Critical Reviews in Environmental Science and

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Abatement technologies for high concentrations

of NOx and SO2 removal from exhaust gases: A
review

Yongxia Sun, Ewa Zwolińska & Andrzej G. Chmielewski

To cite this article: Yongxia Sun, Ewa Zwolińska & Andrzej G. Chmielewski (2016) Abatement
technologies for high concentrations of NOx and SO2 removal from exhaust gases: A
review, Critical Reviews in Environmental Science and Technology, 46:2, 119-142, DOI:
10.1080/10643389.2015.1063334

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CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY
2016, VOL. 46, NO. 2, 119
142
http://dx.doi.org/10.1080/10643389.2015.1063334

Abatement technologies for high concentrations of NOx and

SO2 removal from exhaust gases: A review

ska and Andrzej G. Chmielewski
Yongxia Sun, Ewa Zwolin
Institute of Nuclear Chemistry and Technology, Warsaw, Poland

ABSTRACT KEYWORDS
Nitrogen oxides (NOx) and sulfur dioxide (SO2) are the main air Nitrogen oxides; sulfur
pollutants. Both of them are mostly formed during the process dioxide; off gases; control
of fossil fuels combustion, while some processes generate very technologies; review
high concentrations of NOx and SO2. In this review the authors
describe and summarize the currently used methods and the
new techniques that are under investigation. They also give a
detailed description of the regulations and sources of SO2 and
NOx emissions, as well as their impact on human health and the
environment. The authors focus primarily on the environmental
protection technologies used in power plants, vehicles, ships,
and the chemical industry.

1. Introduction
Environmental protection is becoming an important social and economical
issue within modern civilizations. All over the world environmental protection
awareness is increasing, with stricter laws in recent years regulating acceptable
ambient air pollution levels. On the other hand, the number of vehicles, power
plants, and factories in operation are also increasing. As a result, scientists are
developing new cost-effective control technologies to keep clean air, water, and
soil clean without producing and depositing wastes. Thanks to continued tech-
nological developments, new liquid and gaseous effluent purification techniques
are available for use. These technological enhancements can be used to optimize
existing pollutant control methods or in creating an entirely new purification
process.
Energy demand and its consumption are growing annually forcing power plants
to produce more electrical and heat energy, which is connected with larger volumes
of pollution gases (Chmielewski, 2013). This causes the level of air pollution to be
higher, especially in urban areas. Combustion processes of fossil fuels (which takes
place in power plants and vehicles) are the main sources of air pollution, forming

CONTACT Yongxia Sun y.sun@ichtj.waw.pl Institute of Nuclear Chemistry and Technology, Dorodna 16,
03-195 Warsaw, Poland.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/best.
© 2016 Taylor & Francis Group, LLC
120 Y. SUN ET AL.

harmful chemical compounds such as CO2, SO2, NOx, unburned hydrocarbons, and
particulate matter. These compounds are detrimental to human respiratory system
and the environment, causing acid rain, stratospheric ozone depletion, photochemi-
cal smog, and a greenhouse effect. Power plants, based on the combustion of fossil
fuels, are still the most common. In Europe more than 50% of energy is produced as
a result of combustion processes and is not likely to change in the near future
(Chmielewski, 2013).
The concentration of SO2 in off-gases is dependent on the sulfur content in fuels
(Chmielewski and Licki, 2008). Additionally, different forms of nitrogen oxides are
formed during the combustion processes. In different parts of the world there are
large deposits of fuels containing sulfur, which range from 1.5% to even 4%. The
combustion of this fuel results in the production of exhaust gases with high concen-
trations of SO2 and NOx, which significantly exceeds the levels required by the
global regulations. Furthermore, the exhaust gases from nitric acid manufacturing
plants, the high temperature ovens used for heat treating the automotive catalysts
and vehicles also yield high concentrations of NOx (Tsai et al., 2007).
There are many available technologies to remove SO2 and NOx from off-gases.
Some are used commercially and some are still at laboratory level. The most popu-
lar methods used commercially to remove SO2 are flue gas desulfurization pro-
cesses, which work by reacting with lime or limestone (Srivasta and J
ozewicz,
2001). The most widely used technology for NOx removal is selective catalytic
reduction (SCR; P^arvulescu et al., 1998). However, these techniques are limited to
removing low inlet concentrations of harmful off-gases only. Studies of removing
high inlet concentrations of pollutants such as SO2 and NOx are very rare. There is
an urgent need for developing technologies with good removal efficiency for high
inlet concentrations of SO2 and NOx, emitted from diesel engineering, marine
resources and/or industrial processes, to meet the new stricter regulations, espe-
cially in maritime Sulfur Emissions Control Areas.
The aim of this article is to provide a systematic review on the current levels of
control technology that can be used for the abatement of high inlet concentrations
of SO2 and NOx pollutants from waste off-gases. Although some review articles
have been published in recent years describing the level of knowledge and the tech-
nology required in cleaning these two pollutants from exhaust gases (Bell and
Buckingham, n.d.; Karatepe, 2000; Liu et al., 2010; P^arvulescu et al., 1998; Skalska
et al., 2010; Srivasta and J
ozewicz, 2001), but none of the articles highlighted the
methods for cleaning gases with high concentrations of NOx and SO2 neither indi-
vidually nor simultaneously.

1.1 SO2 and NOx

SO2 is a poisonous, colorless gas, which is the product of sulfur and sulfur compo-
nents as a consequence of combustion (Saito, 2004). Sulfur dioxide is one of the
 CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 121

main air pollutants. Sulfur dioxide can be oxidized to SO3, which reacts with water
to form sulfuric acid (H2SO4), which has been associated with acid rain.
Nitrogen oxides that include N2O, NO, N2O3, NO2 N2O4, NO3, and N2O5 exist
in the environment. However, NOx represents two nitrogen oxides: nitrogen mon-
oxide (NO) and nitrogen dioxide (NO2), which are both products of the combus-
tion of fuels that cause air pollution. The NO2/NOx ratio is generally temperature
dependent, with high exhaust temperatures favoring NO formation. The propor-
tion of NO and NO2 in off-gases is 95% and 5%, respectively (Skalska et al., 2010).
At room temperature both NO and NO2 are in a gaseous state. NO is a colorless
gas that is partially soluble in water, although this is negligible. The majority of
NO pollution originates from anthropogenic sources (U.S. Environmental Protec-
tion Agency, 1999) while <10% originates from biogenic sources. Contrastingly,
NO2 is a red-brown gas that is highly soluble in water, meaning that when NO2
reacts with water it becomes nitric acid (HNO3), which is a component of acid
rain.

1.2 Sources and regulations

Between 1990 and 2011 all European countries significantly reduced total sulfur
dioxide (SO2) emissions. The biggest source of SO2 pollution is from energy pro-
duction and distribution (Figure 1), which has been significantly reduced by 76%
from 1990 to 2011 (European Environmental Agency, 2014a). The majority of
European Union (EU) countries are on track to reach the target total SO2 EU emis-
sions limit by 2020, although this does not include Germany, Lithuania, and Esto-
nia who need to further reduce total SO2 emissions to meet future EU emission
targets.
To stop high emission of SO2 worldwide organizations prefer to prevent rather
than solve air pollution problems. This is evident in the International Maritime

Figure 1. Sulfur dioxide emission sources in 2011 in the EU (European Environmental Agency,
2014a).
122 Y. SUN ET AL.

Organization, which decreased the limit of sulfur content in ship fuels for diesel
engines to 3.5% (from 4.5%) (European Union, 2012). This limit will be progres-
sively reduced to 0.5% by 2020. Furthermore, sulfur concentrations in fuels within
Sulfur Emission Control Areas (where for example Baltic and North Sea belong)
was reduced to 1.0% in 2010 and will be further reduced to 0.1% by 2015. How-
ever, the technology required to remove sulfur from fuels is expensive, with alter-
native methods potentially more efficient and cheaper for cleaning sulfur dioxide
from off gases.
In addition, the majority of countries in 2011 have reported reduced NOx emis-
sions in comparison to 1990 (European Environmental Agency, 2014b). Figure 2
shows the percentage contribution of the different sources in NOx emissions in
2011. Road transport is the main NOx emission source (40.5%) and the second is
energy production and distribution (22.5%). However, both sources were signifi-
cantly reduced by 48% from 1990. Most EU countries are on track to reach the
reduced emission limits that come into force in 2020. However, Malta, Estonia,
Bulgaria, Finland, Lithuania, Poland, Slovenia, and Cyprus need to significantly
reduce their heightened NOx emissions to fulfill future EU regulations.

1.3 The impact of SO2 and NOx on health and the environment
Sulfur dioxide mainly penetrates into the human and animal body through the
respiratory system (WBK and Associates, 2003). In the alveoli where gas exchange
takes place SO2 dissolves in the aqueous surfaces present in respiratory system and
convert into sulfite and bisulfite, which are then transported to the body’s cells.
Exposure to SO2 can cause several respiratory diseases. The product of SO2

Figure 2. Nitrogen oxide emission sources in 2011 in the EU (European Environmental Agency,
2014b).
 CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 123

dissolution-sulfite (in high concentrations) is proven as a genotoxic agent and car-

cinogen. Observational studies reveal that long exposure to SO2, especially in pol-
luted urban areas, can even shorten a life span.
Similarly to SO2, nitrogen oxides enter the body via respiratory system, which
causes respiratory pathologies (U.S. Environmental Protection Agency, 1998). After
NOx reacts with ammonia or moisture, it forms nitric acid vapor and penetrates into
the lung tissue. Exposure to NOx can cause emphysema and bronchitis, as well as
aggravate existing cardiac diseases, which potentially lead to premature death.
These toxic gases when adsorbed on small particulate matter (2.5) are very dan-
gerous for humans and animals, as they are deposited in the alveoli and may con-
tain other acid soluble heavy metals.
Both pollutants are components of acid rain (U.S. Environmental Protection
Agency, 1998). SO2 and NOx react in atmosphere with water vapor, oxygen, and
other compounds, resulting in various acidic compounds falling to the earth as
rain. Acid rain causes significant damage to historical monuments or buildings
and nature (e.g., lakes and coniferous forests). Nitrogen oxides also cause the
eutrophication of lakes, which leads to a lower level of oxygen in water and extinc-
tion of aquatic organisms. Both pollutants affect visibility in polluted, urban areas
by blocking the transmission of light. Additionally, in the presence of sunlight
NOx reacts with volatile organic compounds, which results in smog. One of the
oxides represented in the NOx formula-nitrous oxide (N2O) is a greenhouse gas,
which accumulates in the atmosphere and leads to an increase in the earth’s tem-
perature. Furthermore, NOx gases can react in atmosphere with common organic
compounds and the ozone, forming the toxic products such as nitrate radicals,
nitroarenes, and nitrosamines.
Both pollutants are very hazardous to human health and the environment. There-
fore, controlling emission levels is of great importance, with scientists working hard
on the development of new, more efficient methods for the abatement of SO2 and
NOx.

2. Removal methods of high concentration SO2 and NOx in exhaust gases

2.1 Selective catalytic reduction
The most commonly used method of cleaning exhaust gases of NOx is SCR, which
uses ammonia (NH3-SCR), urea, or hydrocarbon (HC-SCR) reductants to convert
NO and NO2 to nitrogen. Ammonia reductants are the most commonly used (Guo
et al., 2012) and the reaction processes are displayed in the following equations:

4NH3 C 4NO C O2 ! 4N2 C 6H2 O (1)

4NH3 C 2NO2 C O2 ! 3N2 C 6H2 O (2)
2NH3 C NO C NO2 ! 2N2 C 3H2 O (3)
124 Y. SUN ET AL.

It is necessary to use a catalyst to stimulate a reaction at lower temperatures

(300
400 C). Previously, this method was used to filter low initial concentrations
of NOx, but scientists have developed new type catalysts with higher efficiency that
enable the use of SCR also to process high concentrations of NOx.
Catalysts are useful for a number of practical applications such as cleaning
exhaust gases from lean burn gasoline and diesel. To be successful the catalysts
must work under large volumes of oxygen (2
10 vol%) and moisture (10
15
vol%). The efficiency of the majority of catalysts linearly decreases with increas-
ing concentrations of H2O and SO2. Furthermore, the temperature range needs
to be wide (400
1000 K) and the hourly velocity spaces need to be bigger than
1 £ 105¢hr¡1 (Ueda et al., 1997).
Modern catalysts are based on nanotechnology. In recent years, the majority
of research has focused on new ideas, which involve nanotubes and nanopar-
ticles in catalyst production. Li et al. (2011) added carbon nanotubes to tradi-
tional catalyst V2O5/TiO2 using sol-gel methods. The results of this study
showed that a removal efficiency of 89% could be achieved with a high NO
inlet concentration of 500 ppm at 300 C. It is 19% higher in comparison to
traditional catalysts without nanotubes. The new catalyst also had higher oxi-
dation efficiency of NO to NO2 and a high resistance to water and sulfur
dioxide.
Additionally experiments using carbon nanotubes in SCR is described by Chen
et al. (2011). Chen et al. impregnated carbon nanotubes with cerium oxide (CeO2)
to enhance the efficiency of NOx removal. Pure CeO2 only achieved 25% removal
efficiency and was not enough to meet current commercial demands. The most
efficient conditions for the removal of NOx using a new CeO2 catalyst was achieved
at a temperature of 353 C, which removed 95% of NOx, with an inlet concentra-
tion of NO being 600 ppm. The authors also noticed that the catalyst could work
in a wide temperature range (250
420 C) and maintain removal efficiency above
70%. Advantageously, this process lowers the potential of N2O by-product
production.
Composeco et al. (2014b) indicated that not only carbon nanotubes can be used,
but also titanic acid nanotubes (TAN) can be used to remove NOx. After adding
vanadium oxide V2O5 and tungsten oxide WO3 to TAN, the efficiency of NO
removal was maintained at 92% at a temperature range of 350
420 C, with an
NO inlet concentration of 500 ppm. This catalyst showed only a slight 10% deacti-
vation resistance to water and sulfur dioxide due to the increased reaction site
competition between NH3 and H2O. Another example of a nanostructured catalyst
synthesized by Composeco et al. (2014a) is V2O5/NTiO2-Al2O3. The authors
obtained TiO2-Al2O3 nanotubes by hydrothermal synthesis of TiO2-Al2O3 nano-
crystals, which was then impregnated with vanadium oxide. The catalyst showed
high activity that reached 96% in a wide temperature range of 300
450 C, with
inlet NO concentration of 500 ppm. At this temperature range the production of
N2O was also low (~15%).
 CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 125

Nanotechnology is a very promising method but it is not the only one in exis-
tence. Researchers are also working hard to examine and optimize current meth-
ods, which are based on traditional solutions. Chen et al. (2010) investigated SCR
on chromium and magnesium mixed oxide catalyst. Results indicated that despite
a low temperature range of 120
220 C the catalytic activity was high. Efficiency
exceeded 98.5% for the initial concentration of NO at 1000 ppm. The oxidation
properties of the catalyst at lower temperatures increased significantly with addi-
tion of chromium, which enable it to oxidize NO to NO2 and increase the SCR
rate. In addition, the catalyst also showed a satisfactory degree of stability and
regeneration. The poisonous properties of SO2 temporarily affected the removal
efficiency of NO (decreased by 15%), although the reversibility of the reaction
means that this process is not permanent.
Bin et al. (2014) studied the zirconium promoting Cu/ZSM-5 catalyst, which is
an enhancement of an existing metal ion exchanged zeolites-crystalline silicate
(e.g., Cu/ZSM-5) catalysts (Skalska et al., 2010). Study results indicated that the
addition of zirconium significantly raised catalyst activity using a wide tempera-
ture range of 167
452 C, while achieving a NOx removal of almost 100% with
a NOx inlet concentration being 1000 ppm. This is a more optimal temperature
range in comparison to reactions without zirconium catalysts (Cu/ZSM-5)
that have a narrower range of 197
404 C and/or when utilizing traditional
V-W/TiO2 catalysts, which require temperatures between 320
450 C. Advanta-
geously, zirconium also has a higher sulfur tolerance and optimizes the NO to
NO2 conversion.
Brandin et al. (2012) suggested an alternative approach by using a two-stage
SCR unit. After the examination of a variety of different commercial catalysts, the
authors found that efficiencies exceeding 98% could be achieved even with NOx
inlet concentrations as extreme as 5000 ppm.
The combination of two methods working together presents one of the best solu-
tions in attaining a highly efficient process. To enhance the removal efficiency of
NO during the SCR process, scientists added nonthermal plasma (produced during
dielectric-barrier discharge) to increase the oxidation of NO to NO2 (Broer and
Hammer, 2000; McAdams et al., 2008; Miessner et al., 2002). McAdams et al. exam-
ined the treatment of exhaust marine diesel gases containing high concentrations of
NOx (1200 and 1800 ppm). Results showed a high removal efficiency of greater than
50%, in optimal conditions that peaked at 90%.
In the developed world the SCR process is the main method for NOx removal
because of its very high efficiency (Guo et al., 2012). New emerging catalysts can
also be useful for cleaning exhaust gases that contain high concentrations of gas-
eous pollutants. However, they have a number of disadvantages such as high costs
of catalysts, ammonia slip and/or corrosion of equipment. Furthermore, catalysts
have a limited life span and can be poisoned by SO2 or H2O. This process is also
not waste free, as a result of the reaction between nitrogen oxides and NH3, urea
or hydrocarbons.
126 Y. SUN ET AL.

2.2 Wet scrubbing

By using the process of absorption wet scrubbing methods can be used for the
removal of SO2 or NOx and/or both pollutants simultaneously. There are a
few types of absorbents used in the process of wet scrubbing, such as NaOH,
Na2SO3, Ca(OH)2, NH4OH, and Mg(OH)2. Absorption is not a very efficient
method because NO is only slightly soluble in water. This means that some
additives are used for oxidation (H2O2, HClO3) complexation (ferrous chelate)
or reduction of the NO (Guo et al., 2012). Current research has aimed to
identify new absorption solutions and new additives that are highly efficient
without high processing costs.
Recently, researches have focused on the simultaneous removal of SO2 and NOx
by absorbing solutions that contain urea (NH2)2CO (Fang et al., 2011; Wei et al.,
2009), which is a low cost reagent comprising other absorbents. In addition, urea
is nontoxic and can be obtained quite easily.
Wei et al. (2009) investigated the effect of NaClO2/(NH2)2CO solution with
an initial concentrations of NO and SO2 being 1000 and 2000 ppm, respec-
tively. Results demonstrated a removal efficiency of greater than 97% for NO
and approximately 75% for SO2 in optimal conditions. Furthermore, Fang
et al. (2011) studied urea solution using different additives such as H2O2,
NaClO, KMnO4, and NaClO2. This absorption solution showed almost 100%
SO2 removal efficiency and a NO removal efficiency of greater than 50% when
initial concentrations of SO2 ranged between 1000 mg/m3 and 3000 mg/m3
and NO was 1250 mg/m3.
Chien and Chu (2000) studied the effectiveness of NaClO2 in isolation when ini-
tial concentrations of SO2 ranged between 500
2000 ppm and NO 300
800 ppm.
Results showed that the simultaneous removal efficiencies of SO2 and NOx during
this process ranged from 88% to 100% and 36% to 72%, respectively.
Studies conducted by Mondal and Chelluboyana (2013) indicated that NaClO
could be used as an efficient low-cost absorbent for pollutant removal. NaClO is
an absorbent as well as an oxidant, which when used in optimal conditions,
resulted in removal efficiencies for SO2 and NO reaching 100% and 92%, respec-
tively. The initial concentrations of pollutants were at high levels of 6340.41 ppm
for SO2 and 816.67 ppm for NO. The removal of SO2 is relatively easy and inde-
pendent to conditions, but the efficiency of NO removal is strictly dependent on
parameters such as temperature, concentration of SO2, or the concentration of
NaClO.
Chlorine dioxide ClO2 was also considered by Deshwal et al. (2008). Similarly to
NaClO, this compound works as an absorbent and an oxidant simultaneously.
Deshwal et al. showed that ClO2 can oxidize 100% of NO and 60% of NOx because
of its high removal efficiency, even with an initial concentration of NO being
1180 ppm. This compound in comparison to others is also a cheaper option that
can work within a wide range of pH.
 CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 127

One of the simplest methods using hydrogen peroxide was examined by Li
e-
mans et al. (2011). They utilized it to oxidize NOx and SO2 to HNO3 and H2SO4 to
absorb them into an acidic solution. The high inlet concentrations of gases were
examined (600
2000 ppm for SO2 and 5000 ppm for NOx) with results showing
high absorption rates for both pollutants.
An alternative method using hexamminecobalt (II) ions as a catalyst and
iodide ions as a cocatalyst were suggested by Long et al. (2005). This tech-
nique was based on the catalytic oxidation of NO and SO2 by Co(NH3)62C
ions, which involved the reduction of Co(III) to Co(II). The scrubbing solu-
tion was aqueous ammonia and the process was further enhanced by UV irra-
diation. As a result, removal efficiencies reached 100% for SO2 and 95% for
NO with a high initial concentration for both pollutants (800
2500 ppm and
250
900 ppm respectively).
A similar method was investigated by Chung and Moon (2013), who used Ag
(II) ions as a product of Ag(I) ions in an electrochemical cell. These ions were then
used to oxidize the NO to NO2, which was absorbed in HNO3 aqueous acid solu-
tion. This process was conducted under optimized conditions with a high concen-
tration of NO (400
1200 ppm) and obtained a 94% and 73% removal efficiency
for NO and NOx respectively.
An alternative method was suggested by Sun et al. (2011) who removed NOx
and SO2 through oxidation using ozone and MnO2 followed by absorption with
pyrolusite slurry. High efficiencies were obtained for SO2 and NOx by 100% and
70%, respectively, for the initial 2000 ppm concentration of SO2 and 750 ppm of
NOx. The advantage of this method is that low-grade and cost effective pyrolusite
slurry can be used, making the process economically beneficial.
Ding et al. (2014) described the method in which ¢OH radicals were produced
from H2O2 over hematite catalysts, before being used to oxidize NO and SO2. The
products of oxidation were absorbed into an ammonia solution. Encouragingly,
high efficiencies for both pollutants were obtained (100% for SO2 and over 80% for
NO) for high inlet concentrations of SO2 and NO being 17,000 and 550 ppm,
respectively.
The advantage of wet scrubbing techniques is that it can be conducted under
low ambient temperatures and is highly adaptable to flue gas load (Guo et al.,
2012). Additionally, the lack of a catalyst means that there is no chance of catalytic
poisoning or deactivation. However, this process produces a high volume of liquid
waste. Fortunately, some of the waste is recyclable but the remaining waste requires
extensive transport and storage. Overall, the use of new compounds and process
modifications make it possible to clean exhaust gases with a high initial concentra-
tion of SO2 and NOx. However, some of the techniques reviewed do not have
enough high removal efficiency to be considered for commercial use. The method
using the electrochemical cell has high removal efficiencies for both pollutants,
although the energy required is high and the absorption of a large amount of com-
pounds is also high.
128 Y. SUN ET AL.

2.3 Adsorption
The process of adsorption is used for cleaning off-gases from NO or SO2 indepen-
dently or simultaneously. This method is dry and is based on waste materials.
Recently numerous publications focused on sorbents that were made from wastes
(Atanes et al., 2011; Dahlan et al., 2009, 2011; Lau et al., 2011, Sumathi et al.,
2010). Atanes et al. studied the SO2 removal efficiency by adsorption onto activated
carbon, which was prepared from waste cork powder. Results indicate that SO2
uptake increased even with the increasing concentration of sulfur dioxide to
10000 ppm, especially when the carbon was chemically activated with potassium
hydroxide (KOH).
De Wilde and Marin (2000) concurrently examined the adsorption efficiency of
SO2 and NOx on Na-g-alumina in a fixed bed plug reactor. The authors found that
high efficiencies could be obtained even with very high inlet concentrations of
pollutants. Similarly Gao et al. (1996) also used a sorbent based on alumina (CuO
supported on alumina) but alternatively in a powder-particle fluidized bed.
Encouragingly, high removal efficiencies were obtained for SO2 and NOx as 80%
and 95%, respectively.
Adsorption is a dry method, which does not generate any liquid wastes (Guo
et al., 2012). In optimized conditions high efficiencies can be achieved when the
inlet concentrations of pollutants are very high. Furthermore, the equipment
required is simple and the operation is convenient to users. However, this tech-
nique comes at a very high financial cost and uses huge equipment.

2.4 Electron beam

The electron beam (EB) is a very promising, new technique that is continu-
ously developing within the environmental protection field (Chmielewski,
2007). It was first demonstrated in Japan in the early 1970s for the process of
desulfurization, and later it was developed to simultaneously remove SO2 and
NOx. In the 1980s and 1990s the EB flue gas treatment method continued to
be developed thanks to an international research effort from the United States,
Japan, Poland, Germany, Bulgaria, and China. After conducting successful lab-
oratory based experiments, two pilot plants, one in Japan (Namba et al., 1995)
and one in Poland, were built in the early 1990s (Chmielewski et al., 1993;
Chmielewski et al., 1995). The industrial installations were then built within
an Electropower Station called “Pomorzany” in Szczecin, in the north of
Poland (Chmielewski et al., 2004) and in Chengdu in China (Doi et al., 2000).
Additional industrial installations were then added in China and Bulgaria
(Kim et al., 2011).
Electron beam flue gas treatment technology is a dry-scrubbing process used for
the removal of SO2 and NOx (Chmielewski, 2007). Flue gas is irradiated with the
EB, causing the fast electrons to interact with molecules existing in gas generating
ions and radicals. The most important species are ¢OH, HO2¢, and O(3P), which
 CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 129

are formed from the radiolysis of air and water vapor. Ammonia is injected
before the irradiation chamber and reacts with NOx and SO2 inside the irradi-
ation chamber under EB irradiation to form the final products (NH4)2SO4 and
NH4NO3, which are collected at the retention chamber to be used as a com-
mercial fertilizer.
During the process of NOx removal, the reactions mainly go through oxidation
pathway. The most important reactions of the oxidation of NO to NO2 are the fol-
lowing (M€atzing and Paur, 1992):


NO C O 3 P C M ! NO2 C M ðM is a third body in the reaction systemÞ
(4)


O P C O2 C M ! O3 C M
3
(5)
NO C O3 C M ! NO2 C O2 C M (6)
NO C HO2 ¢ C M ! NO2 C ¢OH C M (7)

NO2 reacts with ¢OH to form nitric acid HNO3:

NO2 C ¢OH C M ! HNO3 C M (8)

In the presence of ammonia, the by-product is formed:

HNO3 C NH3 ! NH4 NO3 (9)

The removal of SO2 can also go through different pathways, including radio-
thermal reactions as shown in reaction 10 (Tokunaga and Suzuki, 1984):

SO2 C ¢OH C M ! HSO3 C M (10)

The by-product is then created according to reactions 11
13:

HSO3 C O2 ! SO3 C HO2 (11)

SO3 C H2 O ! H2 SO4 (12)
H2 SO4 C 2 NH3 ! ðNH4 Þ2 SO4 (13)

Some thermal reactions (14, 15) also occur:

SO2 C 2 NH3 ! ðNH3 Þ2 SO2 (14)

ðNH3 Þ2 SO2 C 1 6 2 O2 C H2 O ! ðNH4 Þ2 SO4 (15)

The majority of research based on EB flue gas treatment technology was con-
ducted with relatively low initial concentrations of SO2 and NOx. However, in
recent years scientists have attempted to optimize the process to make it possible
to clean exhaust gases with higher concentrations.
130 Y. SUN ET AL.

Figure 3. Dependence of NOx removal efficiency on dose during EB irradiation (Chmielewski et al.,
2012a).

Removal of SO2 is significantly easier than NO, as it requires much less energy
(i.e., lower dose) than NOx removal. The removal efficiency of both pollutants
can be increased with the optimization of the EB process, as demonstrated in the
recent literature (Basfar et al., 2008; Chmielewski et al., 2012a; Chmielewski
et al., 2012b; Chmielewski et al., 2002; Kikuchi and Pelovski, 2009; Lakshmipa-
thiraj et al., 2013; Licki et al., 2002; Namba et al., 1998; Polyanskii et al., 2012;
Radoiu et al., 2003). The first optimization step was to increase the EB dose
(Figure 3). Previous publications investigated the optimal EB dose for obtaining a
higher removal efficiency of NO and SO2 pollutants. However, a higher dose is
required to remove NO successfully in comparison to SO2. As a result dose rate
was also examined (Chmielewski et al., 2012a), it shows that a lower dose rate is
more efficient in the removal of NO (Figure 4). Basfar et al. studied the influence
of temperature and found that NO removal efficiency increases, but SO2
decreases with an increase in temperature. Previous results also showed that an
increase in humidity also enhances the process (Basfar et al., 2008; Licki et al.,
2002). Furthermore, Calinescu et al. (2013) proved that the presence of fine water
droplets increases the efficiency of SO2 and NOx removal because of the higher
density of the reaction medium. In addition, increasing in SO2 concentration in
exhaust gases concurrently increases NO removal efficiency (Figure 5). To further
improve the process, Chmielewski et al. (2002) suggested using scavengers such
as ammonia and/or alcohol (Figure 6). After the consideration and optimization
of all of these conditions it is possible to achieve high removal efficiencies for
both NO and SO2 pollutants.
Exhaust gases from different fuels with high sulfur concentrations have been
examined. Namba et al. (1998) worked on lignite-burning flue gases that contained
 CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 131

Figure 4. Dose rate influence on removal efficiency of NOx (Chmielewski et al., 2012a).

4800 ppm of sulfur dioxide. In optimal conditions the removal efficiency of

SO2 achieved 97% in 70 C. On the other hand Basfar et al. (2008) worked on
exhaust gases produced from the combustion of a variety of heavy fuel oils
from Saudi Arabia. Results indicated that 98% removal efficiency could be
achieved when the concentration of sulfur dioxide was above 1200 ppm. As
previously mentioned, a commercial scale plant for SO2 and NOx removal had
been operated in Chengdu in China. The inlet concentration of SO2 within
the process vessel was 1800 ppm and the removal efficiency was above 80%
(Doi et al., 2000). Furthermore, the quality of the by-product (which is used
as a fertilizer) was examined by Kikuchi and Pelovski (2009). The authors

Figure 5. Dependence of NOx removal efficiency on SO2 concentration (Chmielewski et al., 2012a).
132 Y. SUN ET AL.

Figure 6. Removal efficiency of NOx in the presence of scavengers (Chmielewski et al., 2002).

found that a good quality fertilizer was produced after cleaning the exhaust
gases generated from the combustion of lignite.
Combining the EB with microwaves can also enhance the efficiency of EB flue
gas treatment. Many researchers in recent years focused their experiments on the
examination of this process (Ighigeanu et al., 2005; Kwon and Han, 2010; Mani-
vannan et al., 2014; Radoiu et al., 1998; Radoiu et al., 2003; Zimek et al., 1995).
Microwave irradiation without the EB was also investigated (Ighigeanu et al., 2005;
Manivannan et al., 2014; Radoiu et al., 2003). In all these studies the removal effi-
ciencies of SO2 was high although the removal of NOx was a complicated process.
In addition, Ighigeanu et al. and Radoiu et al. (2003) found that the concentration
of NO increased rather than decreased when the low dose of microwave irradiation
was used. All authors agree that microwave irradiation has a positive effect on the
removal efficiency of pollutants in high concentrations, when using the EB simul-
taneously. In comparison, using EB treatment alone requires double dose (up to 40
kGy) to achieve the same removal efficiency (Ighigeanu et al., 2005). This high-
lights the energy savings that can be achieved by using both methods in
combination.

2.5 Corona, dielectric barrier, and radiofrequency discharge methods

The removal of high concentrations of NOx was also studied using nonthermal
plasma generated by pulsed corona discharge, dielectric barrier discharge (DBD)
and radiofrequency discharge.
Pulsed corona discharge is generated when fast-rising, narrow high voltage
pulses are applied to nonuniform electrode geometry (Mok and Ham, 1998). Dur-
ing this process high-energy electrons (5
10 eV) are produced. The removal of
NO and SO2 by pulsed corona discharge can be divided into three stages. In the
 CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 133

first stage, radicals are formed because of a direct electron dissociation impact with
neutral molecules. The second stage involves rapid reactions between excited oxy-
gen atoms and background molecules, which create additional radicals. In the final
stage molecules of NO and SO2 react with radicals, which conduct to remove these
pollutants. The main reactions that occur during this process are the following
(Mok and Nam, 2002; Vinogradov et al., 2008).

NO C O3 ! NO2 C O2 (16)
NO C HO2 ! NO2 C OH (17)
NO C O C M ! NO2 C M (18)
NO2 C OH ! HNO3 (19)
SO2 C O ! SO3 (20)
SO2 C OH ! HSO3 (21)
HSO3 C OH ! H2 SO4 (22)
HSO3 C O2 ! SO3 C HO2 (23)
SO3 C H2 O ! H2 SO4 (24)

Similarly to the EB method the corona discharge process can be optimized

to achieve higher removal efficiency of SO2 and NOx. Wu et al. (1998) studied
the removal of high concentration of SO2 (2000
2400 ppm) using the corona
discharge process. Results indicated that by introducing some modifications
(e.g., reducing the stray inductance and/or by regulating the relative humidity)
the removal efficiency of SO2 could be increased to 75
80%. Dors et al.
(1998) studied removal of NOx by DC and pulsed corona discharges in a wet
electrostatic precipitator model, they found that positive corona discharge pro-
cess is more efficient than the negative corona discharge processing for
removal of NO2 and NOx, about 62% NO2 and 42% NOx were removed by
positive corona discharge process. Vinogradov et al. (2008) demonstrated that
a removal efficiency of SO2 and NOx over 80% could be achieved with some
geometric and electrical modifications to the reactor. Moreover, Wang et al.
(2005) discovered that using fly ash could further enhance the process of
removal for both pollutants. Results showed that the addition of water vapor
causes a synergistic effect with the fly ash, which improves the removal of NO
by 5
15%. However, the majority of articles highlighted that the energy con-
sumption during this process is very high and that the corona discharge
method needs further improvement and optimization to become a viable
method for industrial applications.
DBD is a process that uses a current acting between two metal electrodes with
one or more insulating layers (Kogelschatz et al., 1997). During DBD electrons
with energy between 1 and 10 eV are produced and then exposed to the NO in
exhaust gases to convert NO to NO2. The addition of ammonia is then used to cre-
ate NH4NO3 to remove NO permanently. The main reactions that occur during
134 Y. SUN ET AL.

this process without the presence of oxygen are the following (Yamamoto et al.,
2004):

NH3 C e ! NH2 C H C e (25)

NH3 C OH ! NH2 C H2 O (26)
NH2 C NO ! N2 H C OH (27)
N2 H C OH ! HO2 C N2 (28)
HO2 C NO ! HNO3 (29)

HNO3 reacts with NH3 to form NH4NO3, which was described in reaction 9.
If oxygen is present in the exhaust gases, the removal of NO occurs in the path-
way shown (Yamamoto et al., 2004);

NH2 C O2 ! HNO C OH (30)

NH2 C O ! NH C OH (31)
Ox C NO ! NO2 C Ox ¡ 1 ðx D 1 ¡ 3Þ (32)

However, NO is also reproduced in the reaction between ammonia radicals and

oxygen (Yamamoto et al., 2004):

NH2 C O2 ! NO C H2 O (33)
NO2 C O ! NO C O2 (34)

Rajanikanth and Rout (2001) worked on the NO removal from exhaust gases
with a variety of contents within the NO pollutant (350, 540, and 914 ppm) using
DBD. The authors found that the removal efficiency decreased with the increasing
concentrations of NO, reaching 77% for 350 ppm, 62% for 540 ppm, and 45% for
914 ppm. The authors recommended that the process could be enhanced by a cata-
lyst, but experiments supporting this recommendation were conducted only with
low initial concentrations of NO. Yamamoto et al. (2004) described an alternative
process based on the DBD method. Only ammonia gas was exposed to DBD to
produce radicals, which were mixed with the exhaust gas containing NO to initiate
a removal reaction. The removal efficiencies varied, ranging between 80% and
100% in temperatures over 500 C with an initial concentration of NO being 1000
and 3000 ppm, respectively. Moscosa-Santillan et al. (2008) designed DBD wire-
cylinder reactor and examined only the conversion of NO to NO2. Promisingly, a
high NO2 yield conversion rate was also achieved for high inlet concentration of
NO that reached 1000 ppm. However, similarly to corona discharge based methods
the consumption of energy is high, thus increasing process costs.
The new method of radiofrequency discharge has recently emerged to reduce
NO to N2 (Tsai et al., 2007). This appears to be superior to other methods based
on nonthermal plasma, where nitrogen oxides are converted to NO2 and HNO3
 CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 135

before being removed in wet scrubbers.

NO C N2 ! N2 C N C O (35)
NO C N ! N2 C O (36)

Investigations by Tsai et al. (2007) found that even very high concentrations of
NO (2000
10000 ppm) can be removed with very high removal efficiencies that
reached 97.2%. Moreover, Tsai et al. (2008) discovered that the addition of ethyl-
ene to the exhaust gas enhanced the reduction and the conversion efficiency that
reached up to 99.6%. However, the radiofrequency-based method is still not a
practical solution in comparison to other technologies because of its lower operat-
ing pressure and also lower energy efficiency.

2.6 Electrochemical-catalytic cells

Electrochemical-catalytic cells (ECCs) technology is a new technology that enables
the removal of NOx without using any reductant. This process involves reactions
of direct decomposition of NO and NO2 (Huang and Wu, 2011).

2NO ! N2 C O2 (37)
2NO2 ! 2NO C O2 (38)

Pure hydrogen (H2) is used as an anode gas and is needed to create the differ-
ence in reducing and oxidising potentials between the anode and the cathode,
which results in self-generated voltage (Huang and Wu, 2011). Oxygen (O2) is
used as a cathode gas and is an oxidant that takes part in the mechanism of decom-
position of NOx.
Treatment of high inlet concentrations of NOx was examined in a variety of
conditions so as to optimize the process of removal. Huang and Wang (2011)
showed that even for very high inlet concentrations of NOx (e.g., 3000 ppm) the
NO conversion was high, in accordance with the rule stipulating that higher NOx
concentrations result in the high NO conversion (this rule is only true for high
NOx concentration ranges). Another advantage of ECC technology is its ability to
also remove hydrocarbons, carbon oxide (CO), and particulate matter (Huang
et al., 2011). Huang et al. (2013) suggested that this process can be optimized fur-
ther by an addition of CO2 and H2O.
ECC technology is in the earliest stage of development and still requires signifi-
cant optimization and research. However, this is a promising method that is espe-
cially viable for use in automobiles. The biggest advantage of this process is that
the reductant is not consumed during the ECC processes, while its ability to
remove high concentrations of NOx is also clearly advantageous to the commercial
sector.
136 Y. SUN ET AL.

3. Summary
In conclusion, previous articles demonstrate that researchers on a global scale
are focusing their research to optimize and develop new and current technolo-
gies that treat flue gases containing NOx and SO2 in high concentrations.
Table 1 shows a comparison of the current stage of technologies in develop-
ment. There are two ways to obtain a successful method for the abatement of
these pollutants. One is to improve existing and currently working technolo-
gies in power plants, industry and automobiles; the other is to create an
entirely new method based on our current knowledge in the field of environ-
mental protection science in combination with current and future technologi-
cal innovations.
Recent advancements in nanotechnology have enabled researchers to create
new, more efficient catalysts for the SCR process, which was previously not
possible. Optimizing methods based on nonthermal plasma (EB, corona dis-
charge, DBD, and radiofrequency discharge) can significantly improve their
ability to work with exhaust gases with high concentrations of SO2 and NOx.
They are very promising methods, because no waste is produced, while the
by-products can be used as fertilizers. Efforts to create new technological
innovations are underway, which could be based on the wastes from other
processes, such as methods using adsorption processes. Furthermore, research-
ers continue to focus on the development of new methods, which can remove
both pollutants simultaneously. The latter presents a cost-effective option,
which is economically justified as the costs for utilizing two installations for
cleaning every pollutant separately are decreased to only one and runs concur-
rently. A very encouraging idea is the combination of methods to achieve
higher efficiency of removal, such as connecting the EB with microwave
irradiation.
However, further research and development is still needed to address existing
problems. In a world where the global energy consumption continues to
increase, some current methods need to address the problem of high waste pro-
duction by developing means to reducing it and/or recycle it. Costs of reagents,
energy, and installations should also be reduced and optimized in accordance
with process modifications that aim to find the most ideal conditions for
removal reactions to occur. The cooperation between different pathways within
environmental protection science (e.g., nanotechnology, material engineering,
and chemical engineering) should be intensified to create more suitable materi-
als and installations, which could be useful for the efficient cleaning of high
concentrations of SO2 and NOx from exhaust gases. As a result it is hoped that
successful, sustainable, and environmentally friendly methods will emerge and
be suitable for a wide range of commercial sectors, such as power plants, heavy
industry, and/or vehicles.
Table 1. A comparison of all methods used for the abatement of high concentrations of SO2 and NOx.
Highest concentration
Method successfully treated Efficiencies Advantages Disadvantages Ref.

Selective catalytic reduction NO 5,000 ppm 89
100% High efficiencies High costs of catalysts Ammonia Brandin et al. (2012)
slipCorrosion of equipment
Limited life span of
catalystLarge amount of wastes
Wet scrubbing NO 5,000 ppm 36
100% Conduct in ambient temperature High volume of liquid wastes Li
emans et al. (2011)
SO2 17,000 ppm 75
100% Highly adaptable to flue gas load Lower efficiencies Ding et al. (2014)
Adsorption NO 4,000 ppm Up to 95% Dry methodNot generate liquid wastes High costs of investment Huge De Wilde and Marin (2000); Atanes et al. (2011)
SO2 10,000 ppm Up to 80% High efficiencies Simple equipment equipment
Electron beam NO 1,000 ppm Up to 80% Dry methodNo wastes Useful by- High costs of energy Chmielewski et al. (2012a); Namba et al. (1995)
SO2 4,800 ppm Up to 98% product
Corona discharge NO 620 ppm Up to 42% Dry methodNo wastes Useful by- High costs of energy Vinogradov et al. (2008); Wu et al. (1998)
SO2 2,400 ppm Up to 80% product
Dielectric barrier discharge NO 3,000 ppm 80
100% Dry method No wastesUseful by- High costs of energy Yamamoto et al. (2004)
product
Radiofrequency discharge NO 10,000 ppm Up to 99.6% Dry methodNo wastes High costs of energy Low energy Tsai et al. (2007)
efficiency Low operating
pressure
Electrochemical catalytic cells NO 3,000 ppm Up to 70% Not consuming any reductant In earliest stage of development— Huang and Wang (2011)
still lots of mechanisms
unknown
CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY
137
138 Y. SUN ET AL.

Funding
This work was partly financed by Institute of Nuclear Chemistry and Technology, in the
frame of Ministerial statutory funding, task 4.4, and co-financed project Nr W141/7. PR
UE/2014 “Zastosowanie wi azki
˛ elektron
ow w przemy
sle i ochronie
srodowiska,” akronim:
EuCARD-2, in a framework 7. PR EuCARD-2, WP4 Applications of Accelerators.

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