due order homogeneous reaction: 2NO + O2 → 2NO2, in which the rate
to higher availability and lower cost of O2. constant k is independent of variations, such as the total pressure, the
Since SO2 is easily oxidized by O2 when it is captured by H2O in the absolute concentration of NO or the MR of [NO]/[O2] [55]. The loga­
flue gas, more attention is paid to the oxidation of NOx. Several reaction rithm of the rate constant is inversely proportional to the absolute
routes have been proposed to describe the homogeneous oxidation of temperature, and the orders of the reaction are, namely, 2 for NO and 1
NO by O2 [55]. Initiation of NO oxidation is the synchronous trimo­ for O2. Specifically, k = 7.0 × 103 L2/(mol2⋅s) near the ambient tem­
lecular reaction (Eq. (26)), specifically, two NO molecules and one O2 perature and decreases by only 0.04 × 103 L2/(mol2⋅s) per degree with
molecule simultaneously collide to form a transient complex, which the increase of temperature, which is well within the limits of
then takes a single step to form two molecules of NO2. Based on Eyring’s
transition state theory and reasonable molecular properties, proved that
each O atom of an O2 molecule is partially bound to the N atoms of two
NO molecules to form NO2 [56]. However, the idea of a reaction with a
negative activation enthalpy is not convincing, because the alternatives
are steady-state formulation with normal chemical physics. To solve this
problem, two-step pre-equilibrium mechanisms with dimer of NO or
NO3 as an intermediate, have been proposed. The former mechanism
suggests that the weak but rapid dimerization of NO in equilibrium with
the monomer occurs (Eq. (27)), followed by the speedy conversion of the
dimer to NO2 when contacts with O2 (Eq. (28)). For the latter mecha­
nism, a weak but rapid addition equilibrium between NO and O2 is
assumed (Eq. (29)), and then the adduct (NO3 as an intermediate)
recombines with a second NO molecule to form NO2 (Eq. (30)).
Trimolecular reaction:

2NO + O2 → [ONOONO]* → 2NO2 (26)

Preequilibrium mechanism with dimer of NO as an intermediate:
NO + NO →(NO)2 (27) Fig. 4. Profile of singlet PES of 2NO2 + O2 → 2NO2, obtained at the CCSD(T)/
cc-pVDZ level. The solid and dotted lines indicate the minimum energy path­
ways at the CCSD (T)/cc-pVDZ and CAS (26,16)/cc-pVDZ levels, respectively.
(NO)2 + O2 → 2NO2 (28)
Bond lengths are indicated in Ångstroms, and the relative energies are in ki­
lojoules per mole. Modified from [58].

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R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

uncertainty of absolute value of k. That is to say, the oxidation of NO by changes [64,65]. However, few available kinetic models describe the
O2 is a homogeneous gas–gas reaction and obeys the differential rate effect of moisture at low concentrations (<1 vol%), and the inhibition
law. mechanism of moisture is rarely explained clearly. Since H2O is inevi­
In order to increase the oxidation efficiency, various catalysts are tably present and can react with high-valence gas oxides whether in the
introduced to provide the contact surface for both NO and O2. Micro­ atmosphere or in industrial exhaust gas, more attention should be paid
porous siliceous frameworks have remarkable reactivity at near ambient to the effect of moisture on the oxidation process of NO in a future study.
temperature (− 10–200 ◦ C) with identical reaction orders (1 for NO and
2 for O2) for gas–gas homogeneous reaction [61]. However, neither the 2.1.3. Chlorine (Cl2) and chlorine dioxide (ClO2) oxidants
precise structure nor the formation pathways of transition states can be Chlorine (Cl2) is internationally recognized as highly effective oxi­
derived according to the framework of the transition state theory. In dants, which has been widely applicated in the fields of bleaching,
contrast, Jason A et al. deduced [62] that the reaction mechanism at oxidation, and disinfection. Chlorine dioxide (ClO2) is more oxidant
150 ◦ C changes due to transform of activation energy and the reaction with higher oxidizability compared to Cl2, as the standard oxidation
orders, then a high temperature mechanism for NO oxidation reaction potentials of ClO2 in gas and solution phase is − 0.95 V and − 1.27 V,
over high-silica chabazites (CHA) has been proposed. In this sequence, respectively. SO2 and NO have been well known to react with Cl and Cl2
NO is oxidized to NO+ at acid sites of zeolite (aluminum positions of to yield SO2Cl/SO2Cl2 and NOCl/NOCl2 (Fig. 5), which can be absorbed
zeolite framework) shown as Eq. (31), then the absorbed NO+ (Z- NO+ in by water readily to form H2SO4, HNO3 and HCl. Under light conditions,
Eq. (32)) is oxidized by O2 to form N- O3 + , which reacts with NO to other active free radicals (such as HO•, ClOH•− , etc. [71,72]) are also
Z- NO2 + and NO2 (Eq. (33)). Acid site of zeolite (Z⋅) can be regenerated
during Z- NO2 + releasing NO2 (Eq. (34)). Therefore, Z- NO+ is a reactive
intermediate, and step B is regarded as the RDS, which are consistent
with the experimental reaction orders and intermediates. Assuming all
other steps are equilibrated with step B, the rate expression can be
derived as Eq. (35). When the coverage of Z- NO+ is low, the expression
can be simplified to r~(PNO)( PO2 ). For high Z- NO+ coverage, the rate
expression is better approximated by r~(PNO)α( PO2 ), where 0 < α < 1.
Oxidation mechanism of NO over H-SSZ-13 at high-temperature
(>150 ◦ C):

Step A : Z⋅+ NO ⇌ Z− NO+ Z⋅, the oxidized zeolite acid site (31)

Step B : Z− NO+ + O2 ⇌ Z− NO+

3 (32)

Step C : Z− NO+ − +
3 + NO ⇌ Z NO2 + NO2 (33)

Step D : Z− NO+
2 ⇌ Z⋅+ NO2 (34)

K app (PNO )(PO2 )

rNO2 = (35)
1 + K [Link] (PNO )

Available kinetics models for NO oxidation by O2 in consideration of

temperature, humidity and gas composition are summarized in Table 2.
Notably, the presence of moisture can significantly diminish the oxida­
tion efficiency of NO [63], according to the change of reaction orders Fig. 5. The oxidation and removal processes of SO2 and NOx by Cl2 and ClO2.

Table 2
Kinetics models for NO oxidation by O2 process proposed in literatures.
Kinetic model Reaction condition Reaction order Ref.

NO O2
∏ vi,j ∏ vi,j
a
rj = kj ⋅ cG,i ⋅ θS,i ⋅cpt Temperature: 100–370 ◦ C Gas component: NO (75–450 ppm), O2 (6%), H2O/CO2/CO (1–6%), 0.28 0.49 [66]
i i N2 balance
1/2
r = kf cO2 cNO − kb cNO2 Temperature: 150–650 ◦ C Gas component: NO (495 ppm), NO2 (15 ppm), O2 (8%), CO2 (5%), 1.00 0.50 [67]
H2O (5%), N2 balance
⎛ ( )⎞
y2NO yO2 − y2NO2 Temperature: 200–350 ◦ C Gas component: NO (1000 ppm), NO2 (200 ppm), O2 (6%), N2 1.00 0.50 [68]
kP3t ⎝ ⎠ balance
Pt Ke2
b
r = ( )3
( 1 + )( KNO2 Pt yNO2 )
− E cNO2 Temperature: 150–450 ◦ C Gas component: NO (500–1000 ppm), O2 (2–10%), H2O (1–10%) N2 1.00 0.50 [69]
r = k⋅exp ⋅ cNO y0.5O2 −
R⋅T Kep balance
( )
- E ( ) Temperature: 150–550 ◦ C Gas component: NOx (500 ppm NO2/NOx = 0.25), O2 (5%), H2O 0.90–1.00 0.55–0.59 [70]
k⋅exp ⋅ XNO ⋅X0.5O2 - XNO2 /Keq
R⋅T (2–5%), N2 balance
r =
XH2 O ( )
(
− E
)
cNO2 cn−
o2
0.5 Temperature: 200–500 ◦ C Gas component: NO (200–1000 ppm), NO2 (0–200 ppm), O2 1.00 0.75 [63]
k⋅exp ⋅cNO ⋅cno2 − (0.2–3.7%), H2O (0.11–1.07%), N2 balance
R2T K0.5
eq
r = ( )
1 + KNO2 2cNO2 + KH2 O cm H2 O

a. Where rj is rate of catalytic reaction j (mol m− 3 s− 1), kj the rate constant (s− 1), cG,i the concentration of gas species (mol⋅m− 3); θS,i the surface coverage (unitless); cPt
the site concentration (mol m3); Vi,j the molar fraction of component j (unitless).
b. Where rsi is rate of catalytic reaction i (mol g−cat1 s− 1), rgi the rate of gas-phase reaction i (mol L−gas1 s− 1), Ct the total molar concentration (mol L− 1), yj the molar fraction
of component j and Pt is the total pressure (1 atm).

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R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

created in the system, which can further oxidize SO2/NO more NTP is a partially ionized gas consisting of atoms, ions, chemically active
efficiently. molecules, and a highly energetic electron with 5–10 eV, which can be
Due to the inconvenience and high-risk during transportation and induced by dielectric barrier discharge (DBD), pulsed corona discharge
storage, Cl2/ClO2 are normally generated on-site and produced from (PCD), electron beam generated plasma (EBGP) and microwave plasma
acid solutions of either sodium chlorite or sodium chlorate by chemical (MP). Up to now, NTP has been widely applied for the degradation of
or electrolytic method. Therefore, the application of Cl2/ClO2 for de-SO2 volatile organic compounds (VOC), due to its non-equilibrium proper­
and de-NOx fully embodies the combination of liquid phase scrubbing ties and ability of inducing physicochemical reactions in gas at relatively
and gas–gas oxidation with expectedly high removal efficiency. Gener­ low temperatures. Since free radicals (H•, N•, O•, OH•, O3•, HO2•, etc.)
ally, chlorate-chloride solution is mainly used to continuously generate in plasma can convert gaseous pollutants into inert or treatable sub­
ClO2 [73], and the release rate of ClO2 is closely linked to the pH value, stances [75], NTP has been extended to simultaneously remove of NOx
temperature, and concentrations of species of the solution (discussed and SO2 in exhaust gas at atmospheric pressure with relatively lower
detailly in gas–liquid oxidation, section 2.2.3). Finally, simultaneous investment, maintaining cost and energy requirement [42]. As set out in
removal efficiency of SO2 and NOx from exhaust gases can be as high as Table 3, available NTP processes for de-NOx and de-SO2 are summarized
almost 100% and 66–72%, respectively. from the point view of plasma generation, additives, gas composition,
reaction condition and removal efficiency.
2.1.4. Non-thermal plasma (NTP) In general, the removal process of SO2 and NOx by the collision of
Plasma is generally an ionized gas (also called the fourth state of electrons with neutral molecules consist of three stages as described in
matter), which consists of a significant number of energetic electrons, Fig. 6 [94]. During the first nanoseconds, the energetic electrons in
free radicals, excited species and photons, etc. [74]. Based on the energy plasma collide with gaseous molecules (main components, such as H2O,
level, temperature and ionic density, electricity-generated plasma is N2, O2), with inducing primary radicals (HO•, O•, N•) and ions. Then
normally classified into thermal plasma and non-thermal plasma (NTP). excited molecules, like oxygen (O1D), react rapidly with the main gas to

Table 3
Experimental conditions and removal efficiencies of available NTP processes for simultaneous de-NOx and de-SO2.
Generator Additives Gas composition Reaction condition Maximum Ref.
removal
efficiency

PCD H2O (3%) NO (105 ppm), SO2 (200 ppm), HCl Energy density: 15 J/L Gas residence time: 13.33 s Reaction NO: 43% SO2: [76]
(30 ppm), O2 (10%), N2 balance temperature: 90 ◦ C Gas flow rate: 3.5 L/min 25%
H2O (2%) NO (165 ppm), NO2 (46 ppm), SO2 Pulse frequency: 38 Hz Capacitor-charging voltage: 25 kV Gas NO: 64% [77]
(254 ppm), O2(10%), N2 balance residence time: 66.4 s Reaction temperature: 25 ◦ C Gas flow rate:
10 L/min
H2O (1%) NO (479 ppm), SO2 (1040 ppm), N2 Pulse frequency: 300 Hz Capacitor-charging voltage: 53 kV Gas NO: 80% SO2: [78]
balance residence time: 6.0 s Reaction temperature: 25 ◦ C 43%
H2O (4%) Fly ash NO (330 ppm), SO2 (333 ppm), air Energy density: 65 J/L Gas residence time: 4.0 s Reaction NO: 56% SO2: [79]
(2.58 g/m3) balance temperature: 25 ◦ C Gas flow rate: 150 L/min 92%
H2O NO (200 ppm), NO2 (33 ppm), SO2 Energy density: 39 J/L Gas residence time: 1.2 s Reaction NOx: 64% SO2: [80]
(200 ppm), air balance temperature: 25 ◦ C Gas flow rate: 4 L/min >95%
Ca(OH)2 solution NO (180 ppm), SO2 (1013 ppm), air Energy density: 45.8 J/L Gas residence time: 4.4 s Reaction NO: 40% SO2: [81]
balance temperature: 25 ◦ C Gas flow rate: 72 L/min 75%
(NH4)2SO4 + NO (120 ppm), SO2 (525 ppm), O2 Energy density: 80 J/L Gas residence time: 5.0 s Reaction NOx: 71% SO2: [82]
(NH4)2S2O2−
3 (6%), CO2 (12%), H2O (3%), N2 temperature: 25 ◦ C Gas flow rate: 6 L/min 100%
balance
MP + EBGP H2O (12–18%) NOx (900 ppm), SO2 (1350 ppm), CO2 EB irradiation: 2.4 kGy MW irradiation: 550 W Reaction NOx: 81% SO2: [83]
(5000 ppm), air balance temperature: 70 ◦ C Gas flow rate: 10 L/min 91%
H2O (25%) NH3 NOx (730 ppm), SO2 (2000 ppm), CO2 EB irradiation: 40 kGy MW irradiation: 550 W Reaction NOx: 98% SO2: [84]
(10%), argon (7%) temperature: 65–70 ◦ C Gas flow rate: 17 L/min 80%
EBGP NH3 (700 ppm) NOx (240 ppm), SO2 (230 ppm), air Capacitor-charging voltage: 600 kV Gas residence time: 0.9 s NOx: 80% SO2: [85]
balance Reaction temperature: 90 ◦ C Gas flow rate: 5000–166667 L/min 75%
DBD TiO2 NO (570 ppm), SO2 (420 ppm), N2 Pulse frequency: 900 Hz Capacitor-charging voltage: 11 kV Gas NO: 65% SO2: [86]
balance residence time: 1.0 s Reaction temperature: 90 ◦ C Gas flow rate: 75%
5 L/min
TiO2 NO (300 ppm), SO2 (260 ppm), N2 Pulse frequency: 900 Hz Capacitor-charging voltage: 12 kV Gas NO: 85% SO2: [87]
balance residence time: 1.0 s Reaction temperature: 25 ◦ C Gas flow rate: 100%
5 L/min
TiO2 NO (400 ppm), NO2 (49 ppm), SO2 Pulse frequency: 900 Hz Capacitor-charging voltage: 15 kV Gas NO: 73% SO2: [88]
(400 ppm), air balance residence time: 2.0 s Reaction temperature: 25 ◦ C Gas flow rate: 100%
5 L/min
H2O (16%) NO (523 ppm), SO2 (163 ppm), O2 Energy density: 10 J/L Gas residence time: 20 s Gas residence NOx: 36% SO2: [89]
(8%), CO2 (14%), N2 balance time: 0.3 s Reaction temperature: 25 ◦ C Gas flow rate: 3 L/min 100%
H2O (12%) NO (250 ppm), SO2 (270 ppm), O2 Energy density: 21 J/L Gas residence time: 7.0 s Reaction NOx: 90% SO2: [90]
(17%), CO2 (4%), N2 balance temperature: 75–95 ◦ C Gas flow rate: 2500 L/min 100%
Na2SO3 (0.1 M), and NO (64 ppm), NO2 (18 ppm), SO2 Pulse frequency: 60 Hz Capacitor-charging voltage: 18 kV Gas NOx: 60% SO2: [91]
Na2S (0.1 M) (11 ppm), O2 (17.6%), N2 balance residence time: 3.3 s Reaction temperature: 150 ◦ C Gas flow rate: 91%
2 L/min
H2O (6%) NO (250 ppm), SO2 (1000 ppm), O2 Pulse frequency: 60 Hz Capacitor-charging voltage: 25 kV Gas NOx: 95% SO2: [92]
(6%), CO2 (12%), N2 balance residence time: 5.3 s Reaction temperature: 130 ◦ C Gas flow rate: 32%
2.7 L/min
Na2CO3 (0.0014 M) and NO (400 ppm), SO2 (1000 ppm), O2 Pulse frequency: 60 Hz Capacitor-charging voltage: 28 kV Gas NOx: 87% SO2: [93]
NaHCO3 (0.004 M) (3%), N2 balance residence time: 5.3 s Reaction temperature: 130 ◦ C Gas flow rate: 99%
8.3 L/min

Note: DBD represents dielectric barrier discharge; PCD represents pulsed corona discharge; EBGP represents electron beam generated plasma; MP represents mi­
crowave plasma.

9
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Fig. 6. Removal process of SO2 and NOx by the collision of electrons with neutral molecules: Radicals production, excitation transfer, and de-SO2 and de-NOx.

quench and generate more O• and HO•. Afterward, the electron–ion and As shown in Fig. 7(a), SO2, one of the most abundant pollutants in
ion-ion reactions create more secondary radicals, which have higher flue gas, is removed almost solely by HO•, which can be produced from
energy than those of gas molecules. Even though these radicals are short- hydrated ions, O(1D) plus H2O reactions, and excitation of H2O directly
lived under atmospheric pressure and ambient temperature conditions, by the fast electrons. When the HO• is produced primarily from ion-
they can oxidize NOx and SO2 into HNO3 and H2SO4 in a very short time molecule reactions, these reactions also generate hydronium ions
(usually<10− 3 s). These reactions are intense and rapid, almost simul­ (H3O+•nH2O), the dominant positive ions in moist gas. Ion recombi­
taneously, with no apparent sequential response. Finally, the HNO3 and nation reactions (charge neutralizations) produce H• that combines with
H2SO4 can be neutralized by the ammonia usually used in the pulse O2 to form HO2•, which reacts with NO or O3 to produce HO• in a
corona discharge process, and then the NH4NO3 and (NH4)2SO4 are combined pollutant oxidation/radical regeneration reaction. Since HO•
collected and recycled as fertilizer. also reacts with other molecules (O3, NO, NO2, etc.), thereby reduce the

Fig. 7. Schematic illustrations of dominant pathways and chemical reactions to remove SO2 (a) and NOx (b) by radicals under NTP. Modified from [96,97].

10
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

efficiency of HO• for SO2 removal, which is mainly depended on the 2.2. Gas-liquid oxidation
concentration of SO2 compared to those of the competing molecules.
The NOx removal mechanism in Fig. 7(b) is much more complicated, The wet flue gas de-SO2 (WFGD) contributes to > 95% of installed
as NO and NO2 can be removed by comparable contributions of several de-SO2 capacities in the world due to the mature, reliable and stable
reactive species, including HO•, N•, O•, HO2• and O3. The reaction devices. However, nearly all WFGD have nearly no ability to remove
between N• and NO releases N2 and O•, and the latter is also produced NOx simultaneously because of the low solubility of NO. Therefore,
by the reaction of N2 (A3Σ+ u ) with O2. The O• is removed by reaction updating the WFGD to increase the de-NOx function has attracted more
with NO2 to release NO and by reaction with O2 to form O3. The HO2• is and more attention recently. Since the solubility of NOx in water in­
formed by reaction of H• and O2, and then reacts with NO to form NO2 creases significantly with their valence, the simultaneous removal of SO2
and HO•. Moreover, the O3 reacts with NO to form NO2, and the OH• and NOx by the oxidation-scrubbing method can be achieved if NO is
reacts with NO2 to form HNO3. Though a few reactions account for the efficiently oxidized. Representative oxidants and their redox potentials
majority of NO and NO2 removal, many reactions must be included to used in gas–liquid oxidation are collected in Table 5.
obtain only fairly good agreement with experimental results. This According to removal mechanism, gas–liquid oxidation and then
complexity is exacerbated by the large number of oxidized nitrogen scrubbing methods for simultaneous de-SO2 and de-NOx can be divided
species that can be formed and react further, sometimes returning to NO into direct and indirect oxidation as shown in Table 6. In the direct
or NO2. In summary, NO is oxidized to NO2 which in turn can be oxidation process, SO2 and NO in the flue gas directly oxidized by ions in
transformed into species such as HNO3, NO3, and N2O5, all of which solution. In contrast, SO2 and NO are non-selectively oxidize to high
must react further before NOx has been removed from exhaust gases. valence oxide (SO3 and N2O3/N2O5) by free radicals in indirect oxida­
Since the removal efficiency of SO2 by NTP is around 11–22%, many tion process, which are generated by introducing catalysts or physical
additives (methane, ammonia, methanol) have been introduced into the field/phenomenon into the reactor. Compared with the direct oxidation
exhaust gas. Based on the experimental data, other reactions are process, the indirect oxidation process shows numerous advantages: (i)
considered to play a decisive role in addition to the reaction of free the free radical reaction is proceeded by a chain mechanism, that is, the
radicals. Sulphates can be formed in two pathways: radiation induced rate of the overall reaction can be quite significant even if the rate of
homogeneous SO2 oxidation (yielding H2SO4) or a heterogeneous sul­ initial radical formation or the amount of attacking radical is very small.
phate formation in aerosol droplets. Paur et al. [95] suggested that the (ii) the oxidation of free radicals is usually non-selective, so it can
heterogeneous interfacial reaction is the dominant way of de-SO2 and simultaneously remove multiple pollutants from the flue gas. Normally,
de-NOx after formation of aerosol product, and the efficiency depends on de-SO2 and de-NOx processes dominated by indirect oxidation are called
the relative humidity, ammonia concentration and dosage. At higher advanced oxidation processes (AOPs). Recently, AOPs with higher
ammonia-stoichiometry, saturation concentrations of nitrate and amount of radicals generation are found to be more attractive in multi-
ammonium to benefit the reduction of NOx. pollutants removal for high strength industrial exhaust gases, due to
Since the reaction kinetics of de-NOx/de-SO2 by NTP are still obscure their high by-product selectivity, superior carbon balance, rapid and
due to the complexity of the discharge itself and the limitations of efficient removal process, operating at atmospheric pressure and room
measuring instruments, numerous mathematical models are proposed temperature, no secondary pollution, saving space, lower investment
mainly in consideration of the generation of radicals and utilization and operating cost. However, AOPs also have some drawbacks. Such as,
efficiency. Available reaction kinetics models and their rate coefficients the short-lived free radicals may quench during the injection process,
used to calculate the time dependence of the number densities of various then the removal efficiency may be declined due to less oxidizing species
chemical species are given in Table 4. For instance, a mathematical in the reaction zone. Therefore, extending the lifetime of free radicals
model of pulsed corona discharge process has been proposed by Mok and improving their stability by appropriate methods are very important
et al. for the removal of de-SO2 and de-NOx [98], in which the con­ in the application of AOPs for simultaneous de-SO2 and de-NOx.
centrations of radicals are derived by considering direct electron impact
on the dissociation of gaseous molecules (O2, N2, H2O) and subsequent 2.2.1. H2O2 oxidant
excitation transfer reactions of excited O atom to produce O• and HO•. The HO• has strong oxidation ability (the redox potential is 2.80 eV,
To estimate the validity of the proposed models, effects of various second only to F2) to simultaneously remove SO2 and NOx from flue gas.
operating parameters, such as, gas flow, concentrations of the main Various physic-chemical processes, such as Fenton reaction, sono­
components, humidity, peak voltage and pulse repetition rate on the chemical oxidation, photocatalysis, ozonation, plasma oxidation and
removal efficiency have been verified and compared with the calculated their combination, have been introduced into AOPs to generate HO•.
results. In simulated gas stream (N2/O2/H2O/SO2) with applying DBD, Notably, hydrogen peroxide (H2O2), an environment-benign oxidant,
the conversion rate of SO2 to primarily H2SO4 is controlled by the has been received great attention as a precursor of HO•. Furthermore,
generation of OH radicals [92]. As an initial step, collisions of electrons the easy availability (million metric ton-scale) and low price (about 1.0
with gaseous molecules should be a focus for the generation of neutral $/kg of 100% H2O2 solution) have facilitated large-scale applications of
species (O•, HO• and N•), which play a central role in removing NOx H2O2-based oxidation processes [171]. Though H2O2 hold a strong
and SO2 rather than the charged radicals. The rate coefficients of NO/ oxidizing ability, NO could not be effectively oxidized into the target
SO2/N2/O2 dissociation reactions in NTP increase with the increase of product (NO−3 ) due to slow self-decomposition of H2O2, thus transition
electron temperature [99], which can be fitted by the Arrhenius metal ions (e.g., Fe2+, Cu2+, Cr3+), transition metal oxides (e.g., CrO3,
equation. Al2O3), as well as physical field/phenomenon are employed to catalyze
Although the NTP as an emerging technology has promising pros­ the decomposition of H2O2 into HO• [172]. For instance, during
pects, its practical applications is still restricted due to various de­ generalized Fenton reaction by involving Fe ions, large amount of
ficiencies, such as, the feasibility of reactor configuration for practical reactive oxygen species (ROS, such as O2− •, HO•, HO2•) with strong
use, the cost and life time of the plasma power supply, the change of the oxidation ability are produced and then oxidize SO2 and NO to more
physicochemical property in the remediation process the disposal of soluble high-valence species (H2SO4 and HNO3 respectively), which can
byproducts (e.g. O3) and the scale-up of equipment [100,101]. Thus, be further absorbed by detergents (NaOH, NaSO3, (NH3)2SO3, etc.).
there are still many works needed to be done to achieve industrial Although the chemistry behind the Fenton process can be simply
application. described as interacting between Fe cations and H2O2, numerous re­
actions proposed can be divided into two main mechanisms. The first
mechanism is based on a strong intermediate oxidant (FeO2+), and the
other mechanism, the most popular mechanism is based on the

11
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Table 4
Plasma reactions and their rate constants used in available kinetics models for de-NOx and de-SO2.
No. Reactions Rate constanta Ref. No. Reactions Rate constanta Ref.
− 11
Electron − molecule interactions H2 O + +
O→O+2 + H2 5.5 × 10 [102]
e + N2 →e + N2 (A3 Σ+
u)
4.7 × 10− 13(E/N = 40); [103] H2 O+ + O2 →O+
2 + H2 O 2.6 × 10− 10
[102]
5.7 × 10− 11(E/
N = 70);3.5 × 10− 10(E/
N = 100); 1.3 × 10− 9(E/
N = 150)
e + N2 →e + N2 (a
′
1 −
Σu ) 2.7 × 10− 10 [102] H2 O+ + N→NO+ + H2 9.0 × 10− 11
[102]
e + N2 →e + N + N 3.0 × 10− 16(E/N = 40); [103] H2 O+ + NO→NO+ + H2 O 6.0 × 10− 10
[102]
4.7 × 10− 13(E/
N = 70);9.1 × 10− 12(E/
N = 100); 9.0 × 10− 11(E/
N = 150)
e + N2 →2e + N+ + N 2.4 × 10− 17 [102] H2 O+ + NO2 →NO+
2 + H2 O 3.0 × 10− 10
[102]
− 12 − 10
e + N2 →2e + N+
2
2.4 × 10 [102] CO + O→O + CO
+ + 1.4 × 10 [102]
e + O2 →e + O2 (a1 Δg ) 3.4 × 10− 11(E/N = 40); [103] CO+ + O2 →O+
2 + CO 1.0 × 10− 10
[102]
2.5 × 10− 10(E/
N = 70);3.8 × 10− 10(E/
N = 100); 7.2 × 10− 10(E/
N = 150)
e + O2 →e + O + O( 1
D) 1.0 × 10− 12(E/N = 40); [103] CO+ + NO→NO+ + CO 3.3 × 10− 10
[102]
1.2 × 10− 10(E/
N = 70);6.9 × 10− 10(E/
N = 100); 2.3 × 10− 9(E/
N = 150)
e + O2 →2e + O + O+ 4.6 × 10− 16 [102] CO+ + NO2 →NO+
2 + CO 3.0 × 10− 10
[102]
− 15 − 10
e + O2 →2e + O+
2
1.7 × 10 (E/N = 40); [103] CO + OH→OH + CO
+ + 2.5 × 10 [102]
2.7 × 10− 12(E/
N = 70);6.2 × 10− 11(E/
N = 100); 8.0 × 10− 10(E/
N = 150)
e + O2 →O− + O 1.5 × 10− 13(E/N = 40); [103] CO+ + OH→CO+
2 + H 2.1 × 10− 10
[102]
4.6 × 10− 12(E/
N = 70);1.6 × 10− 11(E/
N = 100); 3.2 × 10− 11(E/
N = 150)
e + O2 →O−2 1.3 × 10− 11(E/N = 40); [103] CO+ + H2 O→H2 O+ + CO 1.3 × 10− 10
[102]
1.0 × 10− 11(E/
N = 70);7.0 × 10− 12(E/
N = 100); 5.6 × 10− 12(E/
N = 150)
e + O2 + H2 O→O−2 + H2 O 7.6 × 10− 34 [102] CO+ + CO2 →CO+
2 + CO
8.5 × 10− 10
[102]
34 10
e + O2 + CO2 →O−2 + CO2 7.6 × 10− [102] CO+
2 + O→O+
2 + CO 1.3 × 10− [102]
34 10
e + O2 + O2 →O−2 + O2 3.7 × 10− [102] CO+
2 + O→O + CO2
+ 1.3 × 10− [102]
34
e + O2 + N2 →O−2 + N2 5.9 × 10− [102] CO+
2 + O2 →O+
2 + CO2 6.5 × 10− 9T− 0.78
[102]
11 10
e + H2 O→e + O( 1
D) + H2 8.1 × 10− [102] CO+
2 + NO→NO+ + CO2 1.2 × 10− [102]
12 12 10
e + H2 O→e + H + OH 2.6 × 10− ; 6.8 × 10− [96] CO+
2 + NO2 →NO2 + CO2
+ 3.0 × 10− [102]
20 10
e + H2 O→2e + H+
2 + O 1.0 × 10− [102] CO+
2 + OH→OH + CO2
+ 3.0 × 10− [102]
15 9
e + H2 O→2e + H2 + O+ 1.9 × 10− [102] CO+
2 + H2 O→H2 O + CO2
+ 1.7 × 10− [102]
16 14
e + H2 O→2e + OH + H+ 4.4 × 10− [102] NO+ + O3 →NO+
2 + O2 1.0 × 10− [102]
14 10
e + H2 O→2e + H + OH+ 2.6 × 10− [102] NO+ + N2 O5 →NO+
2 + 2NO2
5.9 × 10− [102]
12 10
e + H2 O→2e + H2 O+ 1.1 × 10− [102] NO+
2 + NO→NO + NO2
+ 2.9 × 10− [102]
e + H2 O→H− + OH 2.0 × 10− 13(E/N = 40); [103] Reactions involving excited species
1.0 × 10− 11(E/
N = 70);3.5 × 10− 11(E/
N = 100); 7.2 × 10− 11(E/
N = 150)
e + H2 O→O− + H2 5.3 × 10− 13 [102] O2 (a1 Δg ) + N→NO + O 1.0 × 10− 16
[102]
11 10
e + CO2 →e + CO + O 8.7 × 10− [102] O( 1
D) + H2 O→2OH 2.3 × 10− ; [102,103]
10
2.2 × 10−
13 11
e + CO2 →2e + CO+ + O 5.0 × 10− [102] O( 1
D) + H2 O→O2 + H2 2.3 × 10− [102]
14 11
e + CO2 →2e + O+ + CO 8.7 × 10− [102] O( 1
D) + H2 O→H2 O + O 1.2 × 10− [102]
12 10
e + CO2 →2e + CO+
2
2.6 × 10− [102] O( 1
D) + O3 →O2 + 2O 1.2 × 10− [102]
e + CO2 →O− + CO 1.6 × 10− 14(E/N = 40); [103] O( 1
D) + O2 →O2 + O 6.3 × 10− 12
[102]
7.1 × 10− 13(E/
N = 70);2.5 × 10− 12(E/
N = 100); 5.2 × 10− 12(E/
N = 150)
e + SO2 →SO + O + e 3.0 × 10− 8 [99] O( 1
D) + O2 →O2 + O( 3
P) 3.2 × 10− 11
exp(67/T) [104]

(continued on next page)

12
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Table 4 (continued )
No. Reactions Rate constanta Ref. No. Reactions Rate constanta Ref.
7 11
e + SO2 →S + O + O + e 3.1 × 10− [99] O( 1
D) + N2 →N2 + O( 3
P) 1.8 × 10− exp(107/T) [104]
11
Electron − ion recombination O2 (a1 Δg ) + N→NO + O 1.8 × 10− [102]
− 12 − 11
N + e→N
+ 3.5 × 10 [102] O( 1
D) + N2 →O + N2 2.6 × 10 [102]

2 + e→N + N
N+ 2.8 × 10− 7(300/Te)0.5 [102] N2 (A3 Σ+
u ) + O2 →O + O + N2
1.5 × 10− 12
[105]
12 10
N+
2 + e→N2
4.0 × 10− [102] N2 (A3 Σ+
u ) + O2 →N2 O + O
4.7 × 10− [106]
12 12
O+ + e→O 4.0 × 10− [102] N2 (A3 Σ+
u ) + O→NO + N
7 × 10− [102]
12 7 10
2 + e→O2
O+ 4.0 × 10− ; 2.0 × 10− [102,103] N2 (A3 Σ+
u ) + CO2 →CO + O + N2
1.5 × 10− [102]
O+
2 + e→O + O 2.1 × 10− 7(300/Te)0.5 [102] N2 (a
′
1
Σ−u ) + O2 →O + O + N2 2.8 × 10− 11
[102]

N+
4 + e→N2 + N2 2.0 × 10− 6(300/Te)0.5 [102] N2 (a
′
1
Σ−u ) + NO→O + N + N2 3.6 × 10− 10
[102]

O+
4 + e→O2 + O2
1.4 × 10− 6(300/Te)0.5 [102] N2 (A3 Σ+ + N2 (a
′
1
Σ−u )→N+ +e 5 × 10− 11
[107]
u) 4
7 10
H2 O+ + e→OH + H 3.8 × 10− [102] N2 (a
′
1
Σ−u ) + N2 (a
′
1 −
Σu )→N+ + 2 × 10− [102]
4
e
7 10
H2 O+ + e→H2 + O 1.4 × 10− [102] O2 (a1 Δg ) + O3 →2O2 + O 5.2 × 10− [102]
7 10
H2 O+ + e→2H + O 1.7 × 10− [102] 1
O2 (a Δg ) + N2 →O2 + N2 1.7 × 10− [102]
12 18
NO+ + e→NO 4.0 × 10− [102] O2 (a1 Δg ) + O2 →2O2 2.2 × 10− [102]
7 15
NO+ + e→O + N( 2
D) 4.3 × 10− [102] O2 (a1 Δg ) + H→OH + O 1.83 × 10− [102]
7 11
NO+
2 + e→O + NO
3.0 × 10− [102] O2 (a1 Δg ) + HO2 →OH + O + O2 1.66 × 10− [102]
11
Ion − ion recombination N2 (A3 Σ+
u ) + N2 →2N2
2.7 × 10− [102]
7 11
N+ + O− →N + O 2.6 × 10− [102] N2 (A3 Σ+
u ) + H2 O→OH + H + N2
4.2 × 10− [102]
7 12
N+ + O−2 →N + O2 4.0 × 10− [102] N2 (A3 Σ+
u ) + NO2 →NO + O + N2
7.83 × 10− [105]
7 11
N+
2 + O →N2 + O
− 4.0 × 10− [102] N2 (A3 Σ+
u ) + N2 O→2N2 + O
8.0 × 10− [102]
7 11
N+
2 + O2 →N2 + O2
− 1.6 × 10− [102] N2 (A3 Σ+
u ) + N2 O→N2 + NO + N
8.0 × 10− [102]
7
O+ + O− →2O 2.7 × 10− [102] Reactions involving neutral at the background state
7
O+ + O−2 →O + O2 4.0 × 10− [102] N + O2 →NO + O 5.5 × 10− 12exp [108,109]
(− 3220/T);
1.1 × 10− 14Texp
(− 3150/T)
O− + O+
2 →O + O2
9.6 × 10− 8; 1.0 × 10− 7
[102,103] N + N + M→N2 + M 3.9 × 10− 33 [102]
− 7 11
O+
2 + O−2 →2O2 4.2 × 10 [102] N + NO→N2 + O 3.0 × 10− ; [102,103]
11
5.9 × 10−
− 7 13
O+
4 + O →O2 + O3
− 4.0 × 10 [102] N + NO2 →N2 + O + O 9.1 × 10− [102]
O+
4 + O−2 →2O2 + 2O 2.0 × 10− 6; 2.0 × 10− 7
[102,103] N + NO2 →2NO 6.0 × 10− 13
; [102,103]
12
9.0 × 10−
− 7 12
H2 O + O →H2 O + O
+ − 4.0 × 10 [102] N + NO2 →N2 O + O 3.0 × 10− [102]
7 11
H2 O+ + O−2 →H2 O + O2 4.0 × 10− [102] N + HO→NO + H 4.9 × 10− [102]
7 11
NO+ + O− →NO + O 4.9 × 10− [102] N + HO2 →NO + OH 2.2 × 10− [102]
7
NO+ + O−2 →NO + O2 4.0 × 10− [102] N + O3 →NO + O2 1.0 × 10− 16; [96,103]
5.0 × 10− 17
− 7
NO+
2 + O →NO + O2
− 4.0 × 10 [102] N + CO2 →NO + CO 3.2 × 10− 13exp [102,103]
(− 1711/T); 8 × 10− 33
7
NO+
2 + O2 →NO2 + O2
− 4.0 × 10− [102] O + O + N2 →N2 + O2 2.76 × 10− 34exp(720/ [110]
T)
7
H− + O−2 →H + O2 2.0 × 10− [102] O + O + O2 →O2 + O2 2.45 × 10− 31T− 0.63 [110]
Electron detachments O + N2 + O2 →O3 + N2 6.0 × 10− 34(T/ [111]
300)− 2.8[N2]
10 10
O− + O→O2 + e 5.0 × 10− ; 1.4 × 10− [102,103] O + O2 + O2 →O3 + O2 6.0 × 10− 34(T/ [111]
300)− 2.8[O2]
− 10
O + N→NO + e
−
2.6 × 10 [102] O + O3 →O2 + O2 2.0 × 10− 11exp [102]
(− 2300/T)
− 15
O− + O2 →O3 + e 5.0 × 10 [102] O + N + M→NO + M 1.76 × 10− 31T− 0.5 [102]
10
O− + H2 →H2 O + e 6.5 × 10− [102] O + NO + O2 →NO2 + O2 1.0 × 10− 31(T/ [111,112]
300)− 1.6[O2];
9.1 × 10− 28T− 1.6
10
O− + NO→NO2 + e 2.6 × 10− [102] O + NO + N2 →NO2 + N2 1.0 × 10− 31(T/ [111]
300)− 1.6[N2]
9
O− + SO2 →SO3 + e 2.0 × 10− [103] O + NO2 →NO + O2 1.13 × 10− 11(T/ [102]
1000)0.18
− 10
O + O2 (a Δg )→O3 + e
− 1 3.0 × 10 [103] O + NO2 + M→NO3 + M 5.0 × 10− 32 [102]
10 11
O−2 + O→O3 + e 1.5 × 10− [102] O + NO3 →NO2 + O2 1.0 × 10− [102]
19
O−2 + H→HO2 + e 1.0 × 10− [102] O + CO + M→CO2 + M 6.6 × 10− 33exp [102]
(− 2173/T)
10
O−2 + N→NO2 + e 5.0 × 10− [102] O + N2 →NO + N 1.06 × 10− 6T− 1exp [102]
(− 38400/T)
− 12
O−2 + N2 →O2 + N2 + e 1.9 × 10 exp(− 4990/T) [102] O + H2 O→2OH 2.5 × 10− 14T1.14exp [102]
(− 8624/T)
− 10
O−2 + O2 →O2 + O2 + e 2.7 × 10 exp(− 5590/T) [102] O + OH→H + O2 3.8 × 10− 11 [102]

(continued on next page)

13
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Table 4 (continued )
No. Reactions Rate constanta Ref. No. Reactions Rate constanta Ref.
10 14
O−2 1
+ O2 (a Δg )→2O2 + e 2.0 × 10− [103] O3 + OH→HO2 + O2 6.5 × 10− [102]
15
Charge transfers and ion conversions H2 + OH→H2 O + H 6.7 × 10− [102]
12 10
N +
+ O→N + O + 1.0 × 10− [102] HO2 + OH→H2 O + O2 1.1 × 10− [102]
10 11
N+ + O2 →O + NO+ 2.6 × 10− [102] OH + NO2 →HNO3 3.5 × 10− [102]
10 13
N +
+ O2 →N + O2+ 3.0 × 10− [102] OH + CO→CO2 + H 2.6 × 10− [102]
11
N +
+ O2 →NO + O + 3.6 × 10− [102] OH + OH→H2 O + O 6.6 × 10− 33exp [102,103]
12
(− 2173/T); 2 × 10−
10
N +
+ O3 →O2 + NO + 5.0 × 10− [102] NO2 + OH→NO + HO2 3.03 × 10− 11exp [102]
(− 3400/T)
10
N +
+ NO→NO +
+ N 5.1 × 10− [102] NO3 + OH→NO2 + HO2 2.6 × 10− 11 [102]
11 27 − 1.66
N +
+ NO→N2+ + O 5.0 × 10− [102] CO + OH→CO2 + H 1.01 × 10− T [102]
10 23 − 2.6
N +
+ NO2 →NO +
+ NO 5.0 × 10− [102] OH + H + M→H2 O + M 1.1 × 10− T [102]
10
N +
+ NO2 →NO2+ + N 3.0 × 10− [102] H + OH→O + H2 1.38 × 10− 14Texp [102]
(− 3500/T)
10
N +
+ OH→HO +
+ N 3.4 × 10− [102] O3 + H→OH + O2 2.8 × 10− 11 [102]
− 10 16
N +
+ OH→NO +
+ H 3.4 × 10 [102] O3 + N→NO + O2 5.0 × 10− [102]
9 14
N +
+ H2 O→H2 O +
+ N 2.4 × 10− [102] O3 + NO→NO2 + O2 4.6 × 10− [102]
10 12
N +
+ H2 O→NO +
+ H2 4.0 × 10− [102] HO2 + H→H2 O + O 6.7 × 10− [102]
10 11
N +
+ CO→CO +
+ N 4.9 × 10− [102] HO2 + H→2OH 6.4 × 10− [102]
9 12
N +
+ CO2 →CO2+ + N 1.3 × 10− [102] HO2 + O3 →OH + 2O2 3.0 × 10− [102]
10 15
N +
+ CO2 →CO +
+ NO 2.5 × 10− [102] HO2 + NO→NO2 + OH 2.0 × 10− [102]
29 11
N +
+ O + M→NO +
+ M 1.0 × 10− [102] H + O2 + M→HO2 + M 1.1 × 10− [102]
29 32
N +
+ N + M→N2+ M 1.0 × 10− [102] 2NO + O2 →2NO2 5.9 × 10− [102]
10 38
N2+ + O→NO +
+ N 1.4 × 10− [102] NO + O→O2 + N 1.4 × 10− [102]
12 12
N2+ + O→O +
+ N2 6.0 × 10− [102] NO + OH→HNO2 6.6 × 10− [103]
12
N2+ + O2 →O2+ + N2 4.7 × 10− [102] NO + NO3 →2NO2 1.39 × 10− 11exp [113]
(− 19400/T)
17
N2+ + O2 →NO +
+ NO 1.0 × 10− [102] NO + NO3 →O2 + 2NO 2.71 × 10− 11T− 0.23exp [114]
(− 947/T)
− 10
N2+ + O3 →O + O2+ + N2 1.0 × 10 [102] NO2 + M→NO + O + M 1.8 × 10− 8exp [115]
(− 33000/T)
11
N2+ + N→N +
+ N2 1.0 × 10− [102] NO2 + NO3 →NO2 + NO + O2 2.3 × 10− 13exp [114]
(− 1600/T)
29
N2+ + N2 + M→N4+ M 5.0 × 10− [102] NO2 + OH + M→HNO3 + M 2.71 × 10− 11T− 0.23exp [102]
(− 947/T)
− 9
N2+ + H2 O→H2 O +
+ N2 2.0 × 10 [102] NO2 + O3 →NO3 + O2 1.2 × 10− 13exp [114]
(− 2450/T)
− 14
N2+ + NO→N2 + NO + 2.35 × 10 [116] NO2 + NO3 →N2 O5 5.3 × 10− 20T− 4.1 [113]
14 12
N2+ + N2 O→N2 + N2 O + 3.61 × 10− [117] NO2 + H→NO + OH 1.1 × 10− [102]
9 10
O +
+ H2 →HO +
+ H 1.8 × 10− [102] NO2 + N→O2 + N2 5.8 × 10− exp(− 740/ [102]
T)
9 13
O +
+ N2 →N2+ + O 4.9 × 10− [102] NO3 + HO2 →HNO3 + O2 7.0 × 10− [102]
− 12
O +
+ N2 →NO +
+ N 1.2 × 10 [102] 2NO + O2 →2NO2 3.3 × 10 − 39exp(526/ [115]
T)
11
O +
+ O2 →O2+ + O 2.9 × 10− [102] NO3 + HO2 →NO2 + OH + O2 4.8 × 10− 12 [102]
− 10 15
O +
+ O3 →O2+ + O2 1.1 × 10 [102] 2NO3 →2NO2 + O2 1.2 × 10− [102]
10 15
O +
+ OH→OH +
+ O 3.3 × 10− [102] HNO3 + O→NO3 + OH 3.0 × 10− [102]
10 13
O +
+ OH→O2+ + H 3.6 × 10− [102] HNO3 + OH→NO3 + H2 O 1.3 × 10− [102]
12 11
O +
+ NO→NO +
+ O 1.0 × 10− [102] HNO2 + OH→NO2 + H2 O 0.5 × 10− [103]
9 15
O +
+ NO2 →NO2+ + O 1.6 × 10− [102] HNO2 + O→NO2 + OH 3.0 × 10− [103]
10
O +
+ NO2 →NO +
+ O2 5.0 × 10− [102] N2 O5 →NO2 + NO3 73.0 [102]
9 19
O +
+ H2 O→H2 O +
+ O 2.7 × 10− [102] N2 O5 + N2 →NO2 + NO3 + N2 1.6 × 10− [102]
9 19
O + CO2 →O2+ + CO
+ 1.0 × 10− [102] N2 O5 + O2 →NO2 + NO3 + O2 1.6 × 10− [102]
O - + O2 →O2- + O 1.0 × 10− 7
[103] N2 O5 + H2 O→2HNO3 5.0 × 10− 21
[102]
10
O2+ + N→NO +
+ O 1.8 × 10− [102] SO2 + OH→HSO3 7.5 × 10− 12; [96,103]
5.0 × 10− 31exp(300/
T)3.3[M]
16
O2+ + N2 →NO +
+ NO 1.0 × 10− [102] HSO3 + OH→H2 SO4 1.0 × 10− 12; [96,103]
9.8 × 10− 12
− 10
O2+ + NO→NO +
+ O2 3.5 × 10 [102] SO2 + O + N2 →SO3 + N2 1.4 × 10− 33; [103,118]
4.0 × 10− 32exp
(− 1000/T)[N2]
10
O2+ + NO2 →NO2+ + O2 6.0 × 10− [102] SO3 + O + N2 →SO2 + O2 + N2 8.0 × 10− 30 [103]
11
O2+ + NO2 →NO +
+ O3 1.0 × 10− [103] SO3 + H2 O→H2 SO4 6.0 × 10− 15; [103,119]
3.9 × 10− 41exp(6830/
T)[H2O]2
(continued on next page)

14
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Table 4 (continued )
No. Reactions Rate constanta Ref. No. Reactions Rate constanta Ref.
10
O2+ + N2 O5 →NO2+ + NO3 + O2 8.8 × 10− [102] HSO3 + O2 →SO3 + HO2 4.0 × 10− 13; [118,120]
1.34 × 10− 12exp
(− 330/T)
30
O2+ + 2O2 →O4+ + O2 2.8 × 10− [102] SO2 + HO2 →SO3 + OH 2.25 × 10− 16exp(300/ [121]
T)
− 10
OH +
+ NO→NO +
+ OH 4.6 × 10 [102]
10
OH +
+ NO2 →NO2+ + OH 3.0 × 10− [102]
9
OH +
+ H2 →H2 O +
+ H 1.3 × 10− [102]
10
OH +
+ OH→H2 O +
+ O 7.0 × 10− [102]
9
OH +
+ H2 O→H2 O +
+ OH 1.5 × 10− [102]

a 3 − 1 − 1 6 − 1 − 1
Note: in units of cm molecule s or cm molecule s ; M represents N2, O2, CO2, or H2O.

However, Fenton process has poor cyclic redox property, thereby

Table 5
reduces its possibility for recycling of the homogeneous catalyst and
Standard reduction potentials of representative oxidants used in gas–liquid
then leads to secondary pollution. In addition, the de-NOx efficiency is
oxidation [122].
drastically decreased with the pH of the reaction solution up to 3.5
Oxidant Half-cell reaction Oxidation potential
[133], which mainly attributes to the hydrolysis and precipitation of
(eV)
Fe2+/Fe3+ [129,136,182]. The precipitation of Fe(OH)3 not only leads
Fluorine (F2) F2 + 2e− → 2F− 3.03 to secondary pollution, but also blocks the propagation of the light
Hydroxyl radical (HO•) HO• + H+ + e− → H2O 2.80
source in the photo-Fenton process and then further inhibits the pro­
Sulfate radical (SO−4 •) SO−4 • + e− →SO2−
4 2.50–3.10
Ozone (O3) O3 + 2H+ + 2e− → O2 + H2O 2.07 duction of HO•. In order to overcome these shortcomings of Fenton
Persulfate (S2O2−
8 •) S2O2−
8 • + 2e → 2SO4
− 2−
2.10 process (homogeneous catalysis), Fenton-like process is proposed by
Peroxymonosulfate HSO−5 + H+ + 2e− → 2.10 replacing Fe2+ with transition metal (e.g., Cu, Co, Mn, Ce, Al, Cr and Ru)
(HSO−5 ) H2O + SO2− 4
ions and their interactions with H2O2 can be described as Fig. 8 (similar
Hydrogen peroxide H2O2 + 2H+ +2e− → 2H2O 1.78
(H2O2) to reaction (36)). Different from homogeneous catalysis in Fenton-like
Permanganate (MnO−4 ) MnO−4 + 4H + 3e →
+ −
1.68 process with Fe2+, both heterogeneous and homogeneous catalysis are
2H2O + MnO2 involved by introducing other metal ion(s)/metal ion-organic ligand
Chlorine dioxide (ClO2) ClO2 + 4H+ + 5e− → 1.50 complexes to spur H2O2 decomposition. However, it is more difficult to
2H2O + Cl−
separate the catalysts and the products, which lead to secondary
Chloine (Cl2) Cl2 + 2e− → 2Cl− 1.36
Chromate (Cr2O2−
7 ) Cr2O2−
7 + 14H + 6e →
+ −
1.33 pollution. Recently, solid Fe-bearing species are commonly used in
7H2O + 2Cr3+ heterogeneous Fenton-like process to active H2O2 and then oxide SO2
Molecular oxygen (O2) O2 + 4H+ + 4e− → 2H2O 1.23 and NO, due to their relatively stable physicochemical properties and
stability in a wide pH range of solutions [140,142,183].
Numerous literature proved that the dissociation of M− OH (M = Fe,
transformation of Fe2+ and Fe3+ [173]. Specifically, HO• is produced by
Al, Ce, Co, etc.) bonds on the surface of ferric oxides are the source of
the interaction of H2O2 with Fe2+ (Eq. (36)), and then further reacts with
active HO• [183–185]. Thus, there are many factors influencing the
SO2 and NO in the flue gas as described in table 7. Then the Fe3+ can be
production of HO• though the catalytic decomposition of H2O2
further reduced by H2O2 to regenerate Fe2+ (Eqs. (37)–(39)). Liu et al.
[138,139], particularly for the type and dosage of catalysts. Fig. 9 (a)
[174] found that the reaction rate constant of reaction (37) and (38) are
shows the production of HO• through the interaction of H2O2 and sol­
3.1 × 10− 3 and 2.7 × 10− 3 S− 1 respectively, indicating that reaction (38)
uble of Al3+ [186]; the other way to generate HO• is decomposition of
is the RDS of the chain reactions in the Fenton process. Moreover,
H2O2 under surface acid catalyzing through Ce3+/Ce4+ cycle as shown
physical field/phenomenon, such as the photo field, electro field, cavi­
in Fig. 9 (b). Therefore, increasing the amount of H2O2 or catalyst are
tation effect and microwave field, has been applied during oxidation-
generally adopted to increase HO• and then improve the removal effi­
scrubbing process to increase the removal efficiency. Guo et al. [175]
ciency. However, excessive H2O2 leads to the quenching of free radicals
introduced microbubbles into the catalytic phase, which can dissociate
(Eqs. (40)–(43)), and the excessive loading of the catalyst also can result
more hydroxyl radicals, as the interfacial area of H2O2 with gas is also a
in the quenching of free radicals, such as Eq. (44) for Fe2+-based cata­
key factor influencing the oxidation of SO2 and NO. Liu et al. [126]
lysts [140,187].
reported that the removal efficiency of SO2 and NOx increase up to 100%
and 96.8% respectively in a Vacuum Ultraviolet (VUV)-Activated O2/ HO⋅+ OH →H2 O2 (40)
H2O/H2O2 System. SO2 can be removed completely under all experi­
mental conditions by inletting UV light Liu et al. [176–179], while the HO⋅+ H2 O2 → HO2 ⋅+ O2 (41)
removal efficiency of NO (>90%) is greatly influenced by the concen­
tration of H2O2/NaOH/Fe2+ and energy density per unit solution [180], HO2 ⋅+ HO2 ⋅→ H2 O2 + O2 (42)
as the oxidation of NO by HO• plays a key role in NO removal [181].
Choi et al. [123] achieved the removal efficiency of SO2 and NO of both HO2 ⋅+ HO⋅→ H2 O + O2 (43)
nearly 100% by aerosolizied H2O/H2O2 under UV light conditions.
( ) Fe2+ + ⋅OH → Fe3+ + OH− (44)
H2 O2 + Fe2+ → Fe3+ + HO⋅ + OH K = 63 − 76 M− 1 S− 1 (36)
As an endogenous iron-containing material, FeO can be oxidized in
situ, and its crystal form also determines that Fe2+ can be replaced by
Fe3+ + H2 O2 → FeOOH2+ + H+ (37)
other cations (such as Co, Mn, Cr, Cu, Al, Mg, Ti, Ni) [122], which may
benefit the production of HO• due to more defects and vacancies formed
FeOOH2+ → Fe2+ + ⋅OH (38)
on the surface. In addition, when a solid solution is formed, the incor­
porated atoms can change the points of zero charge (PZC) values of the
Fe3+ + ⋅OOH → Fe2+ + O2 + H+ (39)

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R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Table 6
Main oxidants, catalyst/activation, and related direct and indirect oxidations of available gas–liquid oxidation and then scrubbing methods.
Oxidant Catalyst/Activation method Direct oxidation Indirect oxidation Ref.

H2O2 Photo/Electro/Cavitation/Microwave- SO2: H2O2 + SO2 → SO2−

4 + 2H NO:
+
SO2: 2HO• + SO2 → H2SO4 NO: NO + HO• [123–128]
Fenton-like activations 3H2O2 + 2NO → 2NO−3 + 2H+ + 2H2O → NO−2 (NO2) + H+(H•) NO2 + HO• →
Metal ion (such as Fe2+, Fe3+, Ce3+, Cu2+, NO−3 (NO3) + H+(H•) [129–133]
Co2+, Mn2+, Ag+, Cr3+)
Nano materials: nano zero-valent iron (nZVI), [134,135]
nano a-Fe2O3, nano CuO, nano-ferroferric
Mineral materials: goethite (α-FeOOH), pyrite [136–138]
(FeS2), hematite (α-Fe2O3), magnetite,
ferrihydrite, akageneite, maghemite,
schwertmannite, pseudobrookite,
lepidocrocite, wüstite, CoO3, ZrO2
Composites: Fe2+/AC, α-Fe2O3/S, CuO/Al, [139–142]
Fe2+/magnetic NdFeB-AC, layered fetitanate,
FeOOH-C, iron(III)-alginate fiber, iron oxide/
SiO2, Cu/MCM-41, iron-loaded mangosteen,
TiO2/glass sphere and the magnetite-based
catalysts, Fe3-xCr(Mn,Co,Ti,Ni,V,Al)xO4, Fe2-
xNbxO3, Fe3-x-xOTixVxO4, La1-xCaxFeO3
NaClO2/ Alkali, Photo/Electro/Cavitation/Microwave SO2: 2SO2 + ClO−(2) + 2H2O → 2SO2−
4 + 4H +
+
SO2: 5SO2 + 2ClO2 + 6H2O → 12H+ + [143–149]
HClO3/ activations Cl− NO: 4NO + 3ClO−(2) + 2H2O → 4NO−3 + 4H+ 5SO2−4 + 2Cl NO:
−

NaClO + 3Cl− 5NO + 3ClO2 + 4H2O → 5NO−3 + 8H+ +

3Cl−
KMnO4 Alkali SO2: 3SO2 + 2MnO−4 + 2H2O → 3SO2−
4 + – [150–154]
2MnO2 + 4H+ NO: 3NO + 2MnO−4 +
H2O → 3NO2 + 2MnO2 + 2OH −

K2CrO7; – SO2: 3SO2 + Cr2O2−

7 + 8H → 2Cr
+ 3+
+ – [155–158]
(NH4)2CrO7; 3SO3 + 4H2O NO: Cr2O2−
7 + 8H +
+

Na2CrO4 3NO → 3NO2 + 2Cr3+ + 4H2O

Yellow O2, water – SO2: SO2 + O3 + H2O → SO2−
4 + 2H +
+
[159–161]
phosphorus O2NO: O3 + NO + H2O → NO−3 + O2 + H+
PS/PMS Thermal activation, alkali, ultraviolet light, SO2: SO2 + HSO−5 + H2O → 2SO2−
4 + 3H NO:
+
SO2: 2SO−4 • + SO2−
3 + H2O → 2HSO4 +
−
[162–168]
activated carbon, transition metal (such as 2NO + 3HSO−5 + H2O → 2NO−3 + HSO−4 + 2SO2−
4 SO2−
4 NO: SO4 • + NO → NO2 + SO3
− −

Fe0, Fe2+, Cu2+, Co2+, Ag+), ultrasound and + 4H +

hydrogen peroxide
Fe(Ⅳ) – SO2: SO2 + 3HFeO−4 + 3⋅.5H2O → SO2−
4 + OH +
−
– [169,170]
1.75O2 + 3Fe(OH)3NO: NO + 3HFeO−4 +
4H2O → NO−3 + 2OH− + 1.5O2 + 3Fe(OH)3

Note: PS represents peroxydisulfate; PMS represents peroxymonosulfate.

Table 7
Main reactions and their rate constants of de-SO2 and de-NOx by H2O2 AOPs.
Main reaction Rate constants
1 − 1
k1 (λ < 300 nm) k1 = 19.6 M− s
H2 O2 + hv ̅̅̅̅̅̅̅̅̅̅̅̅̅̅→ 2HO⋅
k2 k2 = 5.5 × 1014 M− 1 − 1
s
NO + ⋅OH → HNO2
10 14 − 1 − 1
k3 k3 = 10 –10 M s
NO + ⋅OH → NO2 + H⋅
k4 k4 = 3.0 × 1010 M− 1 − 1
s
NO2 + ⋅OH → HNO3
9 − 1 − 1
k5 k5 = 1.5 × 10 M s
HNO2 + ⋅OH → HNO3 + H⋅
k6 k6 = 5.5 × 1014 M− 1 − 1
s
SO2 + ⋅OH → HSO3 ⋅
8 12 − 1 − 1
k7 k7 = 10 –10 M s
HSO3 ⋅ + ⋅OH → H2 SO4
k8 k8 = 108–1012 M− 1 − 1
s
O2 + ⋅OH → O⋅ + H2 O
8 10 − 1 − 1
k9 k9 = 10 –10 M s
NO + ⋅O → NO2
k10 k10 = 2.7 × 107 M− 1 − 1
s
H2 O2 + ⋅OH → HO2 ⋅ + H2 O
9 − 1 − 1
k11 k11 = 5.5 × 10 M s
⋅OH + ⋅OH → H2 O2
k12
2NO + 3H2 O2 → 2HNO3 + 2H2 O Fig. 8. Schematic illustration of H2O2 activation mechanisms using different
k13 non-ferrous Fenton-type catalysts. Modified from [190].
SO2 + H2 O2 → H2 SO4

MeOH + H+ → MeOH+ (pH < PZC) (45)

catalyst surface, and then the surface charge of catalyst is in equilibrium 2

by the surface coordination reactions according to Eqs. (45) and (46) MeOH + OH− → MeO− + H2 O (pH > PZC) (46)
[189]. For instance, the PZC value increases with the replacement of
Fe2+ by Al3+, resulting in more HO• generation [141]. However, Removal efficiency and related mechanism of de-SO2 and de-NOx by
introducing Ti and Si decreases the PZC value of the surface, leading to H2O2 have been extensively investigated, but few studies classify reac­
the generation of non-radical (release O2) rather than HO• [175,190]. tion kinetics of de-SO2 and de-NOx. Available reaction kinetics and rate

16
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Fig. 9. The generation mechanisms of HO• through: (a) interaction of H2O2 and soluble of Al3+; (b) decomposition of H2O2 under surface acid catalyzing through
Ce3+/Ce4+ cycle. Modified from [188].

constants of simultaneous de-SO2 and de-NOx by H2O2 are summarized dissolution) and ammonium salt (easy decomposition), sodium salt is
in Table 7 [191]. Based on the law of mass action (the steady-state more commonly used in in-situ chemical oxidation (ISCO) process.
approximation method), the total reaction kinetics of NO removal by Similarly, PMS origins from the Caro’s acid (H2SO5), which is usually
wet UV/H2O2 method can be expressed as Eq. (47). By changing the found in a more stable form of a white triple salt­
H2O2 concentration, UV lamp power, NO concentration and reaction —2KHSO5⋅KHSO4⋅K2SO4 (potassium hydrogen PMS).
temperature, the kinetic model, actually a pseudo-first-order reaction, If these two precursors are directly introduced into de-SO2 and de-
has been verified and agrees very well with the experimental results. NOx process, highly effective oxidation reactions will not occur, as the
However, the HO• is mainly produced by UV, the kinetic model cannot oxidability of these salts is mainly maintained by the activity of free
be applied to Fenton processes. Therefore, the reaction kinetics of radicals [162,193]. Therefore, these two salt need to be catalyzed to
simultaneous de-SO2 and de-NOx by H2O2 needs to be further clarified. generate more free radicals, when they are used in practical applica­

(( ) )
d[NO] k8 [O2 ]0 k1 [H2 O2 ]0 [hv]0
rNO = − = (k2 + k3 ) + × + k12 [H2 O2 ]0 × [NO] (47)
dt [NO]0 2(k2 +k3 )[NO]0 +2k6 [SO2 ]0 +2k8 [O2 ]0 +k10 [H2 O2 ]0 +k11 [gOH]

tions. As listed in Table 8, the types and amounts of free radicals

generated vary significantly depending on activation methods, which in
turn influence the oxidation efficiency. It can be inferred that the acti­
2.2.2. Peroxydisulfate/Peroxymonosulfate (PS/PMS) oxidants vation mechanism of PS and PMS is mainly related to the splitting of O-O
SO−4 • is also used to oxidize SO2 and NOx simultaneously due to its bonds in their molecule, and PMS is theoretically more stable and
higher oxidation potential, more selectivity, higher efficiency and wider difficult to decompose than PS, according to the bond length and
pH adaptability of solutions than HO• [192]. Generally, the source of dissociation energy of O-O bonds.
SO−4 • has two precursors—peroxydisulfate (PS) and peroxymonosulfate There are many factors influencing the oxidation process of SO2 and
(PMS), which have standard redox potentials of 2.01 V and 1.82 V, NOx by SO−4 •, such as temperature, pH value of the solution and catalyst
respectively. PS is a salt formed by H2S2O8, generally having sodium/ dosage, may even both have positive and negative effects. For instance,
potassium and ammonium salt. Compared to potassium salt (sparingly according to the Arrhenius equation, increasing temperature can

Table 8
Activation methods, mechanisms and main reactions for PS/PMS to generate radicals.
Activation method Mechanism Reaction equation Predominant Ref.
radical species

Transition metal One electron transfer S2O2−

8 +M
n+
→ M(n+1)+ + SO2− 4 + SO4 •HSO5 + M
− − n+
→ M(n+1)+ + OH− SO−4 • [193,194]
+ SO−4 •
Heat Homolysis of peroxide bond S2O2−
8 + heat → 2SO4 •HSO5 + heat → SO4 • + HO•
− − −
SO−4 •/ HO• [195]
UV Homolysis of peroxide bond S2O2−
8 + hv → 2SO4 •HSO5 + hv → SO4 • + HO•
− − −
SO−4 •/ HO• [192,195]
Alkali Hydrolysis of PS to hydroperoxide, and OH- OH- SO−4 •/O−2 • [171,194]
2S2O2− 2−
8 + 2H2O → 3SO4 + SO4 • + O2 • + 4H 4HSO5 + 2H2O →
− − + −
then initiates radical formation 2−
3SO4 + SO4 • + O2 • + 4H
− − +

Electrolysis Fe2+ generation due to chemical and S2O2− − 2−

8 + e → SO4 + SO4 •HSO5 + e → SO4 • + HO•
− − − −
SO−4 •/ HO• [193,195]
electrochemical corrosion of iron
Radiation Homolysis of peroxide bond S2O2−
8 +(((→2SO−4 •HSO−5+ (((→SO−4 • + HO• SO−4 •/ HO• [194]
Carbonaceous Homolysis of peroxide bond AC − surface − OH(− OOH) + S2O2−
8 → SO4 • + AC −
−
surface − O⋅ SO−4 • [171,195–197]
materials (OO⋅) + HSO−4 HSO−5 + C − π /C = C = O → OH + SO−4 • + C − π/
+ −

C = C − O+

Note: M represents the metal ion; (((represents radiation; AC represents active carbon.

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R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

accelerate the generation of active radicals and leads to an increase in 2HO⋅→H2 O + 0.5O2 (54)
the reaction coefficient, which are conducive to the oxidation of SO2 and
NOx [162]. However, excessive increase in temperature reduces the Hydrogen-ion catalyzed reaction:
solubility of reactants and temperature transfer coefficients, and unde­
S2 O−8 + H+ → HS2 O−8 → SO4 + HSO−4 (55)
sirable side reactions, such as recombination of HO• and SO−4 • (Eqs.
(48)–(50)) may proceed, thereby reducing the removal efficiency of NO SO4 → SO3 + 0.5O2 (56)
and SO2 [168,198].
SO4 + H2 O → H2 SO5 (57)
SO−4 ⋅ + SO−4 ⋅ → S2 O2−8 (K = 4 × 108 M− 1 s− 1 ) (48)
kf
(49) kf = 1.2 × 1010 M− kb = 9.3 × 107 s−
1 2
SO−4 ⋅ + S2 O2−8 → SO2−4 + S2 O−8 ⋅ (K = 6.1 × 105 M− 1 s− 1 ) HO⋅+ OH− ⟷O− ⋅+ H2 O
kb

(58)
HO⋅+ S2 O2−8 →OH− + S2 O−8 ⋅ (K = 1.2 × 107 M− 1 s− 1 ) (50)
The main components of industrial exhaust gases are O2 (2–15%),
The alkalinity of the reaction solution also has significant influence CO2 (10–36%) and rest N2. In general, CO2 and N2 have no impact on the
on the de-SO2 and de-NOx, which is mainly attributed to the conversion de-SO2 and de-NOx process under normal temperature and pressure,
of free radicals. Numerous studies have shown that the SO−4 • gradually while O2 can oxidize NO in the presence of H2O as described by Eqs.
converts to HO• with the increase of pH value of solution (Eq. (51)) (59)–(62) [168]. It is generally accepted that the removal of SO2 is
[162,166,199]. The main free radical in the solution is SO−4 • at pH < 7, mainly achieved by the absorption in the liquid phase, and has little to
both HO• and SO−4 • coexist at pH around 9, and HO• and O−2 • are do with the oxidation of NO, while the presence of sulfite is beneficial to
predominate free radicals when the pH is further raised to about 12 as the reduction of NO2 as Eq. (63). However, studies have demonstrated
shown in Fig. 10 (a) [200]. Two pathways have been proposed to that in the presence of SO2, the removal path of NO may change. In
illustrate the decomposition of PS in aqueous solutions [164,201]. One addition, the concentration of ions in the reaction solution changes
is uncatalyzed reaction, a S2O2− 8 symmetrically decomposes into two greatly during the de-SO2 and de-NOx process [163,203], leading to
SO−4 •, and then further transforms to HO• as described by Eqs. (52)– capture or inhabitation of free radicals. The order of inhibitory effect
(54). The other pathway is hydrogen-ion catalyzed reaction, the S2O−8 reported is reported as S2O2− − 2−
3 > HCO3 > CO3 > NO2 > HCOO > Cl >
− − −
undergoes unsymmetrical decomposition to form sulfur tetroxide and HPO2−4 > NO3 > H2PO4 > SO4
− − 2−
> CH3COO− [193]. For kinetic study,
bisulfate, and sulfur tetroxide can react with water to form Caro’s acid the removal process of NO by the PMS–Fe(II) process is suggested as a
(H2SO5, also known as persulfuric, peroxymonosulfuric, and perox­ pseudo-first-order reaction [204,205], while the kinematic model of
ysulfuric acid) under strong acidic condition as shown by Eqs. (55)– simultaneous de-SO2 and de-NOx by PS/PMS AOPs has not been clarified
(57)). Therefore, acidic condition reduces the efficiency of PS due to yet.
acid-catalyzed reaction (generation of Caro’s acid), even though the
decomposition rate of PS is increased. In contrast, the removal efficiency 2NO + O2 → 2NO2 (59)
of SO2 and NO can be further improved due to the synergistic oxidation
3NO2 + H2 O → 2HNO3 + NO (60)
of HO• and SO−4 • under neutral conditions. Under alkaline condition,
HO• is the main oxidant with higher oxidability, but HO• is prone to
NO + NO2 → N2 O3 (61)
decomposition under alkaline condition (Eq. (58)) [202], which can
reduces the efficiency of de-SO2 and de-NOx. Transition metal ions are
N2 O3 + H2 O → 2NO−2 + 2H+ (62)
widely used to active PS/PMS as shown in Fig. 10 (b), in which the
regulation of pH is extremely important to prevent the agglomeration of
4SO2−3 + 2NO2 → 4SO2−4 + N2 (63)
metal ions. To improve the efficiency of de-SO2 and de-NOx, the optimal
pH range of the reaction solution is suggested between 6.5 and 8.5
2.2.3. NaClO/ NaClO2 oxidant
[163].
Due to high oxidability, sodium chlorite (NaClO2) is the most
SO−4 ⋅ + OH− → SO2−4 + ⋅OH K = 1.4 × 107 M− 1 s− 1
(51) commonly used precursor for producing chlorine-containing oxidants
for de-SO2 and de-NOx, and the main chemical reactions are listed in
Uncatalyzed reaction: Table 6. Based on an extensive literature review, Table 9 summarizes the
S2 O−8 → 2SO−4 ⋅ (52) main factors influencing the removal efficiency of SO2 and NOx, in terms
of the gas component, the concentration of absorbent, reaction tem­
2SO−4 ⋅ + 2H2 O →2HSO−4 + 2HO⋅ (53) perature and time, initial pH value of solution and liquid/gas flow rate.
SO2 can be absorbed in water through hydrolysis reaction and

Fig. 10. Effects of pH value of solution on the generation of free radicals: (a) activation mechanism of PS under different pH value. Modified from [200]; (b)
activation mechanism of PS/PMS using transition metal ions and oxides (Brown and blue lines represent the formation of SO−4 • and SO−5 •, respectively). Modified
from [163]. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

18
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Table 9
Factors influencing the efficiency of de-SO2 and de-NOx by NaClO/ NaClO2 solution.
Oxidant Initial gas component Initial Time Reaction Gas flow rate (L/ Absorbent Maximum Ref.
pH (min) temperature min) concentration removal
SO2 (ppm) NO (ppm) CO2 O2
(◦ C) efficiency
(%) (%)

NaClO2 500–2000 200–800 – 6–12 4–7 0–60 65 4.0–15.0 NaClO2/ SO2:100% [206]
(SO2 + NO) = 0–1.2 NO:72%
(molar ratio)
NaClO + NaClO2 0–4000 500 – – 2–9 – 10–90 1.0–3.0 NaClO (0–0.0006 M), SO2:100% [207]
NaClO2 (0.0001 M) NO:85%
NaClO2 0–500 150–300 – – 4–8 – 35 0.8–5.0 0–0.5000 M SO2:100% [208]
NO:81%
NaClO + NaClO2 1000–3000 200–1000 – – – – 90–150 – NaClO2/NaClO = 0–8 SO2:96% [209]
(molar ratio) NO:74%
NaClO2 + NaBr 0–5000 0–1000 0–15 0–9 4–9 – 80–160 1.0–2.5 NaClO2 SO2:100% [210]
(0.5000–2.5000 M); NO:91%
NaBr (0–0.3000 M)
Ca(ClO)2 600–3000 800 – 4–12 – 0–140 40–80 0.5 0–0.5 (wt.%) SO2:100% [211]
NO:86%
NaClO + NaClO2 800–1200 200–400 – – 2–8 – 20–80 0.3–1.7 NaClO SO2:99% [212]
(0.0010–0.0060 M), NO:90%
NaClO2
(0.0010–0.0060 M)
NaClO2 + H2O2 2000–4000 500–1000 4–8 2–6 3–7 – 90–150 0.5–3.01.0–5.0 NaClO2 SO2:100% [213]
(0.1000–2.0000 M), NO:87%
H2O2
(2.0000–6.0000 M)
NaClO2 0–1200 200–700 0–20 1–15 2–12 0–120 25–70 1.0–3.0 0.016–0.160 (wt.%) SO2:99% [214]
NO:82%
NaClO2 + Na2S2O8 2000–3000 200–700 6–12 2–6 5–12 – 77–157 0.5–30.02.0–6.0 NaClO2 (1–5 wt%), SO2:100% [215]
Na2S2O8 (2–10 wt%) NO:82%
NaClO2 + Ethanol 0–500 200–1000 0–5 0–10 2–8 – 20 1.5 NaClO2 (0.0100 M), SO2:100% [145]
ethanol (0–2 vol%) NO:87%
NaClO 4200–7200 500–820 – – 4–9 20–120 25–50 – 0.0020–0.0100 M SO2:100% [216]
NO:92%
NaClO 0–600 200–1000 – – 3–11 0–70 30–70 0.3 0.0040–0.0024 M SO2:100% [217]
NO > 93%
Ca(ClO)2NaClO 0–3500 200–1200 0–10 0–16 1–12 – 35–65 – 0–0.2000 M SO2:100% [218]
NO:85%
2+
NaClOFenton 0–4000 0–800 0–8 0–8 1–5.5 – 90–150 1.0–5.0 Fe (0–0.5000 M), SO2:100% [219]
NaClO NO:81%
(0.1000–0.5000 M)

mainly produces tetravalent substances (HSO−3 , SO2− 2−

3 , S2O5 , etc.). alkaline conditions (Eq. (64)), and the reduction potential of NaClO2
Equilibrium between the hydrolyzed SO2 in solution and the unhydro­ decreases with the increase of pH according to the Nernst equation, so
lyzed SO2 obeys Henry’s law, and the predominant products depend on there is an optimal pH range of reaction solution for de-SO2 and de-NOx.
the gas partial pressure and the pH value of the reaction solution. For NaClO2 solution, neutral or slightly acidic conditions are suggested to
example, the main product is bisulfite at pH < 6, while the sulfite is remove NO and SO2 [220,221], in which the generated ClO2 is an
dominant when the pH > 8. And under a certain partial pressure of SO2, important active intermediate [143]. The overall reaction of the process
the liquid tetravalent sulfur species increase with the increase of pH can be characterized by Eq. (65). More important, ClO2 can be generated
value, and then the hydrolyzed product is further oxidized in the solu­ following reactions Eqs. (66) and (67). Therefore, extremely high effi­
tion by ClO2 or HClO2, indicating that a relatively high pH is favorable ciency of de-SO2 and de-NOx can be obtained [73,222], even the
for the absorption of SO2. However, these oxidants are not stable under chlorate-chloride is directly introduced to produce ClO2 for gas phase
oxidation. Additionally, a large amount of ClO2 can also be obtained by
the reaction of NaClO2 with NaClO as shown in Fig. 11 and Eq. (68)
[144].
2ClO2 + 2OH− → ClO−2 + ClO−3 + H2 O (64)

4NO + 3NaClO2 + 2H2 O → 4HNO3 + 3NaCl (65)

5NaClO2 + 4HCl → 4ClO2 + 5NaCl + 2H2 O (66)

5NO + 3ClO2 + 4H2 O → 5HNO3 + 3HCl (67)

2ClO−2 + NaClO + H2 O → 2ClO2 + NaCl + 2OH− (68)

Although acidic conditions are conducive to the oxidation of NO, the

excess ClO2 also easily escapes from the liquid phase, resulting in a loss
of effective oxidants [210]. Meanwhile, the generated NO2 needs suffi­
cient time to be converted into N2O3 and N2O4, and consequently be
Fig. 11. Decomposition and redox reactions of NaClO2 solution in the presence absorbed via hydrolysis in the liquid phase (Eqs. (69)–(72))
of chlorine species (HOCl/OCl− ). Modified from [223].

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R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

[144,214,224]. Therefore, the pH value of the absorption solution by CO2 hydrolysis (Eq. (75)) [215] can capture free radicals and change
should be low enough to sufficiently oxidize the NO, and to be suffi­ the pH value of the solution, thereby narrowing the efficiency of de-SO2
ciently high that the NO2 can be absorbed by the liquid phase in time. and de-NOx.
NO + NO2 → N2 O3 (69) 2NO2 + HSO−3 + H2 O → 2NO−2 + 3H+ + SO2−4 (73)

2NO2 → N2 O4 (70) 2NO2 + SO2−3 + H2 O → 2NO−2 + 2H+ + SO2−4 (74)

N2 O3 + H2 O → 2HNO2 (71) CO2 + H2 O → H+ + HCO−3 → 2H+ + CO2−3 (75)

N2 O4 + H2 O → HNO2 + HNO3 (72) Similarly, the reaction temperature also has a double effect on the
removal of NO and SO2. Depending on the Arrhenius law, high tem­
Notably, SO2 has a double effect on the removal efficiency of NO by
perature benefits the generation of ClO2, ions diffusion and increased
NaClO2-NaOH solution [215,220,225–227]. Low SO2 concentration has
reaction rates. On the other hand, high temperature reduces the solu­
a promoting effect on the removal of NO, as the hydrolysis of SO2 fa­
bility of gas reactants and increases the mass-transfer resistance in
cilitates the reduction of pH value of solution and then the production of
gas–liquid interface according to Henry’s law and two-film theory,
ClO2 [208] and the presence of SO2 is also beneficial to the absorption of
finally resulting in decreased mass transfer of NO from gas phase to
NO2 as shown by Eqs. (73) and (74). However, for high SO2 concen­
liquid phase.
tration, SO2 consumes ClO2 prior to NO during solution oxidation,
For kinetic study, the reaction between NO and ClO2 is located in the
thereby reducing the removal efficiency of NO. In addition, the presence
fast pseudo-m-stage reaction zone, and the absorption rate is indepen­
of O2 has a minor effect on the efficiency of de-SO2 and de-NOx, while
dent of the liquid phase mass transfer coefficient [228]. While Sada et al.
CO2 has an inhibitory effect on the removal of NOx, as HCO–3 produced
[229,230] suggested that the reaction rate of NO falls in the fast-reaction

Fig. 12. Oxidation of SO2 and NOx over TiO2 as a photocatalyst: (a) schematic diagram. Modified from [246]; (b) generation pathways of HO• through valence band
holes (1) and conduction band electrons (2). Modified from [245].

20
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

regime, and the reaction between NO and NaClO2 be reflected by Eqs. Fig. 11(b). Therefore, more and more attention is paid to modify the
(76) and (77), which has the reaction orders of 2 for NO and 1 for ClO−2 , structure of TiO2, to generate more radicals and reduce energy con­
respectively. Thus, the absorption rate of NO into scrubbing solution can sumption by reducing the lower limit of light absorption and expanding
be expressed by Eqs. (78) and (79) according to the gas–liquid mass the effective light region. For instance, introducing dopants (such as La
transfer theory [231]. The oxidability of NaClO2 increases with the [239] and Ga [240]) into TiO2 can reduce the band gap, and thereby
decrease pH value of solution, and the reaction rate can be empirically shifts the adsorption edge toward the visible light region. In addition,
correlated by Eq. (80) when the concentration of OH− lies in the range of photocatalytic activity can be improved significantly by incorporating
0.05–0.50 M [225]. TiO2 nanoparticles into porous supports, such as silicate fiber [241,242],
carbon materials [243], zeolites [244], and clay minerals [245].
2NO + ClO−2 → 2NO2 + Cl (76)

4NO2 + ClO−2 + 4OH− →4NO−3 + Cl− + 2H2 O (77) 3. Reduction approach

√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
( ) SO2 and NO in flue gas can be reduced to elemental sulfur (S for
2
RNO = ×k(m+n) ×DNO ×Cm+1 NO,i ×CO.A
n
(78) short) and N2 by numerous reductants, such as light CxHy (e.g. methane,
m+1 ethylene, propane, ethane), H2, elemental carbon, and CO. The potential
economic benefits from S production make catalytic reduction approach
4NO + 3ClO−2 + 4OH− → 4NO−3 + 3Cl− + 2H2 O (79) very attractive especially in view of increasing demand for S [247]. The
reduction of SO2 and NO to S and N2 is straightforward and
kmn = 3.80exp(− 3.73[NaOH]) (80)
thermodynamically-favored, which can proceed even at low tempera­
ture. However, the reaction rate is very slow, and effective catalysts have
2.3. Gas-solid oxidation not been discovered clearly yet. Therefore, developing efficient catalysts
for selective reduction and selecting appropriate reductants are the
Under the irradiation of ultraviolet light over photocatalyst (actually major challenges of catalytic reduction approach. Based on the physical
N-type semiconductor), electron (e− ) and hole (h+) can be generate in state of the reductants, reduction process, mechanism and main factors
pairs due to valence band electrons transition, when the light has a affecting the removal efficiency are reviewed.
higher energy than the forbidden band width of the photocatalyst. At the
same time, substances adsorbed on the surface of photocatalyst are 3.1. Gas-gas reduction
oxidized to free radicals (e.g., HO•, O−2 • and O•) as illustrated in Fig. 12
(a). Then SO2 and NO are simultaneously oxidizing to higher-valence As shown in Table 10, CO, H2 and CxHy are generally used to reduce
nitrogen and sulfur oxides, which combine with the surface moisture SO2 and NO simultaneously. Although both SO2 and NOx are reduced to
to form sulfuric acid and nitric acid due to their high solubility. S and N2, the reduction principles and mechanisms are quite different
Photocatalysts that currently used for de-SO2 and de-NOx include based on reductants.
TiO2 [232,233], ZnO [234], CeO2 [235,236], B2WO6 [237], BiOX (Cl,
Br, I) [238], etc. Among which, TiO2 is regarded as a promising pho­ 3.1.1. CO reductant
tocatalyst to realize flue gas purification due to its strong oxidation CO has attracted considerable interest, as CO usually co-exists with
ability, high chemical stability, and relatively non-toxic. However, the SO2 and NOx in flue gas from coal-firing furnaces, and the reduction is
forbidden band of TiO2 (3.0–3.2 eV) can only be excited by ultraviolet thermodynamically-favored reaction and achieves the simultaneous
light with wavelength of < 380 nm, resulting in a strict application conversion of all three gaseous pollutants into harmless products (N2,
environment. The two pathways for HO• generation over TiO2 are CO2 and salable S). For instance, during de-SO2 and de-NOx through CO
through valence band holes or conduction band electrons as shown in over copper-alumina catalyst, SO2 and NO are directly reduced to S and

Table 10
The reductants, catalysts, and mechanisms of available catalytic reduction de-SO2 and de-NOx processes.
Reductant Catalysts Mechanism Removal Ref.
efficiency

Carbon Mixed oxides (CuO, Fe2O3, etc.)Solid solutions Redox mechanism:Cat − [O] + CO → Cat − [□] + CO2 SO2: [248–252]
monoxide (CeO2-ZrO2/MnO2/TiO2/SiO2/PbO2; SnO2- Cat − [□] + SO2 → Cat − [O] + [SO] Cat − [□] + [SO] → Cat − [O] + S 20–100%
(CO) TiO2, etc.)Perovskite-type oxidesSupported Cat − [□] + 2NO → 2Cat − [O] + N2O NO: 75–99%
transition/noble metals (Fe/Ni/Mn/Mo/Cr/Co/ Cat − [□] + N2O → 2Cat − [O] + N2 [□]: lattice oxygen vacancy COS
Pd/Pt/Rh/Au supported on various substrates intermediate mechanism: CO + M − [S] → COS + M − [□]
as Al2O3/CeO2/SiO2/TiO2/V2O5/La2O3 /ZrO2, 2COS + SO2 → 2CO2 + 3S 2COS + 2NO → 2CO2 + 2S + N2
etc.) M − [□] + S → M − [S] M: metal (oxide)
Hydrogen (H2) Co-Mo/Al2O3 Ir and Rh/SiO2 Nickel-tungsten Redox mechanism: MO − catalysts + 2H2 → M[□] − catalysts + 2H2O M SO2: 15–98% [253–259]
sulphides Iron or copper supported on alumina [□] − catalysts + SO2 → MO − catalysts + 1/nSn M NO: 40–95%
or bauxite Fe group metals (Fe, Co, and Ni) [□] − catalysts → MO − catalysts + N2 H2S intermediate mechanism
supported on porous materials such as asbestos, (SO2): MO − catalysts + H2S → MS − catalysts + H2O
kieselguhr, and porous brick. MS − catalysts + H2 → MSx− 1 − catalysts + H2S SO2 + 2H2S → 1/
nSn + 2H2O (Claus reaction) HS + NO → NS + OH Adsorption/
dissociation mechanism (NO): NO + M ↔ NOad H2 + 2 M ↔ 2Had
O2 + 2 M ↔ 2Oad NOad + M ↔ Nad + Oad 2Nad ↔ N2 + 2 M
NOad + Nad ↔ N2O + 2 M Oad + Had ↔ OHad + M
OHad + Had ↔ H2O + 2 M NOads + Hads ↔ Nads + OHads
Hydrocarbons Zeolite-supported transition metal-oxides (such Taking methane as an example: CH4 + SO2 → H2S + CO + H2O SO2: 15–99% [252,260–266]
(CxHy) a as Zeolite-supported cobalt: Co-ZSM-5, Co- CH4 → C + 2H2 C + SO2 → COS + CO H2 + SO2 → H2S + 2H2O Redox NO: 10–70%
ferrierite, Co-Beta, Co-ZSM-5, Co-mordenite, mechanism COS/H2S intermediate mechanism Adsorption/dissociation
Co-Beta/Y, Pd0.15SiBEA and CoxPd0.15SiBEA mechanism
zeolites) Supported transition/noble metals
(Ag/Al2O3, Rare-earth oxides, La-Mn-Ba dopted
perovskites, etc.)

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R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

N2 as shown by Eqs. (81) and (82) [267]. However, the produced S mechanism has been proposed based on the participation of surface
further reacts with CO to produce carbonyl sulfide (COS), a toxic and oxygen and oxygen vacancy as shown in Fig. 13(b). Oxygen vacancies
undesirable by-product, but the COS can then reduce SO2 to S according generated by the reaction of CO with the surface oxygen are active sites
to Eqs. (83) and (84). A predictive equation for SO2 conversion has been for the reduction of SO2 and NO, and the pre-sulfide procedure has a
proposed as a function of temperature and CO concentration in the range minor effect on the activity of the catalyst, as elemental sulfur reacts
of 0–1000 ppm (Eq. (85)). with CO to form COS [274]. Normally, the redox mechanism is the
Ma et al. [268] prepared a sulfurized La0.8Sr0.2CoO3 (perovskite-type dominant reaction for NO catalytic reduction, compared to the COS
oxide) to catalyze the reduction of NO by CO, and COS is also found as a intermediate mechanism for SO2 catalytic reduction.
significant intermediate in the reduction of NO by CO. Coexisting SO2 Generally, coexisting SO2 in flue gas is poisonous to catalyst, as SO2
appears to play an important role in creating sites for intermediate causes either irreversible or reversible deactivation of catalysts [276].
formation. And the reaction between COS and NO has priority over the However, for noble metal catalysts (Ir/SiO2, Pt/SiO2, Rh/SiO2, and Pd/
reaction with SO2, which contributes to competition for COS from SO2 Al2O3), the presence of SO2 drastically promotes the reduction of NO
reduction [269–271]. Therefore, CO is more preferential for the reduc­ [277–279]. As shown in Fig. 13(c), NO conversion increases rapidly
tion of NO during simultaneous catalytic reduction. Through this SO2- after introducing SO2, and the subsequent removal of SO2 does not result
assisted pathway as described in Fig. 13(a), reduction of NO is a in a rapid decrease of NO conversion, suggesting that surface adsorbed
favorable reaction step for the reduction of SO2 by CO [272]. It can be SO2 plays an important role in the active promotion. Moreover, moisture
deduced that the O released during NO reduction is removed by the S to in flue gas generally inhibits the reduction of SO2 and NO due to the
form SO2, which in turn is reduced back to S again by CO over La2O2S. competitive adsorption between gas molecular and moisture. Never­
When rare earth oxides are used as catalyst [273], a COS intermediate theless, moisture does not damage the structure of catalyst, thus deac­
mechanism has been proposed for simultaneous de-SO2 and de-NOx as tivation is reversible. Sulfites generated from SO2 and consequent
described in table 10, as the occurrence of COS is more prone to the oxidation by O2 in the flue gas contribute to the sub-salt transformation,
generation of active free radicals. which may damage the structure and lead to irreversible deactivation.
CO + NO → CO2 + N2 (81)
3.1.2. H2 reductant
H2 is another reductant investigated intensively for effectively
2CO + SO2 → 0.5S2 + 2CO2 (82)
reduction SO2 and NO. Compared to CO, H2 is non-toxic with water as
CO + 0.5S2 → COS (83) the final converter, presenting a wide application potential due to no
corrosion to the equipment [253]. Simultaneous reduction of SO2 and
2COS + SO2 → 1.5S2 + 2CO2 (84) NO by H2 over sulfided NiW/Al2O3 catalyst has been conducted by Li
et al. [256]. NO and SO2 are firstly adsorbed and reduced, while the
E oxidative leakage of lattice sulfur by NO results in a rapid deactivation of
lnkSO2 = A − + B(CO ratio − 1.4) − C(NO level) (85)
RT the catalyst, and the generated S or the H2S can therefore in turn
In addition to metal sulfides, noble metal supported by metal oxides regenerate the M-[ ] or M-[O], leading to re-sulfidation of catalyst as
can also catalyze the reduction of SO2 and NOx by CO. The redox shown in Fig. 14(a). Similarly, SO2 has a considerable effect to increase
reduction efficiency of NO by H2 over Ir and Rh/SiO2 in the presence of

Fig. 13. Simultaneous catalytic reduction of NO and SO2 by CO: (a) coupling reduction over La2O2S. Modified from [272]; (b) reduction pathway over CuCo/Al-Co.
Modified from [253,274]; (c) response of NO conversion to the intermittent feed of 20 ppm SO2 over 5 wt% Ir/SiO2 at 350 ◦ C under condition of NO = 1000 ppm,
CO = 6000 ppm, O2 = 5%, H2O = 6%, catalytic weight = 0.04 g, gas flow rate = 90 cm3min− 1. Modified from [275].

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R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Fig. 14. Simultaneous catalytic reduction of NO and SO2 by H2: (a) flow chart of sulfur species during the simultaneous reduction of NO and SO2 by H2 over NiW/
Al2O3 (M: metal atom). Modified from [256]; (b) response of NO and H2 conversion to the intermittent feed of SO2 over 0.5% Ir/SiO2 catalyst. Conditions:
NO = 1000 ppm, O2 = 0.65%, H2O = 10%, H2 = 3000 ppm, SO2 = 0 or 20 ppm, T = 400 ◦ C, W/F = 0.0267 g s cm− 3. Modified from [259,280]; (c) mechanistic scheme
to explain the role of sulfates present on the surface of MgO–CeO2 in prohibiting the deactivation of Pt/MgO–CeO2 during the NO/H2/O2 (H2-SCR) reaction in the
presence of 25–50 ppm of SO2 at T < 250 ◦ C. Modified from [283].

excess O2 as shown in Fig. 14(b) [259,280]. One possible reason is that 3.1.3. CxHy reductant
the formation of sulfate-like species promotes the reduction of SO2 and CxHy is also reported as candidate reductants for simultaneous de-
NO, another illustration is that O2 and SO2 promote the adsorption of NO SO2 and de-NO. For instance, methane (CH4) is generally used to reduce
and then reacts with H2 to form NHx species on the surface of Ir/SiO2 SO2 and NO in flue gas regarding its wide availability and reducibility.
catalyst. However, CH4 is a non-polar molecule of tetrahedron with high bond
Originally, coexisting of SO2 is prone to catalyst poisoning presum­ energy, resulting in that the reducibility of CH4 is much lower than those
ably due to the formation of sulfur oxides on the active sites [281]. of H2 and CO [255]. Therefore, the cracking of CH4 is a very important
However, the pre-sulfation of Pt/MgO–CeO2 prior to H2-SCR can countermeasure to improve its reducing ability. Through partial oxida­
significantly improve the sulfur tolerance of the catalyst. Costa et al tion of CH4 at high temperature and in fuel-rich conditions, CO and H2
[282] proposed a mechanistic scheme to explain such extra-ordinary generated over catalysts can increase the reduction efficiency of SO2 and
prohibition of deactivation by involving the role of sulfates presented NO [286,287]. Such that, the reactions in this system become much
on the surface of the catalyst. As shown in Fig. 14(c), SO2 is principally more complicated, and SO2 and NO are not completely reduced to sulfur
chemisorbed on the basic sites (On− ) of the support to form bidentate or and N2 accompanying with various by-products (H2S, COS, CS2, etc.). As
unidentate sulfite species, while SO3 is primarily chemisorbed on the a result, the reduction of CH4 is difficult to realize due to difficulties in
acidic sites (Mg2+/Ce4+) to form bidentate sulfates [283]. Both basic controlling cracking, catalyst poisoning and poisonous COS in­
and acidic sites of MgO and CeO2 are proved to accommodate chem­ termediates at high reaction temperature (550–840 ◦ C).
isorbed NO [284], but the chemisorption of SO2 and SO3 is stronger than C3H6 and C3H8 have also been used as reductants for the reduction of
that of NO on these sites [285]. Thus, the support surface is gradually SO2 and NO, in which moisture and SO2 have an inhibitory effect on the
covered by sulfite and sulfate species (Fig. 14c (1)), leading to the loss of reduction of NO [288–291]. Kinetic models for NO reduction and C3H6
active sites for NO adsorption and further deactivation of the catalyst. oxidation in the presence of SO2 and moisture can be expressed as Eqs.
However, when the support is pre-sulfated, the formed sulfates (SO2− 4 ) is (86) and (87) [292]. Pekridis et al. [293] explored the surface and cat­
adsorbed particularly on Mg2+ rather than two adjacent Mg2+ cations alytic behavior of Rh/γ-Al2O3 catalysts during the selective reduction of
due to geometrical constraints (Fig. 14c (2–4)). As the available space NO by C3H8 in the presence of excess O2, H2O, and SO2. The inhibitory
between two adjacent sulfate species adsorbed is about 2.5 A, which is effect of moisture on the oxidation of C3H8 is totally reversible, while the
not big enough for the adsorption of SO2/SO3 but is suitable for the inhibitory effect on the reduction of NO over Rh/γ-Al2O3 is permanently
adsorption of NO to form an active bidentate nitrate species (Fig. 14c due to the oxidation of Rh at active sites. In contrast, SO2 also has
(4)). Thus, the pre-sulfated MgO–CeO2 forms a support with an irreversible inhibitory effect on the adsorption of gases and conse­
extremely SO2-resistance, and Pt/MgO–CeO2 is suggested to be the most quently the reduction of NO, due to the formation of strongly adsorbed
active and stable catalyst for H2-SCR in the presence of SO2 [281]. sulfates at active sites. A precise kinetic model has been proposed to

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R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Table 11
Kinetic parameters of C3H8-SCR process in the absence/presence of H2O and SO2.
Condition Eactivation(kcal/mol) R = k[NO]a[O2]b[C3H8]c[H2O]d[SO2]e

a b c d e

NO Reduction
absence of SO2 and H2O 29 ± 3.30 0.00 ± 0.02 0.47 ± 0.05 0.46 ± 0.05
presence of H2O 34 ± 2.50 0.94 ± 0.09 0.93 ± 0.08 0.47 ± 0.04 − 1.52 ± 0.25
presence of SO2 52 ± 2.0 0.00 ± 0.03 0.53 ± 0.04 0.48 ± 0.02 − 0.51 ± 0.06
C3H8 Oxidation
absence of SO2 and H2O 24 ± 2.00 0.00 ± 0.01 0.52 ± 0.03 0.49 ± 0.03
presence of H2O 25 ± 1.00 − 0.46 ± 0.05 0.56 ± 0.08 0.55 ± 0.11 0.0 ± 0.01
presence of SO2 47 ± 1.70 0.00 ± 0.01 0.49 ± 0.06 0.51 ± 0.03 − 0.54 ± 0.08

evaluate the effects of H2O and SO2 on C3H8-SCR over the Cu/ 3.3. Gas-solid reductant
Ti0.7Zr0.3O2− δ under different conditions [294], kinetic parameters
influencing the NO reduction and C3H8 oxidation are summarized in There are limited studies using solid reductants for simultaneous de-
Table 11. SO2 and de-NOx. Although the carbon materials itself have a reducing
property under normal conditions, SO2 and NO adsorbed on the carbon
[NOx]0.36 materials tend to be oxidized by O2 due to the presence of O2 and H2O in
r(NOx red) = kred 0.62
(86)
[SO2 ] [C3 H6 ]0.32 [O2 ]0.33 the flue gas. However, some studies have shown that under microwave
irradiation many local hotspots on activated carbon are generated as
[C3 H6 ]0.26 [O2 ]0.21 shown in Fig. 15 [295]. Then, the thermo chemical reactions at these
r(C3 H6 ox) = kox (87)
[NOx]0.29 [SO2 ]0.46 hotspots are faster at high temperatures due to an increase in the
molecule migration rate and thus the collision frequency between
molecules. As a result, SO2 and NO tend to reduce directly by carbon at
3.2. Gas-liquid reductant these active centers [296–298]. However, nearly no literature refers to
the reduction kinetic and clarifies key factors influencing the efficiency
Another simultaneous de-SO2 and de-NOx is to reduce SO2 and NOx of de-SO2 and de-NOx.
in aqueous solutions with aqua ammonia, urea, sodium sulfide (Na2S),
etc. For instance, simultaneous removal of NOx and SO2 can be achieved 4. Absorption/adsorption approach
by absorption process with Na2S as reductant with ozone injection [44].
Specifically, NOx is first oxidized to NO2 by ozone, then NO2 is reduced In addition to the oxidation or reduction approaches, some liquid
by Na2S to N2 according to Eq. (88) and SO2 can be removed as Eq. (89). and solid substances can absorb/adsorb SO2 and NO in the flue gas
For most liquid reductants (e.g. ammonium salts or aqueous urea), SO2 without changing their chemical valence, then SO2 and NO are desorbed
and NOx are generally directly reduced. In practical applications, these and collected by changing the pressure, pH value of solution, tempera­
liquid reductants are often used as absorbents to absorb acidic gases in ture, etc. Therefore, absorption/adsorption approach creates pure gas
the flue gas using their alkalinity, and then fix acidic gas with more substances or useful by-products. As referred in gas–liquid oxidation and
reductants or oxidants. Some results are not agreeable or require further reduction, better absorption/adsorption of SO2 and NO have been a
confirmation, thus more precise experiments are needed to suggest a certain synergistic effect with oxidants/reductants, leading to a higher
meaningful or reliable approach and development. removal efficiency. According to the physical state of absorbents, liquid
phase absorption and solid phase adsorption processes are extensively
2NO2 + Na2 S → N2 + Na2 SO4 (88) reviewed based on available literature.

2SO2 + Na2 S →2S + Na2 SO4 (89)

Fig. 15. Reduction mechanism of SO2 and NOx over activated carbon under microwave irradiation.

24
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

4.1. Liquid absorption the absorption proceeds, then the removal efficiency of NO drops
sharply.
4.1.1. Alkaline solution absorption
NO(g) → NO(aq) (90)
NOx and SO2, weakly acidic gas, can be absorbed by alkaline solu­
tions, such as hydroxides or weak acid salts solutions of an alkali so­
NO(aq) + [Fe2+ − EDTA]2− → [Fe2+ − EDTA(NO)]2− (91)
dium, potassium, magnesium or ammonium. Due to the low solubility of
NOx, Alkaline solution absorption is only suitable for treating exhaust
4[Fe2+ − EDTA]2− + O2 + 4H+ → 4[Fe3+ − EDTA]− + 2H2 O (92)
gas with > 50% NO2, as SO2 and NO in alkaline solution can be con­
verted into sub-salts, which tend to decompose in reverse at high tem­
2NO + [Fe2+ − EDTA]2− + 2H+ → N2 O + Fe3+ − EDTA + H2 O
peratures. Therefore, in order to simultaneously remove SO2 and NO
from the flue gas, it is still a need to further oxidize the sub-salts into (93)
thermodynamically stable nitrates and sulfates. Main reactions during To maintain high removal efficiency of NO and SO2, regeneration of
SO2 and NO absorption by different alkaline solutions and removal ef­ Fe2+-EDTA (converting Fe3+-EDTA and Fe2+-EDTA(NO) to Fe2+-EDTA)
ficiency are summarized in Table 12. This process can recycle SO2 and is the key step in de-SO2 and de-NOx by Fe2+-EDTA solution. Therefore,
NOx into a marketable nitrite/nitrate and sulfate products, while the activated carbon, hydrazine (N2H4), metal (Se, Zn, Fe and Al) powders
absorption efficiency and the ratio of NO2/NO are relatively muted. and compounds, thiosulfates, sulfites, bisulfates, polyphenolic com­
pounds, and bacteria (such as Escherichia coli FR-2 and Klebsiella sp.
4.1.2. Complex absorption strain FD-3) have been employed to efficiently reduce Fe3+-EDTA at
To improve the removal efficiency of NO, various chelating agents ambient temperature, their reduction efficiency are compared and listed
are introduced into the solution to form a complex with NO [314–317]. in Table 13.
By adding metal complexation agents (generally ferrous and cobalt Removal efficiency of SO2 rises with the increase of SO2 concentra­
chelating agents) into wet de-SO2 process, the solubility of NO in solu­ tion in the flue gas, as a higher SO2 concentration enhances mass transfer
tion can be increased dramatically which contribute to improving the rates both in gas and gas–liquid phases. Moreover, when sulfite (SO2− 3 )
efficiency of de-NOx and de-SO2. and hydrosulfite (HSO−3 ) ions are present, Fe3+ is slowly reduced back to
(1) Fe based complex absorbents Fe2+, and a steady state can be reached with a fraction of iron in the form
Chelating agents, such as Fe2+-EDTA (EDTA, ethylenediaminetetra­ of Fe2+ [318]. However, when the SO2 concentration is excessive,
acetic), can increase the solubility of NO via forming steady-going despite mass transfer rate is promoted further, the reaction rate becomes
ferrous-nitrosyl complexes as Eqs. (90) and (91). Although much the RDS, resulting in a decreased removal efficiency due to SO2 accu­
higher removal efficiency of NO can be obtained, the Fe2+-EDTA is mulation. In addition, excess SO2 may compete with NO for the limited
easily oxidized to Fe3+-EDTA by O2, NO and NO2 in flue gas (Eqs. (92) complexant (Fe2+-EDTA) in the solution, thereby reduces the efficiency
and (93)), leading to no ability to bind NO. As a result, the concentration of de-NOx. Moreover, since flue gas generally contains a certain con­
of the active Fe2+-EDTA in the scrubbing solution decreases quickly as centration of O2, which can oxidize Fe2+-EDTA to Fe3+-EDTA, then

Table 12
Absorption mechanism of SO2 and NO by different alkaline solutions with diverse oxidants.
Absorbent Oxidant Chemical reaction Maximum Ref.
removal
efficiency

Ca(OH)2 O2 SO2⋅H2O + Ca(OH)2 → CaSO3 + 2H2O CaSO3 + O2 + NO → CaSO4 + NO2 2NO2 + H2O → HNO2 + HNO3 SO2: 100% NOx: [299]
SO2−
THS
→ 2NO2− + SO2− 70%
3 + NO2 + OH 4 + H2O Ca(OH)2 + 2HNO2 → Ca(NO2)2 + 2H2O Ca
−

(OH)2 + 2HNO3 → Ca(NO3)2 + 2H2O

(NH4)2SO3 O2 SO2⋅H2O + (NH4)2SO3 ↔ NH4HSO3 2(NH4)2SO3 + O2 → 2(NH4)2SO4 2NO2 + H2O + SO2− 2−
3 → 2NO2 + SO4
−
SO2: 90% NOx: [300]
+ 2H+ NO + SO2−3 → NOSO3
2−
75%
(NH4)2S2O3/steel slag O3 SO2⋅H2O + Ca(OH)2 → CaSO3 + 2H2O SO2⋅H2O + Mg(OH)2 → MgSO3 + 2H2O O3 + NO + 2S2O2−3 → SO2: 100% NOx: [301]
slurry O2 + 2S2O2−
3 +2NO2
−
78%
Na2S O2 Na2S + 2SO2 + 2H2O → H2S + 2NaHSO3 2H2S + SO2 → 3/8S8 + 2H2O NO2 + Na2S → Na2SO4 + N2 SO2: 75% NOx: [302]
80%
Na2SO3 O2 SO2 + 2OH− + 0.5O2 + NO → SO2−
3 + H2O + NO2
−
SO2: 100% NOx: [303]
72%
O3 3SO2 + 6OH− + O3 → 3SO2− 2− 2−
4 + 3H2O 2NO2 + H2O + SO3 → 2NO2 + SO4 + 2H
− +
SO2: 99% NOx: [304,305]
2NaSO3 + 2NO → 2NaSO4 + N2 3NaSO3 + NO + NO2 → 2NaSO4 + N2 90%
NaOH SO2 + 2OH− → SO2−
3 + H2O 2NO2 + 2OH → NO2 + NO3 + H2O
− − −
SO2: 100% NOx: [306]
60%
HA-Na O2 4A + NO2 + NO + 2H2O → 4HA↓ +
−
NO−3 + 3NO−2 4A + −
SO2 + HSO−3 + H2O → 2HA↓ + HSO−3 + SO2−
3 SO2: 100% NOx: [307]
65%
Urea O2 SO2 + (NH2)2CO + 2H2O + 0.5O2 → (NH4)2SO4 + CO2 NO + NO2 + (NH2)2CO → 2 N2 + CO2 + 2H2O SO2: 100% NOx: [308]
55%
NH4HCO3 O2 3SO2 + 4NH4HCO3 → 3S + 10H2O + 4CO2 + 2 N2 4NO + 4NH4HCO3 + O2 → 4 N2 + 10H2O + 4CO2 SO2: 99% NOx: [309]
NH4HCO3 → NH3 + H2O + CO2 SO2 + 8NH3 + 2O2 → 4 N2 + 6H2O + S 4NO + 4NH3 + O2 → 4 N2 + 6H2O 86%
Na2CO3 O2 NO2 + NO + H2O + Na2CO3 + O2 → 2NaNO3 + H2O + CO2 SO2: 95% NOx: [310]
SO2 + H2O + Na2CO3 + 0.5O2 → Na2SO4 + H2O + CO2 86%
Seawater HOCl NO + HOCl + H2O → NO−3 + Cl− + 3H+ SO2 + HOCl + H2O → SO2−
4 + Cl + 3H 2NO2 + HSO3 +
− + −
SO2: 100% NOx: [311]
H2O → 2NO−2 + SO2− 4 + 3H
+
92%
CaMg2(CH3COO)6 O2 SO2⋅H2O + Ca(OH)2 → CaSO3 + 2H2O SO2⋅H2O + Mg(OH)2 → MgSO3 + 2H2O CHi SO2: 80% NOx: [312]
(i = 1,2,3,4) + NO → HCN + O2 → N2 50%
Mg(OH)2 SO2⋅H2O + Mg(OH)2 → MgSO3 + 2H2O MgSO3 + O3 + 2NO + H2O → MgSO4 + HNO2 + HNO3 SO2: 100% NOx: [313]
75%
MgO + TEA 2NO2 + H2O → NO−2 + NO−3 + 2H+ NO2 + SO2−
3 → NO2 + SO3
− •−
SO•−
3 + N(CH2CH2OH)3 → SO2−
3 +N SO2: 100% NOx: [52]
(CH2CH2OH)•−
3 HNO 2 + N(CH2 CH2OH)3 → (CH 2CH2 OH)2 − N − CH2CH2ONO + H2O 85–100%

Note: THS represents tetrabutylammonium hydrogen sulfate; TEA represents triethanolamine.

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R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Table 13
Mechanism and efficiency of available methods to reduce Fe3+-EDTA or [Fe2+EDTA(NO)]2− for Fe2+-EDTA regeneration.
Reductants Reduction mechanism Fe3+EDTA reduction Ref.

Reduction Required
efficiency (initial time
concentration)

Sulfur- Na2SO3 2[Fe2+-EDTA(NO)]2− + SO2− 2+

3 → 2[Fe -EDTA]
2−
+ SO3(NO)2− 3+
2 → [Fe -EDTA] + N2O2
− 2−
65.0% (10.0 mM) 120.0 min [322]
bearing Na2S2O4 + SO2− 3+ 2−
3 2[Fe -EDTA] + 2SO3 → 2[Fe -EDTA]
− 2+ 2−
+ S2O2− 3+
6 2[Fe -EDTA] + 2HSO3 →
− −
50.0% (50.0 mM) 15.0 min [323]
derivatives Na2S2O8 2[Fe2+-EDTA]2− + S2O2− 2+
6 + 2H 2[Fe -EDTA(NO)]
+ 2−
+ 4HSO−3 → 2[Fe2+-EDTA]2− + 40.0% (3.6 mM) 10.0 min [324]
2HON(SO3)2− + H2N2O2
Metal Zn 5Zn + 2[Zn2+-EDTA(NO)]2− + 12H+ → 2[Zn2+-EDTA]2− + 5Zn2+ + 2NH+ 4 + 2H2O 98.1% (10.0 mM) 20.0 min [325]
powers Fe 5Fe + 2[Fe2+-EDTA(NO)]2− + 12H+ → 2[Fe2+-EDTA]2− + 5Fe2+ + 2NH+ 4 + 2H2O 67.3% (10.0 mM) 80.0 min [326]
3+ 2+ 2− (1/m)+
Al 2[Fe -EDTA] + M → [Fe -EDTA] + M
−
60.0% (100.0 mM) 50.0 min [327]
Activated carbon 2[Fe3+ -EDTA]- + SO2- + H O ̅̅̅→ SO2- + 2[Fe2 + -EDTA]2- + 2H+ 48.1% (100.0 mM) 60.0 min [328]
AC
3 2 4
Bacteria Escherichia coli FR-2 12[Fe2+-EDTA(NO)]2− + C6H12O6 → 12[Fe2+-EDTA]2− + 6 N2 + 6CO2 + 6H2O 24[Fe3+- 87.0% (6.0 mM) 360.0 min [329]
Klebsiella sp. strain EDTA]− + C6H12O6 + 24OH− → 24[Fe2+-EDTA]2− + 6CO2 + 18H2O 52.4% (10.0 mM) 720.0 min [330]
FD-3
Pseudomonas sp. 25.0% (6.0 mM) 1440.0 min [331]
strain DN-2
Pseudomonas sp. 77.0% (8.0 mM) 540.0 min [332]
DN-2, and
Escherichia coli FR-2
P. denitrificans ZGL1 17.5% (4.8 mM) 180.0 min [333]
P. denitrificans 55.0% (11.9 mM) 360.0 min [334]
(GIMCC1.468)
VC (Ascorbic acid) C6H8O6 + 2[Fe3+-EDTA]− → 2[Fe2+-EDTA]2− + C6H6O6 + 2H+ 100.0% (2.0 mM) 0.5 min [335]
Thiourea dioxide (NH2)2CSO2 + 2[Fe3+-EDTA]− + 4OH− → 2[Fe2+-EDTA]2− + (NH2)2CO + SO2−
3 + 2H2O 100.0% (2.0 mM) 30.0 min [336]

Note: M represents metal powder; for divalent and trivalent metals, m is equal to 1/2 and 1/3, respectively.

Fig. 16. Speciation distribution of complex solutions with equi-molar EDTA/Fe under different pH value: (a) EDTA/Fe3+ and (b) EDTA/Fe2+. Modified from [321].

reduces the absorbent concentration and consequently the efficiency of resistance, while that of SO2 is controlled by the gas-film resistance.
de-NOx. Therefore, resistance to NOx absorption is larger than that of SO2 and the
The pH of the solution is another key factor influencing the efficiency adsorption rate and the concentration of NO at the interface gas–liquid
of de-SO2 and de-NOx. An intermediate pH generally leads to a higher (CAi) can be described as Eq. (94). The average rate constant k of NO can
removal efficiency compared with both low and high pH levels, which also be changed dramatically with reaction conditions as shown in
can be attributed to reduced complex formation constant of EDTA and Table 14. It can be concluded that the higher concentration of NO has
Fe2+. More important, with the pH changing, four complexes can be better competition with SO2 in reacting with Fe2+-EDTA, and some
formed by Fe and EDTA with equilibrium reactions (Y = EDTA) as: additives (such as Na2SO3 or MgSO3) may increase the adsorption rate of
FeHY− , FeY− 2, FeY(OH) − 3 and FeYOH− 4 [319,320]. Fe2+ and Fe3+ NO. The absorption rate constant, highly temperature-dependent, in­
speciation distribution of complex solutions with equi-molar EDTA/Fe creases significantly with the increase of temperature (Table 14).
have been deduced by Hyperquad speciation and simulation software However, the rate constant of backward reaction also increases from 6 to
(Protonic Software, Leeds, UK) in consideration of EDTA/Fe formation 60 s− 1 at 50 ◦ C, resulting in a lower equilibrium constant at the higher
constants [321]. From Fig. 16, it can be concluded that the formation temperature (6 × 107 M− 1S− 1 at 25 ◦ C reduces to 3.7 × 107 M− 1S− 1 at
constants of Fe3+-EDTA and Fe2+-EDTA achieve the largest value at 50 ◦ C) [337]. Finally, the comparative advantage still holds (the effi­
about pH of 4.0 and 6.0, respectively, and then reduce sharply at more ciency of de-NO rises with temperature) due to the synergistic effects of
acidic or more alkaline solution. Fe2+-EDTA and additives.
The adsorption mechanism of SO2 and NOx can be explained by two-
film theory. The adsorption of NO is controlled by the liquid-film

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R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Table 14
The reaction rate constants of de-NO by Fe2+-EDTA complex solutions with additives under different temperature.
1 − 1
Gas concentration (ppm) Absorbent and additive Reaction rate (k, M− s ) Ref.
2+ 8 8 8
NO: 30–300 Fe -EDTA: 0.010–0.300 M, Na2SO3: 15 C, pH = 7.7, k = 0.80 × 10 25 C, pH = 4.6–8, k = 1.70 × 10 35 C, pH = 7.7, k = 2.60 × 10
◦ ◦ ◦
[338]
0–0.75 M
NO: 40–630 SO2: Fe2+-EDTA: 0.010–0.050 M, MgSO3: 7
25 C, pH = 1.5–2.5, k = (3.29 ± 0.18) × 10 25 C, pH = 7, k = (1.23 ± 0.06) × 10 25 C,
◦ ◦ 8 ◦
[339]
500–3000 0.5–5.0 wt% pH = 9.5–10, k = (1.04 ± 0.10) × 108
NO: 40–300 SO2: Fe2+-EDTA: 0.025–0.3 M, MgSO3: 25 ◦ C, k = 1.51 × 108 [340]
500–2500 0–5 wt%
Fe2+-EDTA: 0.004–0.012 M 25 ◦ C, 6.00 × 107 [341]
NO: 650–3000 SO2: Fe2+-EDTA: 0.010–0.050 M, Na2CO3: 25 ◦ C, k = 1.24 × 108 40 ◦ C, k = 1.35 × 108 60 ◦ C, k = 1.43 × 108 80 ◦ C, k = 1.47 × 108 [317]
2000–4000 0.4–2.0 wt%
NO: 300–800 Fe2+-EDTA: 0.010–0.050 M 50 ◦ C, k = 3.70 × 107 [342]
NO: 700–800 Fe2+-EDTA: 0.010 M, Na2S2O8: 0.10 M 25 ◦ C, k = 3.60 × 106 40 ◦ C, k = 6.00 × 105 [319]
NO: 0–670 SO2: 50–300 Fe2+Citrate: Fe2+-EDTA = 1:1, 3:1, 4:1, 25 ◦ C, k = 2.10 × 105 55 ◦ C, k = 1.19 × 105 [337]
7:1

Fig.17. De-NOx and de-SO2 mechanisms by sequential adsorption and catalytic oxidation: (a) over Co(NH3)2+
6 in ammonia solution. Modified from [350]; (b) over Co
(en)3+
3 in ethylenediamine solution.

oxidized to Co(NH3)3+
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
2 6 , which can neither activate O2 nor bind NO,
NA = DA km,n Cm+1 Ai CB0
n
(94) leading to decreased removal efficiency of NO. I− or modified activated
m+1
carbon have been added into the reaction solution to reduce Co(NH3)3+6
to Co(NH3)2+6 (active constituent), the reaction mechanism of catalytic

PA0 − NA PAi 1000 ρH 2 O X CAi

PAi = X = CAiw = × log( ) = − (KB IB + K E IE )
kGA H 18 1− X CAiw

oxidation of NO by Co(NH3)2+
6 is illustrated in Fig. 17 (a) [346,347].
(2) Co based complex absorbents [ ]2+
Long et al. [343] proposed a novel simultaneous de-SO2 and de-NOx
2+
Co(NH3 )6 + NO → Co(NH3 )5 NO + NH3 (95)
process by adding soluble Co2+ salt into aqueous ammonia solution. The [ ]4+
hexamminecobalt(II) formed by ammonia binding with Co2+ is the 2Co(NH3 )2+
6 + O2 → (NH 3 )5 Co − O − O − Co− (NH3 )5 + 2NH3
active component for NO and SO2 scrubbing from flue gas. O2 dissolved (96)
in solution oxides NO into nitrate and nitrite as described by Eqs. (95)–

[ ]4+ [ ]2+ [ ]2+

(NH3 )5 Co − O − O − Co− (NH3 )5 + 2NH3 + H2 O + Co(NH3 )5 NO → 2Co(NH3 )3+ −
6 + 2OH + Co(NH3 )5 NO2 (97)

(98). Meanwhile, SO2 can be scrubbed by dilute ammonia solution and

binuclear complex formed by coordinating of Co(NH3)2+6 with O2 as
shown by Eqs. (99) and (100) [344,345]. However, Co(NH3)2+
6 is easily

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R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

4.2.1. Carbon-based adsorbents

[ ]2+ Activated carbon (AC) is an amorphous material used industrially as
2 Co(NH3 )5 NO2 + H2 O + 4NH3 → NH4 NO2 + NH4 NO3 an adsorbent for gaseous pollutants control due to its high porosity,
+ 2Co(NH3 )2+
6 (98) extensive surface area (up to 3000 m2/g), as well as variable charac­
teristics of surface chemistry. AC can be produced by pyrolysis, gasifi­
SO2 + 2NH3 + H2 O → 2NH+ 2−
4 + SO3 (99) cation, or chemical oxidation of any substance rich in organic carbon,
with the purpose of controlling the volume and size of pores created
[ ]4+
SO2−3 + (NH3 )5 Co − O − O − Co− (NH3 )5 → SO2−4 + 2Co(NH3 )3+ during carbonization.
6
The physisorption of gaseous pollutants on the micropores or surface
(100)
of AC is not high-efficiency, and the absorbed gas tends to be released by
Since the avoidable escape of ammonia may be harmful to human changing temperature or atmospheric pressure. Therefore, AC needs to
being and lead to environmental pollution, ammonia has been replaced be treated by pre-activation or covering components to improve cata­
by ethylenediamine in recent researches. In this way, Co(en)3+ 3 is sug­ lytic performance. As summarized in Fig. 18, both physical activations
gested to accomplish sequential adsorption and catalytic oxidation of (such as steam and CO2 activation) and chemical activations (metal
NO without adding any additives to regenerate active component, the oxides, alkaline metals and acids) can be applied to improve the
whole reaction mechanism of catalytic oxidation of NO and SO2 by Co porosity, surface area and pore size of AC according to target purposes.
(en)3+
3 has been described briefly as Fig. 17 (b) [348,349]. Co(en)2(NO) The co-existing O2 in flue gas can increase the removal efficiency of
OH2+ is formed by the coordination between NO and Co(en)3+ 3 , and then SO2 and NO by AC adsorption, as the adsorbed NO and SO2 on the
oxidized to Co(en)2(NO2)OH2+ under aerobic condition. Under a high surface of AC can be easily oxidized by O2, then NO2 and SO3 can be
pH value, OH− can replace the NO2 in Co(en)2(NO2)OH2+ to form Co captured by H2O to form sulfate and nitrate acids or salts. The oxidation
(en)2OH2+, and the NO2 released hydrolyzes to NO−3 or NO−2 . Then Co mechanisms of SO2 and NO over AC have been well illustrated by
(en)2OH2+ reacts with OH− to regenerate Co(en)3+ 3 . The removal of SO2 Langmuir-Hinshelwood and Eley-Rideal models as detailed in table 15.
follows a similar reaction mechanism. Therefore, a higher pH value of Additionally, surface characteristics of AC (such as pore structure, sur­
the reaction solution is beneficial to the reproduction of Co(en)3+ 3 . face area, functional groups and morphology), flue gas components
Notably, Co(en)3+
3 does not take part in the above net reactions and only (concentrations of O2, SO2 ,NOx, CO etc.), reaction conditions (sorbent
acts as a catalyst to accelerate the oxidation of NO and SO2 to soluble amount, gas velocity, contact time), and reaction temperature have
NO2 and SO3 in the aqueous solution, the O2 coexisted in flue gas is significant influence on the removal efficiency of NO and SO2 as sum­
actually the oxidant. In addition to Co(en)3+
3 , I can also play the role of
−
marized in Table 16.
electron transporter. I in the absorption solution reacts with NO2 to
−
Since SO2 has higher permanent dipole moment and polarizability
form I2 and NO−2 , then the I2 can further be reduced by SO2 along with than NOx, AC presents greater affinity for SO2 than NOx. As a result, the
H2O back to I− [310]. Therefore, KI is suggested as a I− supplying species adsorption of NO is inhibited during the competitive adsorption with
of de-NOx and de-SO2 by sequential adsorption and catalytic oxidation SO2, while the presence of NOx promotes the adsorption process of SO2.
processes. Davini [371] proposed that NO helps to create or to stabilize basic
surface oxides, which improve the adsorption of SO2. However, Guo
et al. [361] argued that the NO adsorption–desorption process increases
4.2. Solid adsorption
the number of C = O groups over the AC surface, which can provide
more active vacant sites for SO2 oxidation, and the replacement of NO in
SO2 and NOx can also be removed from flue gas by porous solid
C-O-NO by SO2 also promotes SO2 adsorption. Additionally, SO2 is
adsorbents through adsorption, which have been investigated exten­
preferential adsorbed chemically on the active sites of AC, then SO2**
sively due to their wide availability and easy cyclicity. In addition to
reacts with NO and O2 to for [(NO2)(SO3)*], meanwhile an active site (*)
metal oxides, zeolites and porous carbons in different forms, new crystal
released facilitates the adsorption of SO2 (Eq. (101)) [372]. On the
structure of metal–organic frameworks (MOFs) and hybrid organ­
contrary, the presence of SO2 inhibits the adsorption of NOx because SO2
ic–inorganic materials-supported amine adsorbents have recently
is somewhat larger molecule and compete more favorably for O2 [356].
developed, their removal process, interactions of SO2 and NOx with
Thus, O2 plays a critical role in the oxidation of the adsorpted-SO2 and
adsorbents, activation methods, and factors influencing the efficiency
NOx.
(such as coexisting gases and humidity) are extensively reviewed.
NO + O2 + SO2** → [(NO2)(SO3)*] + * * active site (101)

Water vapor is usually included in increase the relative humidity of

the adsorbate and consequently enhances removal of NO and SO2.
During the removal process, SO2 is oxidized to form SO3, and then to
form sulfuric acid in the presence of water. However, the pore and
surface of AC may be blocked by layers of sulfates, resulting in early
termination of SO2 removal. Other drawbacks, such as deactivation at
low temperature and poisoning in the presence of SO2, have also been
reported due to the formation of sulfates [373] and sulfation of AC
surface [374].
Impregnation of metal oxides (V2O5, CuO, Fe2O3, MnO2, Cr2O3 and
CeO2) into AC is an effective countermeasure to relieve the above
drawbacks, as these metal oxides act as initiator to oxidize NO or reduce
it to N2. For instance, palm shell activated carbon (PSAC) can only
remove SO2, while PSAC impregnated with metal oxides can remove SO2
and NO simultaneously with extreme efficiency, particularly for PSAC
impregnated with 10 wt% of CeO2 [356,357,369,375]. What else,
impregnating metal oxides into AC also changes the reaction mechanism
Fig. 18. Available activation methods for AC and their main purposes. Modi­ and metal cations, with easily convert between the two valences seem to
fied from [197,351].

28
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Table 15
The oxidation mechanisms of SO2 and NO over AC.
Oxidation Langmuir-Hinshelwood mechanism (L-H) Eley-Rideal mechanism (E-R) Ref.
mechanism

SO2 SO2 (gas) → SO2 (ads.) O2 (gas) → 2O (ads.)SO2 (gas) + O (ads.) → SO3 (ads.) SO2 (gas) → SO2 (ads.)SO2 (gas) + O2 (gas) → SO3 (ads.)H2O [352,353]
H2O (gas) → H2O (ads.)SO3 (ads) + H2O (ads.) → H2SO4 (ads.) (gas) → H2O (ads.)SO3 (ads) + H2O (ads.) → H2SO4 (ads.)
NO NO + Cf ↔ C–NO(a)O2 + 2Cf ↔ 2C–O(b)C–NO + C–O ↔ C–NO2 + Cf(c) NO + Cf ↔ C–NO(a)2C–NO + O2 ↔ 2C–NO2(b) [354]
C–NO2 + C–NO2 ↔ C–NO3 + NO + Cf(d) C–NO2 + C–NO2 ↔ C–NO3 + NO + Cf(c)
C–NO3 + C–NO ↔ C–NO–NO3 + Cf(e)C–NO–NO3 → 2NO2 + Cf(f) C–NO3 + C–NO ↔ C–NO–NO3 + Cf(d)C–NO–NO3 → 2NO2 + Cf(e)

be crucial to the good performance of de-SO2 and de-NOx simulta­ oxides (CuO/γ-Al2O3, MgAl, Ce/MgAl, CuMgAl, CuMgAlFe, etc) [388]
neously. For example, SO2 is catalytic oxidized over V2O5/AC through a have been used as catalyst and adsorbent for simultaneous de-SO2 and
VOSO4-like intermediate species [376], which reacts with O2 to form de-NOx, sometimes reductants, such as NH3, CO, etc. have been involved
SO3 as listed in Table 16. to improve the removal efficiency but once SO2 is inlet in the system,
these metal oxides react with SO2 rapidly to form stable salts, leading to
4.2.2. Zeolite-based adsorbents rapid deactivation of catalysts and further low removal efficiency of NO
Due to high porosity, permeability and unique surface properties, and SO2 [389,390].
both natural and synthetic zeolites have been widely used as catalysts, (1) Metal organic frameworks (MOFs)
adsorbent and membrane in a variety of applications in flue gas purifi­ Metal organic frameworks (MOFs), inorganic–organic hybrid mate­
cation. Although single pollutant (SO2, NO, CO2, etc.) removal through rials, have recently developed and received considerable attention for
zeolites (such as silicalite, zeolite Y, zeolite X, ZSM-5 and so on) adsorption of various gaseous pollutants due to their large surface area,
adsorption have been extensively investigated, only few literatures re­ well-designed pore structure and easy regeneration through desorption.
ported simultaneous removal of SO2 and NOx as listed in Table [Link] Unlike carbon-based materials and zeolites, the novelty of MOFs is that
coexisting of SO2 and NOx in flue gas has obviously influenced on the the intermolecular interactions and metal–ligand interactions can be
adsorption, reaction kinetic, and removal efficiency. Low-frequency SO2 exploited through the tunable design of an extensive array of two- or
adsorption on DC and DA zeolites proceeds via Na+, whereas high- three-dimensional frameworks with substantial porosity, different
frequency SO2 adsorption proceeds via hydroxyl groups [377], and chemical functionalities, unusual ion exchange and various sorption
participation of basic and structural Lewis acid centers are not proved characteristics, providing an opportunity to tailor surface area, pore size
during SO2 adsorption. However, Dmeirbas [378] concluded that be­ and surface functionality [391].
sides OH− , Lewis basic sites (≡Si − O − Al≡ moiety) can also interact Within the past decade, over 20,000 types of MOFs have been syn­
with SO2 by bridging O via donor–acceptor. Similarly, NO can either be thesized, their shape, size and functionality can be adjusted owing to the
physically adsorbed by reversible binding of nitrogen with cations in the great flexibility of microstructure and constituent [392], Selective
framework or be irreversibly bound to the surface and then to form adsorption of SO2 and NO by MOFs in different conditions are summa­
nitrosyl complexes [379]. rized in Table 18. Physisorption and chemisorption are the two major
In general, metal cations (alkali and alkaline earth ions) are often mechanisms for the removal of SO2 and NOx by MOFs. Physisorption is
existed in the structure of zeolite to balance the negative charge. attributed to the surface interactions of SO2/NOx with metal/organic
Modified zeolite-based adsorbents by exchanging with transition-metal groups. As for chemisorption, unsaturated metal sites (CUSs) interac­
ions not only have higher chemical-adsorption capacity of NO, but tion, acid base interaction, electrostatic interaction, π-complexation,
also present larger physical-adsorption capacity of SO2. In addition, NO hydrogen bonding, and breathing effect are regarded as the six main
as an oxidant can react with SO2 on the surface of K − NaX zeolite, de­ adsorption mechanisms between SO2/NOx and active sites of MOFs as
tails about the coadsorption mechanism can be described as follows shown in Fig. 19. Among these host–guest interactions, acid base
(Eqs. (102)–(104)) [380]: interaction, π-complexation, hydrogen bonding, and CUSs interaction
(coordination with accessible metal sites) play major roles in the
SO2(ad) + NO(ad) → SO3 N(ad) (102)
chemisorption [391].
As refereed above, MOFs are regarded as promising SO2 and NOx
SO3 N(ad) + SO3 N(ad) →2SO3 + N2 O(ad) + SO2(ad) (103)
adsorbents owing to the presence of unsaturated metal sites [407],
N2 O(ad) + SO2(ad) → SO3(ad) + N2(ad) (104) which is also a major hurdle to using MOFs in gas purification, as the
dynamic interactions between the ligands and the metal ionic sites are
Combination of zeolite-based adsorbents and NTP is also promising responsible for the collapse of the pristine architectural framework of
and efficient technology for simultaneous de-SO2 and de-NOx. Both MOFs. Moreover, moisture and other gases like NH3 and O2 in flue gas
oxidation and reduction take place in microwave catalytic process with may narrow the stability and adsorption capacity of MOFs. Therefore, a
Cu/zeolite as catalyst and ammonium bicarbonate (NH4HCO3) as number of strategies has been applied to improve the SO2 and NO
reductant [381]. Basically, OH• generated during microwave catalytic storage capacities of MOFs and the stability of MOFs in flue gas,
plays an important role in the oxidation of SO2 to sulfate and NOx to including appropriate selection of ligand design [397], exploitation of
nitrate simultaneously. Moreover, SO2 and NOx can react with ammonia framework flexibility [408], introduction of non-framework cations
(NH3) decomposed by NH4HCO3 to produce sulfur and N2. Additionally, [409], and post synthetic modification [400]. But very few MOFs re­
the dielectric barrier discharge-catalyst (DBD-C) hybrid process and the ported can be stable when exposed to industrial exhaust flue gas [410].
dielectric barrier discharge catalyst-photocatalyst (DBD-C-P) hybrid In recent years, an increasing focus has been paid on optimizing the
process have been introduced to de-SO2 and de-NOx [382,383], the NO stability and selective adsorption capacity of MOFs, and large-scale
and SO2 removal efficiencies of the DBD-C-P hybrid process can be as production of MOFs has not been commercialized yet [411].
higher as 1.02–3.40 times and 1.03–4.00 times, respectively, compared (2) Solid amine adsorbents
with normal scrubbing process [88] as listed in Table 17. Solid amine adsorbents, another emerging hybrid organic–inorganic
adsorbent, has gained increasing attention for de-SO2 and de-NOx due to
4.2.3. Metal oxide-based adsorbents their high surface area and inherent larger adsorption capacity
Historically, basic oxides especially CaO and MgO are employed to [412,413]. Main reactions between solid amine adsorbents and SO2 and
remove SO2, but have nearly no effect for NOx removal. Recently, mixed

29
 R. Chen et al.
Table 16
Selective adsorption of SO2 and NO by AC.
Carbon source Activation condition Removal mechanism BET surface area Reaction condition Maximam Adsorption Ref.
(m2/g) removal capacity (mg/g)
efficiency
(%)

Coconut shell 10% KOH impregnation – 719 Sorbent: 10.70 gTemperature: – SO2: 40.0 mg/ [355]
130 ◦ CSO2 (1000 ppm), NOx gNOx: 22.0 mg/g
(1000 ppm), air balanceLinear
velocity: 30 cm/sContact time:
210 min
Palm shell CO2 activation – Pure PSAC: Sorbent: 1.00 gTemperature: – SO2: 165.0 mg/ [356]
(700–1100 ◦ C) + 10% 1212PSAC-Ce: 100 ◦ CSO2 (2000 ppm), NO gNOx: 115.0 mg/
metal impregnation 997PSAC-Ni: (500 ppm), O2 (10%), N2 g
976PSAC-Fe: balanceGas flow rate: 0.15 L/
1002PSAC-V: minContact time: 90–150 min
991
Palm shell CO2 activation Without Ce: SO2 (L-H); NO (L-H)With Ce: xSO2 + CeO2 ↔ xSO3 + CeO2-x Pure PSAC: Sorbent: 1.00 gTemperature: – SO2: 121.7 mg/ [357]
(700–1100 ◦ C) + 5–12% CeOx+1 + NO → CeO2-x + NO2CeOx+1 + xNO → CeO2 + 1/2xN2 1100Ce5/PSAC: 100–200 ◦ CSO2 (2000 ppm), NO gNOx: 3.7 mg/g
Ce impregnation 1033Ce8/PSAC: (500 ppm), O2 (10%), N2
962Ce10/PSAC: balanceGas flow rate: 0.15 L/
834Ce12/PSAC: minContact time: 125 min
705
Styrene- CO2 (10%) and steam SO2: L-H mechanismNO: L-H mechanismNO2 (ads) + C → 2NO + CO24NO2 1077 Sorbent: 1.50 gTemperature: SO2: 60% – [358]
divinylbenzene (35%) activation at (ads) + 3C → 2N2O + 3CO2 100–200 ◦ CSO2 (2190 ppm), NO NOx: 50%
copolymer 900 ◦ C (1890 ppm), O2 (6.6%), N2
balanceLinear velocity: 3 cm/sGas
flow rate: 0.70 L/minContact
30

time: 150 min

Petroleum pitch CO2 activation – 1240–1360 Sorbent: 0.10 gTemperature: – SO2: 125.0 mg/ [359]
(900 ◦ C) + Fe 100 ◦ CSO2 (1000 ppm), NO gNOx: 50.0 mg/g
impregnation (400 ppm), O2 (5%), N2
balanceGas flow rate: 0.05 L/
minContact time: 150 min
Commercial coconut – SO2 → SO2*NO + 1/2O2 + * → NO2*NO2* + 1/2O2 + SO2* → [(NO2)(SO3)]* 893 Sorbent: 4.00 gTemperature: – SO2: 65.0 mg/ [360]
shell +* 120 ◦ CSO2 (850 ppm), NO gNOx: 54.0 mg/g
(500 ppm), O2 (5%), N2
balanceGas flow rate:0.30 L/
minContact time: 360 min
Coconut shell CO2 activation (800 ◦ C) NO + O2 + SO2 → [(NO2)(SO3)] *C-O-NO + SO2 → C-O-SO2 → C-SO3> 1233 Sorbent: 4.0 gTemperature: – SO2: 150.0 mg/ [361]
C = O + SO2 → [-C(=O)-SO2]* + O → [-C(=O)-SO3]* 120 ◦ CSO2 (1000 ppm), NO gNOx: 4.0 mg/g
(500 ppm), O2 (5%), water vapor
(40%), N2 balanceGas flow rate:

Chemical Engineering Journal 420 (2021) 127588

0.3 L/min
Commercial coconut – – 981 Sorbent: 0.30 gTemperature: – SO2: 75.8 mg/ [362]
shell 120 ◦ CSO2 (0.1 mol%), NO gNOx: 38.1 mg/g
(0.05 mol%), chlorobenzene
(0.025 mol%), O2 (5 mol%), Ar
balanceGas flow rate: 0.30 L/min
Commercial 1 M HNO3 impregnation SO2: L-H mechanismNO: E-R mechanism 1498 Sorbent: SO2: 80% – [363]
activated carbon for 48 h 0.45–0.48 gTemperature: NOx: 60%
fibers 200 ◦ CSO2 (200 ± 10 ppm), NO
(60 ± 3 ppm), air balanceGas flow
rate: 0.06 L/minContact time:
20 min
Commercial Steam activation (850 ◦ C) SO2: L-H mechanismNO: 386 Temperature: 120 ◦ CSO2 (0.3 mol SO2: 67.7% – [364]
activated coke AC
4NO + 4NH3 + O2 → 4N2 + 6H2 OSO2 + H2 O + 1/2O2 → H2 SO4
AC %), NO (1000 ppm), NH3 NOx: 30.4%

(continued on next page)

 R. Chen et al.
Table 16 (continued )
Carbon source Activation condition Removal mechanism BET surface area Reaction condition Maximam Adsorption Ref.
(m2/g) removal capacity (mg/g)
efficiency
(%)

2KOH + 2NO2 + 1/2O2 →2KNO3 + H2 O (1000 ppm), O2 (6.0%), H2O

(11%), N2 balanceGas flow rate:
7.00 L/minContact time:
180 minSorbent: 0.06 g
Commercial V impregnation SO2: SO2 (gas) → SO2 (ads.)SO2 (ads.) + V2O5 → VOSO4 + VO22VOSO4 + 0.5O2 → – Temperature: 200 ◦ CSpace NOx: 70% SO2: 100.0 mg/g [365]
activated carbon V2O5 + 2SO3SO3 + H2O → H2SO4NO: velocity: 6500 L/kg hSO2
AC
4NO + 4NH3 + O2 ̅̅̅→ 4N2 + 6H2 O (1500 ppm), NO (500 ppm), NH3
(500 ppm), O2 (3.4%), H2O
(2.5%), N2 balanceGas flow rate:
7.00 L/minContact time: 150 min
wooden columnar Microwave irradiation SO2: C + SO2 → S + CO22C + SO2 → S + 2CO2CO + SO2 → S + 2CO2NO: C + 2NO → 1421 Sorbent: 40.00 gTemperature: SO2: 100% – [366]
activated carbon N2 + CO22C + 2NO → N2 + 2CO2CO + 2NO → N2 + 2CO2 120 ◦ CSO2 (1500 mg/m3), NO NOx:
(500 mg/m3), O2 (8.9%), N2 88.24%
balanceGas flow rate: 2.00 L/
minMicrowave
irradiation:10 minMicrowave
power: 560 W
Coconut shell Ionic liquid and KOH AC
SO2 : SO2 + H2 O + 1/2O2 → H2 SO4 1114 Sorbent: 3.00 gTemperature: – Breakthrough [367]
impregnation NO2 : 2KOH + 2NO2 + 1/2O2 → 2KNO3 + H2 O 25 ◦ CSO2 (5 ppm), NO2 (5 ppm), time:SO2: 89 min
RH (50%), air balanceGas flow ([C2mim][Ac]-
rate: 30.00 L/minContact time: 30)NO2: 41 min
1200 min (KOH)
Furfuryl alcohol CO2 activation SO2 → SO2*NO + 1/2O2 + * → NO2*NO2* + 1/2O2* + SO2* → [(NO2)(SO3)]* + * 49 Sorbent: 1.0 gTemperature: – SO2: 123.1 mg/ [368]
(350 ◦ C) + HNO3 100 ◦ CSO2 (50–300 ppm), NOx gNOx: 130.2 mg/
31

activation + Co (50–300 ppm), N2 balanceGas g

impregnation flow rate: 0.40 L/minContact
time: 180 min
Palm shell CO2 activation SO2: L-H mechanismNO: NO + O2* + SO2* → [(NO2)(SO2)]* + *NO2* + SO2* → – Sorbent: 1.00 gTemperature: – SO2: 121.7 mg/ [369]
(1100 ◦ C) + Co SO3* + NO + *2NO2 + HSO−3 + H2O → SO2− 2−
4 + 3H + 2NO22NO2 + SO3 + H2O →
+
150 ◦ CSO2 (2000 ppm), NO gNOx: 3.5 mg/g
impregnation SO2−
4 + 2H 2NO2
+
(500 ppm), O2 (10%), N2
balanceGas flow rate: 0.15 L/
minContact time: 300 min
Viscose 30 wt% HNO3 activation SO2: E-R mechanismNO: E-R mechanismC-O-NO + SO2 → C-O-SO2 + NOC-O-NO + 1270 Sorbent: 0.50 gTemperature: – SO2: 67.1 mg/ [370]
HCl → C-Cl + C-HNO2 25 ◦ CSO2 (600 mg/m3), NO gNOx: 8.9 mg/g
(450 mg/m3), HCl (600 ppm), O2
(6%), CO2 (10%), N2 balanceGas
flow rate: 1.50 L/minContact
time: 70 min

Chemical Engineering Journal 420 (2021) 127588

Note: PSAC represents palm shell activated carbon; Ce5/PSAC represents PSAC with a Ce loading of 5 wt%; * represents active sites for adsorption; the subscript ad represents the adsorbed species on the catalyst.
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

NOx can be presented as Eqs. (105)–(109), and the thermal reversibility

[384]

[385]

[378]
[386]

[387]

[380]

[381]

[382]
of adsorption processes decrease in the order as CO2 > SOx > NOx
Refs. [414,415]. It should be noted that an appropriate amount of H2O and O2
is benefit for the absorption of SO2, which can be explained by the
formation of R3 NH+ HSO-3 as shown by Eq. (110). R3 NH+ HSO-3 is

SO2: 113.3 (K − NaX)

Maximum adsorption

NO: 18.3 (K − NaX)

decomposed completely to regenerate adsorbent during heating at

efficiency (%): SO2

efficiency (%): SO2

Maximum removal

Maximum removal
(42.3), NO (71.4)

(95.8), NO (93.4)
100–150 ◦ C in N2 atmosphere with eliminating H2O and SO2 [416,417].
SO2: 128.0

SO2: 267.0
(105)
SO2: 30.0

SO2: 71.5
R1 R2 NH + SO2 ⇌ R1 R2 NH+ SO−2
SO2: 8.0
(mg/g)

R1 R2 NH + NO ⇌ R1 R2 NHNO (106)

–
Temperature: 50 ◦ CSO2 (2000 ppm), H2O (5%), N2 balanceGas

(200 ppm), CO2 (14%), H2O (10%), O2 (6%), HCl (50 ppm), N2 (107)

Temperatures (0 ◦ C)SO2 (1000 mg/m3), NOx (250 mg/m3), air

Temperatures (0 ◦ C)SO2 (1000 mg/m3), NOx (250 mg/m3), air

R1 R2 NHNO + NO ⇌ R1 R2 NHN2 O2

balanceEmpty bed residence time: 0.358 sMicrowave Power:

(1000 ppm), CO2 (10%), O2 (5%), N2 balanceGas flow rate:

balanceEmpty bed residence time: 0.36 sMicrowave Power:

Sorbent: 20.00 gTemperatures (90 ◦ C)SO2 (2000 ppm), NO
Sorbent: 0.15 gTemperature: 25–100 ◦ CSO2 (0.5–5%), air

Sorbent: 2.5 gTemperatures (70 ◦ C)SO2 (10000 ppm), N2

Sorbent: 0.15 gTemperatures (25 ◦ C)SO2 (200 ppm), NO

R1 R2 NHN2 O2 + R1 R2 NH ⇌ R1 R2 NH+ −
2 R1 R2 NHN 2 O2 (108)

R1 R2 NH+ − + −
2 R1 R2 NHN2 O2 + 1/2O2 ⇌ R1 R2 NH 2 NO2 + R1 R2 NNO (109)

R3 N + SO2 + H2 O ⇌ R3 NH+ HSO−3 (110)

Sorbent: 50.00 gTemperature: 80 ◦ C

where R1, R2 and R3 = H or CH3.

280 WGas flow rate: 2.5–5.8 L/min

280 WGas flow rate: 2.5–5.8 L/min

balanceGas flow rate: 0.1 L/min

balanceGas flow rate: 0.3 L/min

balanceGas flow rate: 1.2 L/min

5. Microbial approach
flow rate: 2.0 L/min

Beside physical and chemical de-SO2 and de-NOx methods, microbial

simultaneous de-SO2 and de-NOx approach using autotrophic microor­
ganisms under anoxic condition has been developed recently [418],
Condition

0.3 L/min

which has the advantages of mild conditions, high removal rate, no

chemical catalyst, low energy consumption, no secondary pollution and
generating sulfur recovery resources [419]. The essence of microbial de-
SO2 and de-NOx approach is that inorganic sulfides are used as electron
donor to remove NO−x through biochemical actions, which supply the
Kinetic model

necessary energy for the growth of microorganisms.

Hinshelwood

Hinshelwood
Freundlich

Freundlich
Langmuir-

Langmuir-

Langmuir-

Langmuir-

The process of microbial de-SO2 and de-NOx can be divided into two
kinetics

kinetics

stages: (1) Dissolution stage, SO2 and NOx from gas phase transfer to
liquid phase by passing gas–liquid double membrane; (2) Biochemical
–
–

stage, NOx and SO2 are consumed by microorganisms on a liquid phase

or a solid phase surface [420]. Since the solubility of NO and NO2 in
0.11Ca − NaX: 0.17Mn − NaX:

water are quite different, removal mechanisms are also distinct. As for
The adsorption conditions and removal efficiency of SO2 and NOx by zeolite-based adsorbents.

NO, only a small amount of NO dissolves into solution, and then oxidizes
Micropore vol (cm3/g)

0.08Co − NaX: 0.06

to nitrates via denitrifying microorganisms or reduces to N2 via nitrogen

NaX: 0.22K − NaX:
Porosity (81.2%)

reductase, while most of NO is adsorbed on the surface of microbial cells

and solid phase carrier. In contrast, NO2 is first converted to nitrate/
0.23–0.32

nitrite, and then further reduced to N2 via nitrogen reductase as shown

0.154
0.351

in Fig. 21 [421]. For the removal of SO2, small amount of sulfite is

0.07
–

produced due to dissolution of SO2, then the sulfite is reduced to sulfide

under the action of microorganisms. Once sulfide is available in the
system, polysulfide naturally forms through the reaction between
pore size
Median

4.6
6.6
2000.0

58.0

67.1

elemental sulfur and HS– (generated from hydrolysis of sulfide). And HS–
–
–

–
(Å)

can stimulate indirect sulfur reduction by generating more polysulfide,

although excessive HS– inhibits the reduction of sulfate.
Based on the transfer of electrons, the triple element cycle-based
314.0Ca − NaX: 440.0Mn − NaX:

microbial pollutants removal conception has been proposed as shown

in Fig. 20, in which three biological processes are involved. Organic
BET surface area (m2/g)

carbon is oxidized to CO2 by bacteria and then dissolves as bicarbonate,

242.0Co − NaX: 196.0
NaX: 513.0K − NaX:

during which an electron can be provided for sulfate reducing process by

1014.0–1140.0

the sulfate reducing bacteria. Therefore, the transformation of SO2

170.0–200.0

(SO2 → sulfite/sulfate → sulfide) is accelerated significantly, leading to a

faster removal rate and higher removal efficiency of SO2. Under the
417.8
712.7

590.0

107.9

43.4

transfer of electrons, nitrate is autotrophically reduced to N2. Notably,

–

emission reductions of NOx, SO2 and CO2 can be achieved by the entire
process. In addition, the combination of microorganisms and catalytic
Co–NaXzeolites

de-SO2 by transition metal has received extensive attention [422–424].

CuCl2- MCM-41
MFI (H-ZSM-5)

Natural zeolite

NaXK/Ca/Mn/

In this process, the role of microorganisms is both direct and indirect

FeCu/zeolite
DAY zeolite

5A zeolites

Cu-zeolite

oxidation of SO2. For direct oxidation mechanism, SO2−

zeolite

3 generated from
Silicalite
Table 17

Zeolites

SO2 dissolution is directly oxidized to sulfate in solution via thiobacillus

ferrooxidans (T.f) (Eq. (111)), from which the microorganism obtains

32
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Table 18
Selective adsorption of SO2 and NO by MOFs in different conditions.
MOF BET Temperature Pressure/ Gas component Linker functionality Adsorption Ref.
surface (◦ C) bar capacity
area (mmol/g)
(m2/g)

ZIF-8 − 25 2.500 20 ppm Zn − N⋅⋅⋅N SO2: 8.00 [393]

MOF-177 4100 20 1.000 N2:CO2: Ofuran⋅⋅⋅SSO2OHAl‑chain⋅⋅⋅OSO2Ofuran/ SO2: 25.70 [394]
NH2-MIL-125(Ti) 1150 SO2=84.0:15.0:0.1 carboxylate⋅⋅⋅SSO2 SO2: 10.80
MIL-160 776 (vol) SO2: 7.20
MFM-601 3644 25 1.000 2500 ppm SO2 Terminal hydroxyl of the {Zr6} cluster SO2: 12.30 [395]
MFM-600 2281 (diluted in He: SO2: 5.00
N2 = 1.0:1.0)
SIFSIX-1-Cu 559 25 1.000 SO2:N2 = 0.2:99.8 Synergistic guest–host interactions SO2: 11.01 [396]
SIFSIX-2-Cu − (vol) (Sδ+⋅⋅⋅Fδ− and Oδ− ⋅⋅⋅Hδ+ interactions) SO2: 6.50
SIFSIX-2-Cu-i 630 SO2: 6.90
SIFSIX-3-Zn − SO2: 2.10
SIFSIX-3-Ni 223 SO2: 2.74
K[Ni8(OH)3(EtO)3(BDP_H)5.5] 2055 30 0.025 N2:SO2 = 97.5:2.5 Lewis acid–base interactions: SO2: 3.26 [397]
K3[Ni8(OH)3(EtO)(BDP_O)5] 1830 (vol) [Ni8(OH)6(OH)2]10+ + SO2: 2.54
K[Ni8(OH)3(EtO)3(BDP_NH2)5.5] 1665 SO2 → [Ni8(OH)5(HSO3)2]10+ → SO2: 4.38
Ba0.5[Ni8(OH)3(EtO)3(BDP_H)5.5] 1250 [Ni8(OH)4(SO3)(H2O)]10+M[Ni8(OH)4(SO3) SO2: 4.00
Ba1.5[Ni8(OH)3(EtO)(BDP_O)5] 850 (H2O)(BDP_X)5.5]+→ (MSO3)⋅ SO2: 3.65
Ba0.5[Ni8(OH)3(EtO)3(BDP_NH2)5.5] 1190 [Ni8(OH)4(H2O)(BDP_X)5.5]+ SO2: 5.61
[Zn4(μ4-O)(L1)3] 60 20 1.000 SO2 (4032 ppm) NH − C(O) − NH SO2: 2.20 [398]
[Zn2(L1)2(bipy)] 47 SO2: 10.9
[Zn2(L1)2(bpe)] − SO2: 6.40
Ni(bdc)(ted)0.5 1783 25 1.130 − SO2 − CH2 − ted or SO2 − O − bdc SO2: 9.97 [399]
Zn(bdc)(ted)0.5 1888 1.010 configurations SO2: 4.41
Mg-MOF-74 − 1.020 (OH)2 SO2: 8.60
HKSUT-1 909 25 − NO2 (1000 ppm) Cu–O NO2: 2.30 [400]
Co-MOF − 25 0.020 NO (90 ppm) CUSs NO: 6.00 [401]
Ni-MOF − NO: 7.00
Cu MOFs 89 120–220 − NO (1000 ppm), O2 Cu+/Cu2+Lewis acid sites:Eley-Rideal (E-R) NO removal [402]
(3%), NH3 mechanism efficiency:
(1000 ppm) 90%
Cu-BTC 987 25 − NO (500 ppm), O2 Unsaturated Cu(II) sites NO removal [403]
(8%), N2 balance efficiency:
77%
MFM-300(Al) 1370 25 1.000 NO2 (1666 ppm), CUSs SO2: [404]
SO2 (3334 ppm), He 4.80NO2:
balance 14.10
Zn-MOF-74 774 25 1.000 − CUSs SO2: 8.00 [405]
Mg-MOF-74 1078 (Mg-MOF-
Ni-MOF-74 913 74)
Co-MOF-74 1077

energy. For indirect oxidation mechanism, T.f promotes the oxidation of should be paid on breeding of efficient and inexpensive microorganisms
Fe2+ to Fe3+ under acidic condition, and then Fe3+ catalyzes the con­ in the future, and relative amplification technology should also serve as
version of SO2 to SO2− 2−
3 , which can be oxidized to SO4 in solution (Eqs. developed for industrial application.
(112) and (113)).
T.f
6. Conclusions and perspectives
Direct oxidation : 3SO2−3 + O2 + H2 O ̅̅̅̅̅̅̅̅̅→ 3SO2−4 + 2H+ + energy
(111) From the point view of the removal process, basic mechanisms and
reaction kinetics, simultaneous removal of SO2 and NOx methods were
T.f
Indirect oxidation : 2FeSO4 + H2 SO4 + 0.5O2 ̅̅̅̅̅̅̅̅̅→ Fe2 (SO4 )3 + H2 O systematically reviewed in consideration of removal pathways and the
(112) physical state of reactants. Main conclusions and perspectives that can
be drawn from the present study are as follows:
SO2 + Fe2 (SO4 )3 + 2H2 O → 2FeSO4 + 2H2 SO4 (113)
(1) For catalytic oxidation approach, the oxidation of SO2 and NOx
Other microorganisms, including heterotrophic nitrate-reduction bac­ can be divided into three pathways, in terms of gas–gas,
teria (hNRB), sulfate-reduction bacteria (SRB), sulfide-oxidation, nitrate gas–liquid and gas–solid oxidation. In the presence of catalysts,
reduction bacteria (SO-NRB), and other relevant microorganisms (fermen­ both direct oxidation and indirect oxidation (AOP) by reactive
tative bacteria, FB; methane-producing archaea, MPA) can also been oxygen species (ROSs) are involved in the oxidation mechanism.
employed into microbial de-SO2 and de-NOx process [425]. The effi­ Since the reaction rate of AOP is on the order of magnitude of the
ciency of microbial de-SO2 and de-NOx process is strongly influenced by direct oxidation process, numerous experimental parameters
the concentration of O2, which affecting the growth of nitrifying/ have been optimized to get more ROSs, and then to accelerate the
desulfurization microorganisms. And reaction conditions (temperature, oxidation process of SO2 and NOx. For instance, the optimal
pH, etc.) of microorganisms, bioreactor, etc. also affect the microbial temperature and O3 addition are 60–100 ◦ C and MR of [O3]/
activity, and eventually influencing the efficiency of de-SO2 and de-NOx. [NO] = 1.25–1.75, respectively, to generate more free radicals
Though microbial de-SO2 and de-NOx method is currently at the initial (mainly HO•) in O3 oxidation process. For gas–liquid oxidation,
stage (laboratory research to validate the practicability), more attention catalysts are widely employed to promote the cracking of

33
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

Fig. 19. Main chemisorption mechanisms between SO2/NOx and active sites of MOFs [391,406].

Fig. 20. The triple element cycle-based microbial pollutants removal conception (solid line and dash lines represent favorable and unfavorable pathways,
respectively). Modified from [426,427].

oxidants and then generation of ROSs (HO•, SO−4 • and ClO2). are not completely consistent with experimental data. Therefore,
Notably, the temperature and pH of the solution play an essential more sophisticated methods should be explored to verify the
role in the dominant species and concentration of ROSs by reliability and precision simulation, rather than merely experi­
affecting the activity of catalysts. As for gas–solid oxidation, more mental. In addition, oxidants consumption should be reduced
attention has been paid to changing the structure of catalysts (e.g. significantly by available countermeasures when catalytic
introducing dopants into TiO2) to the lower limit of light ab­ oxidation approach is commercialized, to decrease the cost of SO2
sorption and expand the effective light area, thereby producing and NOx removal.
more ROSs. Due to the rapid response of the AOP and the limi­ (2) For catalytic reduction approach, the simultaneous reduction of
tations of measuring instruments, quantum chemical and SO2 and NOx can be also divided into gas–gas, gas–liquid and
numerous mathematical models are put in place to clarify the gas–solid pathways. In addition to the direct reduction by re­
mechanism and process of AOP, although the simulation results ductants, indirect reduction through intermediate products (COS,

34
R. Chen et al. Chemical Engineering Journal 420 (2021) 127588

H2S, etc.) is existed particularly when sulfurized catalysts are interests or personal relationships that could have appeared to influence
used in the gas–gas reduction. The SO2 in the flue gas can be the work reported in this paper.
reduced and then make up for the S element losing during the
catalytic process, which realizes the cycling of S element in cat­ Acknowledgments
alysts. In this way, the presence of SO2 promotes the removal of
NOx. However, nearly no sulfurized catalysts reported can ach­ This work was funded by the National Natural Science Foundation of
ieve high removal efficiency of NOx under laboratory conditions, China (No. 51872096), the Fundamental Research Funds for the Central
not to mention the actual application environment. Therefore, for Universities (No. 2018MS07), and the Tip-top Scientific and Technical
future research, selection of effective reductants and matching Innovative Youth Talents of Guangdong Special Support Program
catalysts are very important, and catalytic reduction experiments (2015TQ01C312). Their financial supports are gratefully
should be carried out in fully consideration of the practical acknowledged.
environment.
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