Trends in NOx Abatement A Reviewscience of The Total Environment

Science of the Total Environment 408 (2010) 3976–3989
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Science of the Total Environment

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s c i t o t e n v
Review
Trends in NOx abatement: A review

Kinga Skalska ⁎, Jacek S. Miller, Stanislaw Ledakowicz
Technical University of Lodz, Faculty of Process and Environmental Engineering, Wolczanska 213/215, 90-924, Lodz, Poland
a r t i c l e i n f o a b s t r a c t
Article history: Implementation of stringent regulations of NOx emission requires the development of new technologies for
Received 25 November 2009 NOx removal from exhaust gases. This article summarizes current state of NOx abatement strategy. Firstly, the
Received in revised form 31 May 2010 influence of NOx on environment and human health is described. The main focus is put on NOx control
Accepted 2 June 2010
methods applied in combustion of fossil fuels in power stations and mobile vehicles, as well as methods used
Available online 26 June 2010
in chemical industry. Furthermore the implementation of ozone and other oxidizing agents in NOx oxidation
is emphasized.
Keywords:
Air pollution
© 2010 Elsevier B.V. All rights reserved.
Nitrogen oxides
Waste gas treatment
Ozone
Emission abatement
Combustion
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3976
1.1. NOx . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3977
1.2. Sources of NOx . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3977
1.3. Environmental impact . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3978
1.4. Complexity of NOx reactions in the atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3978
2. NOx emission abatement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3979
2.1. NOx abatement methods for industrial and general power plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3979
2.1.1. Pre-combustion and combustion modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3980
2.1.2. Post-combustion methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3981
2.2. NOx abatement for car engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3985
2.3. NOx abatement in chemical industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3987
3. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3988
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3988
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3988
1. Introduction which may harm humans, animals, vegetation and material. The main
source of air pollution are the combustion processes of fossil fuels
In recent years environmental awareness of political circles sig- used in power plants, vehicles and other incineration processes. Key
nificantly grew. This can be attributed to social dissatisfaction with the combustion-generated air contaminants are sulfur oxides (principally
state of the environment. As a result more rigorous environmental SO2), particulate matter, carbon monoxide, unburned hydrocarbons
laws are introduced. and nitrogen oxides (NOx). NOx are considered the primary pollutants
Air pollution constitutes one of the major problems in urban areas of the atmosphere, since they are responsible for such environmental
where many sources of air born pollutant are concentrated (Chalou- problems like photochemical smog, acid rain, tropospheric ozone,
lakou et al., 2008). The notion ‘air pollutant’ covers all substances ozone layer depletion and even global warming caused by N2O.
Further to the above they cause many health problems in humans
exposed to high concentrations of these gases.
⁎ Corresponding author. Tel.: +48 42 6313697; fax: +48 42 6313738. In the face of rising restrictions regarding NOx emission, which are
E-mail address: [email protected] (K. Skalska). being imposed by the Gothenburg and Kyoto Protocols, development
0048-9697/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2010.06.001
K. Skalska et al. / Science of the Total Environment 408 (2010) 3976–3989 3977
Table 1
Properties of selected nitrogen oxides.
Properties N2O NO N2O3 NO2 N2O4 N2O5
Color Colorlessa Colorlessa Blacka Red-browna Transparente Whitea

Solubility in water g/dm3 0.111e 0.032e 500.0e 213.0e 213.0e 500.0e
State of matter (ambient temperature) Gas Gas Liquid Gas Liquid Solid
Density (g/dm3) 1.8 1.3402 (293 K)d 1447 (275 K)d 3.4 1492.7 (273 K)d 2050 (288 K)d
IR absorbents peaks (cm− 1) 1276.5d 1876d,f no data 749.7d 808d 722d
2200–2300g 1908g,i 1322.5d 1262d 743c
1600–1596b 1379.6d 824d
1617.75d 1712d 1050d
1632–1629b 1748d 1247c
2891g 1400d
2917g 1413d
2375d
a
Environmental Protection Agency (1999).
b
Mentel et al. (1996).
c
Mogili et al. (2006).
d
Bailar et al. (1973).
e
Dora et al. (2009).
f
Hadjiivanov (2000).
g
Mok and Yoon (2006).
i
Smeets et al. (2007).
of new technologies and improvement of currently used methods are Global shares of NOx anthropogenic sources are similar to those
necessary. Nowadays, the most popular technology is selective cata- observed in Poland. Cited after Elzey et al. (2008) the primary sources
lytic reduction (SCR) with ammonia in the presence of oxygen, used of NOx emission include motor vehicles (55%) and industrial,
mainly to reduce NOx emission from combustion processes (Brügge- commercial combustion processes (45%). Increased combustion of
mann and Keil, 2008). Of course other techniques like absorption, fossil fuels since the last century has been a primary source of NOx,
adsorption or electrical discharge are also widely used (Mok and Lee, leading to the increase of pollutants concentration in the atmosphere.
2006). Nevertheless, all these methods have their limitations and However, other sources of NOx such as the production and use of nitric
disadvantages. Furthermore, restrictions regarding NOx emission, acid should not be neglected. During nitric acid plant operation as well
imposed on some developed countries, are extremely severe. as nitrification and oxidation of organic compounds with the use of
Therefore, researches are being held throughout the world to obtain nitric acid, nitrous gases in varying concentrations are formed (Dyer-
more efficient techniques or to find a better catalyst. Smith and Jenny, 2005).
The objective of this paper is to summarize the current situation in NOx emitted from incineration processes consist in 95% of NO nitric
the field of NOx abatement. In contrast to a wide array of reviews oxide and 5% NO2 nitrogen dioxide (Gomez-Garcia et al., 2005; Van
already available on the subject of NOx abatement (Javed et al., 2007; Durme et al., 2008; Wang et al., 2007). Therefore, nitrogen dioxide
Liu and Woo, 2006; Muzio and Quartucy, 1997; Roy et al., 2009) this formed in the atmosphere through the photochemical oxidation of
paper tries to present a more overall view. Therefore, we do not focus nitric oxide is a secondary pollutant. However, it has been proved that
on one specific source of emission or method used to reduce the for mobile sources of NOx the share of NO2 primary emission might be
amount of emitted NOx. Instead, this review gives an extensive survey variable. Furthermore, it is dependent on the vehicle type, and
of NOx emission control technologies for three major anthropogenic conditions of operation (Carslaw and Beevers, 2004). Kartenbuch et al.
sources of emission, i.e. power plants, vehicles and chemical industry. (2001) performed experiments estimating the amount of primary
Further to the above, this paper presents new and alternative methods NO2 emitted from petrol, diesel vehicles and diesel trucks. They
like hybrid system of SCR and O3 injection, fast SCR, electron beam gas obtained NO2/NOx mix ratio of b0.2 vol.%, 5.9 vol.% and 11.0 vol.% for
treatment, etc. petrol, diesel vehicles and diesel trucks, respectively. Whereas, nitrous
oxide N2O besides being produced in combustion processes of fossil
1.1. NOx fuel and biomass is also emitted from chemical industry activities such
as adipic acid production for Nylon 6.6 and nitric acid manufacture.
Interest in NOx emission has been steadily increasing since 1952, Natural sources of NOx, in spite of not being as crucial as
when the role of nitrogen oxides in the formation of photochemical anthropogenic ones, are still worth listing: oxidation of NH3, lightning,
smog was formulated (Muzio and Quartucy, 1997). Several types of and volcano activities.
nitrogen oxides exist in the environment: N2O, NO, NO2, N2O3, N2O4,
NO3, and N2O5 (Table 1). The abbreviation NOx usually relates to
nitrogen monoxide NO and nitrogen dioxide NO2, which from
photochemical point of view can be called ‘fresh’ nitrogen oxides
since in these forms they reach atmosphere. Another important
nitrogen oxide is N2O and it may be also called ‘fresh’ for the same
reasons.
1.2. Sources of NOx
In 2007 total nitrogen oxides emission in Poland reached 890 Gg, in

terms of NO2 this was 50 Gg more than in 2000 (Central Statistical
Office, 2009). This is principally a product of power plants and vehicles,
Fig. 1. Following the accession to the EU, Poland agreed to reduce the
emission limits of NOx below 200 mg/m3 after 2015 (Dora et al., 2009). Fig. 1. Nitrogen oxides emission in Poland in 2007 (Central Statistical Office, 2009).
3978 K. Skalska et al. / Science of the Total Environment 408 (2010) 3976–3989
1.3. Environmental impact sources, whereas N2O emission can be considered more as a global
problem.
Air pollution has not only acute but also chronic effect on human
health. It has many pathways of entering human body. Primarily, 1.4. Complexity of NOx reactions in the atmosphere
humans get in contact with air pollutants via inhalation and ingestion,
while dermal contact represents a minor route of exposure (Nakatsuji Majority of environmental problems and health hazards is a result
et al., 1999). Air pollution penetrates to water and soil therefore also of various processes occurring in the atmosphere. The array of
to food which is consumed by humans. The impact of air pollution on potential NOx reactions with different compounds present in the
humans can differ. atmosphere (O3, VOC, etc.) is quite complex. Furthermore, in the
Taking NOx into consideration, only nitric oxide and nitrogen presence of sunlight various photochemical reactions are possible.
dioxide are thought to be toxic. Regardless of being the major Additionally, the type of reactions is dependent on the atmosphere
component of NOx, nitric oxide is less toxic than nitrogen dioxide. It layer that is considered, since different species are present at different
causes eye and throat irritation. As most radicals, NO is unstable and heights with various concentrations. What is more, different ranges of
reacts readily with oxygen to form NO2 which even at low doses can solar radiation are observed in thermo-, meso-, strato- and tropo-
be a source of acute lung injury with pneumonitis and fulminant sphere as a result of the ability of different chemical molecules to
pulmonary edema (Woodrow, 1997). Studies focused on risk absorb different wavelengths of radiation. In connection with these
assessment have showed that high outdoor NO2 concentration factors it is extremely important to have at least basic understanding
observed in residential areas contributes to increased respiratory of processes occurring in the atmosphere. It enables us to understand
and cardiovascular diseases and mortality (Chaloulakou et al., 2008). why NOx abatement is such a complex and crucial matter. Further-
Furthermore, NOx are precursors of tropospheric ozone which in fact more, this knowledge could be a source of new ideas for development
is also toxic. of NOx control technologies.
Taking into account the variety of contaminants emitted to the Some reactions which NOx can undergo in the atmosphere are
atmosphere, it is clear that humans are exposed to a mixture of presented here briefly (Fig. 2). In order to understand the chemistry of
pollutants, so it is difficult to precisely describe all health risks atmosphere, it is necessary to begin with the thermosphere and then
involved. Another important matter is the exposure time and dose of move to consecutive parts of the atmosphere. In this zone atoms and
pollutants as well as individual features of a human being. molecules are exposed to solar radiation in entire range of radiation
Further to the above, NOx emission contributes to many environ- frequencies. For instance highly energetic ultraviolet radiation can
mental problems like acid rain, photochemical smog, greenhouse cause dissociation of dinitrogen and dioxygen present in the
effect, etc. NOx and many volatile organic compounds (VOC) are thermosphere to their atoms according to:
considered ground-level ozone precursors (Anon., 1995). Further-
more, the mixture of NOx and VOC in the atmosphere exposed to N2 þ hvðλ≈126nmÞ→2N ð1Þ
sunlight can result in the formation of photochemical smog, whereas
O2 þ hvðλ≈240nmÞ→2O ð2Þ
NO and NO2 together with sulfur dioxide SO2 are the major
contributors to acid rain. Acid rain is likely to generate further
environmental effects like deforestation and soil and water acidifica- In the mesosphere radiation is absorbed by ozone which causes its
tion. It also causes material losses, e.g. destruction of buildings and dissociation to excited states of molecular oxygen and atomic oxygen
monuments, and crop damage (Devahasdin et al., 2003). (marked with *) (Atkinson, 1995; Van Loon and Duffy; 2005):
It is known that N2O is one of the greenhouse gases, besides it
O3 þ hvðλ≈325nmÞ→O⁎2 þ O⁎ ð3Þ
takes part in complex reactions in the stratosphere which can lead to
a depletion of ozone layer (Aneja et al., 2001). As a greenhouse gas it
In the stratosphere higher concentration of ozone can be observed,
absorbs infrared radiation with 270-time higher intensity than
since it is generated via reactions of atomic oxygen generated in
carbon dioxide (CO2) (Wright, 2003). Moreover, it indirectly affects
photolysis, with molecular oxygen. Nowadays we are exposed to the
the ozone layer through photochemical reactions (Ogawa and
hazards connected with the problem of ozone layer depletion, as a
Yoshida, 2005). Unlike NO and NO2, N2O has a long half-life around
result of various reactions in stratosphere which can be catalyzed by
100 to 150 years (Environmental Protection Agency, 1999). How-
radicals included in three categories (Van Loon and Duffy; 2005):
ever, it is not as reactive as NO and NO2. As a result of these traits NO
and NO2 are mainly the problem in close range of its emission • HOx–•H, •OH and HOO•
Fig. 2. Schematics of atmospheric NOx reactions.

• NOx–•NO and •NO2 reactions (11) and (12) are observed and play a significant role in
• ClOx–•Cl and ClO• the formation of photochemical smog (Wu et al., 1973). N2O5 can be
removed from the atmosphere by reaction involving water (Matsu-
Although NO and NO2 are radicals, from now on they will be
moto et al., 2006; Smith et al., 1995; Wu et al., 1973):
referred to as NO and NO2 without indication.
In our deliberations we will consider barely NOx which in lower N2 O5 þ H2 O→2HNO3 ð14Þ
stratosphere dominate in the catalytic decomposition of ozone
(Atkinson, 1995): N2O5 is considered as a reservoir of NOx and it is usually observed
during nighttime.
NO þ O3 →NO2 þ O2 ð4Þ In daytime NO3 undergoes rapid photolysis to NO and O2:
NO2 + O→NO + O2 ð5Þ NO3 þ hv→NO þ O2 ð15Þ

O þ O3 →2O2 ð6Þ or to NO2 and O
NO3 þ hv→NO2 þ O ð16Þ

The UV radiation is absorbed in the stratosphere, where the ozone
concentration is higher, as a result only some part of radiation reaches In daylight the lifetime of NO3 with respect to photolysis is around
the troposphere. It is posited that around 50% of solar radiation 10 s and thus less N2O5 can be formed (Bailey, 2002; Cox and Coker,
reaches the earth surface. 1983). The NO3 radical exists normally in the thermal equilibrium
NO and NO2 have both short lifetimes (around 4 days) in the with NO2 and N2O5 and it can be present in significant concentrations
atmosphere, since they are removed from the troposphere after their at night (Wängberg et al., 1992).
transformation to HNO3. Consequently, the amount of these gases Furthermore, N2O5 itself also absorbs near-ultraviolet radiation
reaching the stratosphere is small. However, some emission of NOx is and is decomposed according to the reaction (Swanson et al., 1984):
present in the stratosphere as a result of aircraft traffic and reactions
of N2O with exited state oxygen according to (Atkinson, 1995; Van N2 O5 þ hvðλb401nmÞ→2NO2 þ O ð17Þ
Loon and Duffy; 2005): Table 2 gives a wide range of reactions basically between NOx, O3
and H2O and their standard reaction enthalpies calculated according
N2 O þ Oð1DÞ→2NOð60%Þ ð7Þ
to Hess's law and based on standard enthalpies of formation according
N2 O þ Oð1DÞ→N2 þ O2 ð40%Þ ð8Þ to the National Institute of Standards and Technology (National
Institute of Standards and Technology, 2009). Even in such a
Further to the above, N2O undergoes photochemical reactions seemingly uncomplicated system the number of possible chemical
under solar UV radiation into N2 (95%) and NO (5%) (Wright, 2003): reactions is significant and that is without taking into consideration
photochemistry. Majority of the reactions shown in Table 2 are
N2 O þ hv→NO þ N ð9Þ exothermic and thus thermodynamically favorable, however there
are other factors like the coefficient of collision probability and
N2 O þ hv→N2 þ O ð10Þ activation energy that determine if the reaction takes place in the
atmosphere.
The nitrous oxide is stable in the troposphere, hence big amounts It should not be forgotten that in the atmosphere more chemical
of this pollutant reach the stratosphere where after reaction (7) in the substances are present, which can react with each other or catalyze
form of NO it can participate in a wide array of reactions with ozone, formation or decomposition of other chemicals. Thereby chemistry of
i.e. reaction (4) and following reactions (Atkinson, 1995; Van Loon the atmosphere is still profoundly studied, especially as this
and Duffy; 2005): knowledge turns out to be useful in the improvement of NOx
NO2 þ O3 →NO3 þ O2 ð11Þ abatement methods. In Sections 2.1.2 and 2.3 a few examples of
implementing this knowledge are described.
NO3 þ NO2 →N2 O5 ð12Þ
2. NOx emission abatement
Reaction (11) is much slower than reaction (4). Reaction (11)
determines the rate of N2O5 formation (Cox and Coker, 1983). As it was shown in Fig. 1, nitrogen oxides are emitted from various
In the aspect of air pollution the most important part of the sources. In this aspect there is a variety of NOx control techniques. First
atmosphere is troposphere, since basically all the pollutants are of all, these methods can be categorized in three groups taking into
emitted to the troposphere and not many of them reach higher layers account the type of NOx emission source:
of the atmosphere in unchanged state. NOx with other pollutants
contribute to the formation of photochemical smog, tropospheric • control methods in power plants,
ozone and acid rains. One of the most important photochemical • car engines,
reactions taking place in the troposphere is the decomposition of • chemical industry.
nitrogen dioxide (Van Loon and Duffy; 2005; Carslaw and Beevers,
2004): Each of these groups has its own preferred methods of NOx
emission control. However, some technologies can find application
NO2 þ hvðλb440nmÞ→NO þ O ð13Þ in NOx emission abatement for all three types of sources of these
pollutants.
Atomic oxygen formed in this reaction can react with oxygen
molecule to form ozone, this is the main root of the tropospheric 2.1. NOx abatement methods for industrial and general power plants
ozone formation (Van Loon and Duffy; 2005). Nitric oxide does not
absorb radiation above 230 nm and it cannot be an initiator of In the case of incineration processes occurring in power stations
photochemical reactions in the polluted lower atmosphere. However, three approaches to abatement of NOx emission are known: pre-
NO2 absorbs radiation from a wide range of frequencies, thus atomic combustion, combustion modification and post-combustion techni-
oxygen can be formed (Bailey, 2002). Also in the troposphere ques which are further characterized in Sections 2.1.1–2.1.2.
Table 2
The possible reactions occurring in the NOx, O3 and H2O system with the calculated standard reaction enthalpies.
Reactions ΔHreaction(kJ/mol) k298 (mol L s) Reactions ΔHreaction(kJ/mol) k298 (mol L s)
O3 + H = O2 + OH − 321.68 4.408 × 1011 NO + O(+ M) = NO2(+ M) − 306.37 1.363 × 1010

O3 + H = O + HO2 − 109.4 4.520 × 108 NO + OH = HNO2 − 206.01 5.450 × 1014
O3 + OH = O2 + HO2 − 179.57 3.991 × 107 O + HNO2 = NO2 + OH − 100.36 5.338 × 105
O3 + H2O = O2 + H2O2 235.27 6.620 × 10− 2 H + HNO2 = HNO + OH − 2.7 3.175 × 10+ 8
O3 + HO2 = 2O2 + OH − 105.77 2.791 × 1015 H + HNO2 = NO2 + H2 − 108.17 1.823 × 108
O3 + N = O2 + NO − 525.06 6.000 × 104 H + HNO2 = NO + H2O − 292.81 2.953 × 1010
O3 + NO = NO2 + O2 − 199.86 1.080 × 107 O3 + HNO2 = O2 + HNO3 − 200.25 3.010 × 102
O3 + NO2 = O2 + NO3 − 104.64 2.103 × 104 HNO3 + O = NO3 + OH − 4.75 1.810 × 104
O3 = O2 + O 106.51 2.023 × 10− 2 HNO3 + H = NO3 + H2 − 12.56 1.836 × 101
O3 + O = 2O2 − 391.85 6.361 × 108 HNO3 + H = NO2 + H2O − 292.42 3.173 × 1010
H + O2 + M = HO2 + M − 215.91 6.690 × 109 HNO3 + NO = NO2 + HNO2 0.39 4.480 × 100
H + H + M = H2 + M − 436 3.354 × 109 HNO3 + OH = NO3 + H2O − 75.38 4.820 × 105
H + H + H2 = H2 + H2 − 436 3.014 × 109 HNO3 + OH = NO2 + H2O2 264.53 4.820 × 105
H + H + H2O = H2 + H2O − 436 6.439 × 1010 HNO3 = NO2 + OH 206.4 1.979 × 10− 16
H + OH + M = H2O + M − 498.82 1.800 × 1011 HNO + O = NO + OH − 219.48 2.290 × 1010
H + O + M = OH + M − 428.19 2.031 × 109 HNO + HNO = N2O + H2O − 358.94 2.710 × 1013
O + O + M = O2 + M − 498.36 3.872 × 108 HNO + H = NO + H2 − 227.29 4.853 × 1011
H2O2 + M = OH + OH + M − 58.13 5.499 × 10− 20 HNO + NO2 = NO + HNO2 − 119.12 2.128 × 107
H2 + O2 = 2OH 77.98 1.529 × 10− 25 HNO + OH = NO + H2O − 290.11 9.055 × 109
OH + H2 = H2O + H − 62.82 4.220 × 106 H + HO2 = OH + OH − 142.11 7.842 × 1011
O + OH = O2 + H − 70.17 2.091 × 1010 NO2 + HO2 = HNO2 + O2 − 111.92 2.200 × 10− 4
O + H2 = OH + H 7.81 5.909 × 103 NO + HO2 = HNO + O2 7.2 4.599 × 10− 2
O + HO2 = O2 + OH − 33.27 2.286 × 109 NO + HO2 = NO2 + OH − 20.29 1.724 × 109
2OH = O + H2O − 70.63 9.884 × 1011 NO + HO2 = HNO3 − 226.69 5.443 × 1013
H + HO2 = H2 + O2 − 220.09 1.250 × 1010 H2O + HO2 = H2O2 + O2 375.85 2.490 × 10− 14
H2O2 + H = HO2 + H2 − 352.02 2.611 × 106 HO2 = H + O2 215.91 4.220 × 10− 23
N + O2 = NO + O2 − 382.39 4.742 × 104 N + NO2 = O + O + N2 − 7.42 1.300 × 10− 4
N + OH = NO + H − 203.38 3.800 × 1010 NO2 + H = NO + OH − 121.82 7.643 × 1010
NO + M = N + O + M 631.57 0.000 NO + NO = O2 + N2 − 180.58 1.388 × 10− 36
N + HO2 = NO + OH − 345.49 7.015 × 103 NO + N2O = NO2 + N2 − 139.24 5.265 × 10− 21
NO + N = N2 + O − 313.79 1.875 × 1010 NO + NO3 = 2NO2 a − 95.22 1.566 × 1010c
a
NO2 + NO3 = NO2 + NO + O2 19.16 2.211 × 105 NO2 + NO3 = N2O5 a − 92.93 8.431 × 108c
NO3 = NO + Oa2 19.16 3.255 × 10− 3 N2O5 = NO2 + NO3 a 92.93 1.159 × 1017b
N2O5 + H2O = 2HNO3 96.22 1.506 × 10− 1
Reference: Wei et al. (2007); a—Wängberg et al. (1992); b—Mok and Nam (2004); c—Atkinson et al. (2004).
2.1.1. Pre-combustion and combustion modification within different parts of the combustion zone (Gomez-Garcia et al.,
Pre-combustion basically means fuel purification in order to reduce 2005; Javed et al., 2007). This can be achieved through the application
the amount of nitrogen or choosing the fuel with low nitrogen content of various technologies presented in Table 3.
like natural gas instead of diesel oil etc. It is well known that fuel type To handle the NOx emission problem low excess air (LEA) is used.
affects the formation of NOx through the amount of fuel bound nitrogen This method can be explained as limiting the excess air flow under 2%,
(Friebel and Köpsel, 1999). The amount of formed NOx increases for such and has been proved to strongly lower the NOx content in exhaust
fuels as methanol, ethanol, natural gas, propane, butane, ultra-low gases (Environmental Protection Agency, 1999). The ultimate level of
nitrogen fuel oil, fuel oil and coal (Latta et al., 1998). Furthermore, excess air is limited by smoke and CO emission in the stack (Javed et
replacement of air in the combustion process by pure oxygen can also al., 2007).
significantly decrease the formation of NOx. Therefore, neither thermal, Low NOx burners (LNBs) are designed to control air and fuel
nor prompt NOx can be formed (Sterner and Turnheim, 2009). The main mixing to achieve staged combustion (Javed et al., 2007). Their special
drawback of this solution is its high cost. Thanks to pre-combustion construction leads to air staging in the incineration process and
methods it is easier to reach the required levels of NOx emission with the enables reduction of fuel NOx formation or decrease of temperature
use of remaining two ways of NOx emission control. therefore reducing the thermal NOx generation (Muzio and Quartucy,
Combustion modification can be simply described as alteration of 1997). These burners provide stable flame with many zones, e.g.
operational conditions in order to decrease the NOx formation. These primary combustion zone, fuel reburning (FR) zone and final
methods became quite common in Poland, since they enabled to fulfill combustion zone (National Energy Technology Laboratory, 2008).
domestic standards of NOx emissions (500–600 mg/m3) (Dora et al., The main advantage of LNBs is the reduction of NOx generation as high
2009). However, they are not sufficient to meet new much more as 30–50% and the easiness of their application in both existing and
rigorous EU emission limits. new furnaces (Ballester et al., 1997). However, this procedure causes
The first tests on reducing NOx emission by means of combustion an increase of carbon content in ashes and greater CO formation
modification were performed in the late 1950s (Muzio and Quartucy, (Gomez-Garcia et al., 2005). Despite this, low NOx burners are one of
1997). In 1959 the influence of O2 level on nitrogen oxides emission as the most popular NOx control technologies (Ballester et al., 1997).
well as fuel type was assessed in Southern California Edison's El Another popular air staging method in which the combustion air
Segundo Generating Station (Muzio and Quartucy, 1997). It is well (10–25%) is injected into furnace above the normal combustion zone
known that main factors influencing the formation of nitrogen oxides is Over Fire Air (OFA) (Javed et al., 2007; Muzio and Quartucy, 1997;
in combustion processes are combustion temperature (the higher the Environmental Protection Agency, 1999). As a result a fuel-rich
temperature the higher the NOx formation), proportion between the primary combustion zone and fuel-lean lower temperature secondary
amount of air and fuel, mixing degree of air, fuel and incineration combustion zone are formed (Javed et al., 2007; Muzio and Quartucy,
products distribution. Hence, the main target of combustion modifi- 1997). This method is frequently used in combination with LNBs
cation techniques is to create oxygen deficient stoichiometric con- (National Energy Technology Laboratory, 2008). The Advanced Over
ditions, reduce flame temperature or to vary the residence time Fire Air technique, which was first employed in Hommond power
Table 3
The comparison of combustion modification techniques.
Technique Description Advantages Disadvantages General NOx

reduction
Low Excess Air (LEA) Reduces oxygen availability Easy modification Low NOx reduction 10–44%a
Useful for retrofit of existing Incomplete burned out (can lead to high levels of
power plantsa CO)a
Burners Out of Service (BOOS) Staged combustion No capital cost Generally restricted to gas or oil-fired combustion 10–70%a
processesa
Useful for retrofit of existing Higher air flow for CO
power plantsa
Over Fire Air (OFA) All fuelsa Can lead to high levels of COa
High capacity cost
Low NOx Burner (LNB) air staged Internal staged combustion Low operating cost Moderately high capacity costs 25–35%a
Low NOx Burner (LNB) flue gas All fuelsa up to 20%a
recirculation
Low NOx Burner (LNB) fuel staged Useful for retrofit of existing 50–60%a
power plantsa
Flue Gas Recirculation (FGR) b 30% flue gas recirculated with air, High NOx reduction potential Moderately high capital cost and operating cost 20–50%a
decreasing temperature for low nitrogen fuels Affects heat transfer and system pressures
High energy consumptiona
Flame instabilitya
Water/Steam Injection Reduces flame temperature Moderate capital cost Efficiency penalty 70–80%b
NOx reduction similar to FGR Fan power higher
Fuel Reburning Inject fuel to react with NOx Moderate cost Extends residence time 50–60 %a
Incomplete combustion
Moderate NOx removal Less appropriate for retrofit of existing power
plantsa
Reference: Environmental Protection Agency (1999), a—Integrated Pollution Prevention and Control (2006), b—Graus and Worrell (2007).
station, is altered OFA. The main difference is that this method same total fuel flow (Muzio and Quartucy, 1997; Latta et al., 1998). As
includes greater percentage of air injected and new burner design a result, flame temperature and O2 content are reduced thereby NOx
(Javed et al., 2007). formation is also decreased (Muzio and Quartucy, 1997). In studies
Another way to limit the formation of NOx is injection of diluents. performed in Southern California Edison in 1976, effectiveness of
For this purpose water, steam or flue gas can be used. The injection of BOOS reached 30% (Muzio and Quartucy, 1997).
water or steam should be placed in close range of the burner flame. In According to the Environmental Protection Agency, the effective-
this way it lowers the flame temperature and decreases oxygen ness of combustion modification technologies depends on the type of
content, thus reducing the formation of thermal NOx (Anon., 1995; the combustion system. In general, they can achieve 30–70% NOx
Latta et al., 1998). reduction, only for gas turbines higher efficiencies can be obtained
Flue Gas Recirculation (FGR) includes injection of small portion of (70–85%) (Environmental Protection Agency, 1999). More detailed
flue gas back to the secondary air stream prior to entering the boiler information concerning this subject can be found in Environmental
(Javed et al., 2007; Muzio and Quartucy, 1997). It reduces NOx Protection Agency Technical Bulletin (1999).
generation by lowering flame temperature (below 1033 K thermal
NOx formation is negligible) and reducing oxygen concentration 2.1.2. Post-combustion methods
(Anon., 1995; Javed et al., 2007; National Energy Technology Post-combustion methods, as the term suggests, are dealing with
Laboratory, 2008, Environmental Protection Agency, 1999). It was nitrogen oxides in exhaust gases from incineration processes. They
reported that with the 20% flue gas recirculation the 30% reduction can be used as alternative or supplementary to combustion modifi-
could be achieved for hard coal as fuel, whereas for gas and oil the cation. In this chapter the abundance of post-combustion methods
reduction ranged from 65% to 80%, for about 25% flue gas recirculation was presented. They have gained a lot of attention, since they can
(Javed et al., 2007). However, the amount of flue gas recirculated provide high NOx emission reduction. However, nowadays it is
cannot be too high, otherwise it will destabilize the burner flame difficult to fulfill the stringent emission requirements using just one
(Latta et al., 1998). strategy.
The principle of the fuel reburning (FR) technique is to inject part We prepared a scheme (Fig. 3) that summarizes all the post-
(typically 10–25%) of the incinerator fuel above the main burners in a combustion methods described in this chapter. First of all, two main
separate reburn zone (National Energy Technology Laboratory, 2008; approaches can be observed when NOx abatement is considered; the
Javed et al., 2007). In this secondary combustion zone the NOx formed first one is NOx removal from flue gas and the second is NOx
in the primary combustion zone is decomposed as a result of destruction. In the case of the first approach, NOx are usually removed
reduction of NOx by hydrocarbons (Javed et al., 2007). Since the in absorption or adsorption processes. The main drawback of these
amount of added fuel is only partially used in reducing NOx the OFA is techniques is transferring the NOx from flue gas to another medium
injected above the reburning zone in order to complete combustion and thus in many cases generating waste which has to be treated then.
(Environmental Protection Agency, 1999; National Energy Technol- The second approach to the problem does not pose such a threat since
ogy Laboratory, 2008). The reburning was first applied to a full scale NOx are usually transformed to benign products. Currently, the most
coal-fired boiler in Japan by Mitsubishi in the 1980s, with a 50% commonly used NOx control method is selective catalytic reduction
reduction of NOx. (SCR) by ammonia, which can provide up to 85% reduction of NOx
Burners Out Of Service (BOOS) is one of fuel staging techniques (Gomez-Garcia et al., 2005; Barman and Philip, 2006; Brüggemann
which is conducted by fuel flow termination at selected burners, and Keil, 2008). The first commercial SCR system began to appear in
whereas the air flow is left unchanged, hence BOOS are flowing air Japan around 1975 (Muzio and Quartucy, 1997). Then in 1985, the
only (Muzio and Quartucy, 1997; Latta et al., 1998). However, the first pilot-scale SCR tests were performed on a coal-fired unit in the
amount of fuel sent to other burners is increased in order to keep the United States (Muzio and Quartucy, 1997). Generally, SCR is
Fig. 3. Schematic presentation of described NOx abatement post-combustion methods.
performed with ammonia in the presence of oxygen. The stoichiom- by law, so NH3 slip is an important issue. Although SCR is the most
etry of this reaction is: popular NOx control method it is not demerit free. The use of a catalyst
is also a source of other problems like limited catalyst life, catalyst
4NO þ 4NH3 þ O2 →4N2 þ 6H2 O ð18Þ poisoning by constituents present in flue gas, catalyst erosion by dust,
etc. (Javed et al., 2007).
The reaction is promoted by a catalyst which enables the reaction Elzey et al. (2008) investigated selective catalytic reduction of NO2
to proceed at low temperatures. There are many types of catalysts with ammonia at 298 K on nanocrystalline sodium Y (NaY), Aldrich
used in SCR and many new ones are being developed. Basically three NaY and nanocrystalline copper Y (CuY) zeolites. Results of the
main groups of catalysts can be distinguished: studies demonstrated that the kinetics of SCR on nanocrystalline NaY
• Supported noble metal catalysts, e.g. Pt/Al2O3 zeolite was 30% faster than the one on Aldrich NaY. Nanocrystalline
• Base metal oxide catalysts, e.g. those containing vanadium CuY zeolite turned out to be a potential catalyst for SCR with ammonia
• Metal ion exchanged zeolites–crystalline silicate, consisting of since it enhanced NOx reduction.
regularly occurring internal pores of molecular dimensions and Xu et al. (2008) studied Ce/TiO2 catalyst for the process of NH3-SCR
framework of linked cages and channels, e.g. Cu-ZSM-5 (Gomez- in the temperature range 423–723 K. TiO2 anatase has been the most
Garcia et al., 2005; Elzey et al., 2008). widely used as the support material for the SCR catalyst since TiO2 has
excellent sulfur tolerance. In these studies it has been proved that Ce/
Depending on the catalyst used the optimal temperature range for TiO2 catalyst is highly active and selective for the NO reduction in
the reaction varies but usually fits 300–800 K (Muzio and Quartucy, temperature range 548–673 K.
1997; Gomez-Garcia et al., 2005). Recently, metal oxides-based One of many SCR modifications is the fast SCR process, which
catalysts are being replaced by zeolites-based catalysts. Special makes available higher NOx removal efficiency than the standard
attention is devoted to Fe-ZSM-5 catalyst used both in NH3-SCR and SCR by using an oxidation catalyst at upstream of the SCR unit
HC-SCR. The reason for that is its high activity, high resistance to SO2 (Irfan et al., 2008). About 50% of NO gets oxidized to NO2 enabling
and H2O under SCR reaction conditions (Qi and Yang, 2005). the volume reduction of SCR catalyst (Irfan et al., 2008). A number
The effectiveness of the SCR is influenced by many factors like of oxidation catalysts have been investigated: Pt-based catalyst,
catalyst type, positioning of the catalyst, distribution of ammonia, etc. metal oxide catalyst without support (MnOx, CuOx, etc.), commer-
It is extremely important to get NH3 perfectly distributed to ensure cial catalyst like V2O5/TiO2 promoted by WO3 and/or MoO3 catalyst
adequate value of NH3/NOx ratio and limiting NH3 slip to the exhaust (Irfan et al., 2008). Irfan et al. (2008) studied applicability of Co3O4
gas (Gomez-Garcia et al., 2005). At low temperatures (b500 K) the based catalyst for this process. Co3O4 turned out to be a very
efficiency of SCR is strongly dependent on initial NO2 concentration in effective oxidation catalyst, up to 76% NO conversion was obtained
exhaust gas stream (Van Durme et al., 2008), while in general NO2 at 573 K. Instead of oxidation catalyst ozone injection can be
constitutes only 5% of NOx present in exhaust gases (Gomez-Garcia et applied to SCR in order to increase NOx removal efficiency. As it
al., 2005; Van Durme et al., 2008). Gomez-Garcia et al. (2005) was reported by Mok and Yoon (2006) the injection of ozone
reported that SCR can remove 60% to 85% of NOx when using 0.6 and increased NOx removal efficiencies from 51, 67, 76, 93% at
0.9 mol NH3 for 1 mol of NOx and leaves 1–5 ppm of unconverted NH3. temperatures 423, 443, 473 and 503 K up to 80, 86, 90 and 97%,
Not only NOx emission but also the emission of ammonia is regulated respectively.
As mentioned above, NH3 usage causes the problem of slip but also Non-thermal plasma, when combined with absorption process,
difficulty of its transport and storage (Gomez-Garcia et al., 2005). can provide NOx removal by absorbing NO2 formed since it is better
These obstacles can be overcome by replacing NH3 with hydrocarbons soluble than NO. Water, hydrogen peroxide or alkaline fluid can be
(HC-SCR). In 1992 Li and Armor proved that selective catalytic used as sorbents (Environmental Protection Agency, 1999). Depend-
reduction can be performed by methane over Co-ZSM-5 as a catalyst ing on the sorbent used different products are obtained. Yamamoto et
(cited after Gomez-Garcia et al., 2005). Other hydrocarbons were also al. used wet scrubbing technique with Na2SO3 solution to form N2
studied for HC-SCR, e.g. methane, ethylene, propane and higher from NOx previously produced by non-thermal plasma (cited after
hydrocarbons. Niu et al. (2006) compared CH4 with C2H4 and C2H2 as Mok et al., 2003).
reductants over Co-HZSM-5 catalyst in a non-thermal plasma reactor. The second combination is the addition of a reducing agent to non-
The best NOx conversion of 95% was obtained for addition of 500 ppm thermal plasma. This is usually performed with the use of a catalyst.
C2H2 at 573 K, whereas for 500 ppm of C2H4 and 1000 ppm of CH4, Practically, this is a better idea since both methods are dry processes
70% and 29% conversion was reached, respectively. (Mok et al., 2003) and the presence of 30% to 50% of NO2 in fuel gas
Another NOx emission abatement method is selective noncatalytic stream greatly enhances the performance of selective catalytic
reduction (SNCR) performed with the use of ammonia, aqueous urea reduction in NOx removal processes (Van Durme et al., 2008).
(Eq. (19)) or cyanuric acid (Gomez-Garcia et al., 2005; Muzio and Furthermore, it is a good technology to reduce NOx at low temperatures
Quartucy, 1997). (Mok and Lee, 2006). Many researches concerning this subject are being
conducted worldwide (Mok et al., 2003; Mok et al., 2004; Rajanikanth
and Rout, 2001). The non-thermal plasma with a catalyst can be
COðNH2 Þ2 þ 2NO þ 1=2O2 ↔2N2 þ CO2 þ 2H2 O ð19Þ
operated in two configurations: positioning the catalyst in the discharge
zone (in-plasma catalysis) or downflow the discharge zone (post-
In contrast to SCR in the case of SNCR higher temperature (1149– plasma catalysis) (Van Durme et al., 2008).
1423 K) is required to enable NOx reduction (Gomez-Garcia et al., Mok et al. (2003) studied the influence of non-thermal plasma
2005). The main drawback of SNCR is its low efficiency from 30% to addition to catalytic removal of nitrogen oxides over V2O5/TiO2 and
75% (Gomez-Garcia et al., 2005). This method appeared first in the Cr2O3/TiO2. The post-plasma catalysis enabled the removal of 80% and
mid 1970s. In 1974 Wendt and Sterling injected NH3 into the post 40% of NOx over V2O5/TiO2 and Cr2O3/TiO2, respectively, whereas
flame gas and observed a reduction of NO (Javed et al., 2007; Muzio without plasma generation only 50% and 10% reduction was achieved.
and Quartucy, 1997). The SNCR is an attractive strategy to reduce NOx Rajanikanth and Rout (2001) studied the in-plasma catalysis
emission due to its simplicity. Owing to a catalyst-free system all process. The corona reactor was packed with dielectric pellets made of
issues connected with the use of the catalyst present in SCR are absent Al2O3, Al2O3 coated with palladium Pd and barium titanate BaTiO3.
in the SNCR. Thus, the capital and operation costs are lower. Further to With BaTiO3 pellets, almost 99% removal of NO was achieved for an
the above, SNCR is easy to install in existing plants and can be applied initial concentration of 265 ppm. According to Oda et al. (1997), not
in all types of stationary-fired equipments (Javed et al., 2007). only catalysts can improve effectiveness of NTP but also injection of
However, with its low effectiveness it needs to be premised with the additives. The addition of hydrocarbons to the flue gas enhanced the
combustion modification techniques or combined with another post- oxidation of NO and thus improved NOx removal efficiency. Although
combustion method. Apart from these difficulties the SNCR can be also NTP is a highly effective technology with moderate operating and
a source of N2O (up to 70–200 ppm) and CO emission (in the case of capital costs, the use of this method bears a risk of ozone emission and
urea injection) (Javed et al., 2007). the formation of by-products like carbon oxide (Van Durme et al.,
One of the combined methods using SNCR can be a hybrid system 2008; Environmental Protection Agency, 1999). Another important
utilizing a urea-based SNCR with downstream SCR which was issue is the influence of temperature on ozone formation in non-
investigated by Krigmont et al. in 1993 (cited after Muzio and thermal plasma since generation of this oxidative agent decreases
Quartucy, 1997). The studies showed that 72 to 91% reduction of NOx with the increase of temperature (Mok et al., 2003). Furthermore, it
can be achieved, which proves that this hybrid system can be as decomposes faster when temperature rises. Non-thermal plasma is a
effective as the single SCR. The advantage of the hybrid system over promising technology not only for NOx control but also for SO2 and
the conventional SCR is the reduction of operational costs, as a result volatile organic compounds (VOC) (Mok et al., 2003; Rajanikanth and
of lower amount of catalyst needed comparing to the single SCR. Rout, 2001; Van Durme et al., 2008).
According to Javed et al. (2007) another SNCR coupling technology Another promising technology is electron beam flue gas treatment,
is combining selective noncatalytic reduction with back-end process mainly because it is one of multipollutants control technologies,
in which the residual NO can be oxidized to NO2 and removed by capable of simultaneous removal of NOx and SO2. It is a fairly new
scrubbing (Javed et al., 2007). They discussed also combination of approach to the problem of NOx emission reduction, since it was
SNCR with reburning, electron beam or radiation, and plasma developed in the early 1980s in Japan. From that time forth this
technology. Lazaroiu et al. (2007) presented an electron beam non- technology has been widely studied all over the world, e.g. in USA,
thermal plasma hybrid system for simultaneous removal of NOx and Germany, Japan, Poland, Bulgaria and China (Chmielewski, 2007).
SO2. In series of experiments the removal up to 98% for SO2 and 80% Soon after the laboratory scale studies conducted at the end of 1980s
for NOx was obtained. in the Institute of Nuclear Chemistry and Technology in Warsaw, the
Besides SCR and SNCR, various methods find application in NOx pilot plant has been constructed in Kawęczyn Power Station
emission reduction. One of them is non-thermal plasma (NTP) (Chmielewski et al., 1992). Thanks to these studies the first industrial
utilizing pulsed corona discharge or dielectric barrier discharge. Two installation located in Electric Power Station “Pomorzany” in Szczecin,
kinds of reactions are possible in non-thermal plasma for NOx north of Poland (Chmielewski et al., 2001) and two others in China
reduction. NOx can be converted into N2 directly by N radicals or were built.
NOx can be oxidized to higher nitrogen oxides by atomic oxygen and In the electron beam process the irradiation of flue gas with fast
O3 (Wang et al., 2007). (300–800 keV) electrons takes place (Basfar et al., 2008). This
Non-thermal plasma alone cannot achieve enough high NOx produces active radicals which react with SO2 and NOx to form nitric
emission abatement, because it cannot reduce NOx to N2 when and sulfuric acids. In the presence of ammonia these acids are
oxygen is present in the exhaust gas (Mok et al., 2003). By itself non- converted to ammonium sulfate (NH4)2SO4 and ammonium sulfate
thermal plasma generates oxygen ions and ozone within the air flow nitrate (NH4)2SO4–2NH4NO3 (Licki et al., 1998). These by-products
and thus the principal action is the oxidation of NO to NO2. can be filtered and used as an agricultural fertilizer (Licki et al., 1998,
Chmielewski et al., 2004, Basfar et al., 2008). As Basfar et al. (2008) light would be possible can broaden the area for photocatalysis
have informed recently, high removal efficiencies of SO2 up to 95% and application. Various approaches have been studied already in order to
NOx up to 85% were obtained. Apart from the lack of waste, the extend the absorption wavelength range (Anpo, 2000; Ishibai et al.,
electron beam flue gas treatment has more advantages, first the 2007). Ishibai et al. (2007) compared four Pt-modified TiO2 photo-
simplification of installation construction and required space reduc- catalysts with a standard version of TiO2 under UV and visible light.
tion. Furthermore, the total cost of simultaneous removal of NOx and The applied modification improved effectiveness under both UV and
SO2 does not exceed the cost of desulfurization in a conventional VIS range. In the case of UV the NOx removal increased from 76% for
installation (Chmielewski et al., 2004). standard TiO2 up to 82% for Pt-modified. Furthermore, under VIS the
Bioprocesses are a relatively new post-combustion control increase was more significant from 9% up to 68%. Wang et al. (2008)
technology. Biological systems can be operated under ambient studied photocatalytic oxidation over Zn–TiO2. The oxidation of NO
temperature (Yang et al., 2007). Biofiltration has been already achieved for Degusa TiO2 powder and Zn–TiO2 were 50% and 70%,
successfully used for removal of odors and volatile organic com- respectively.
pounds (VOC) (Wang et al., 2006; Yang et al., 2007). This method Instead of photocatalytic oxidation ozone injection can be applied
involves passing contaminated gases through biologically active in order to convert NO to NO2. Mok and Lee (2006) used ozone
material. Soil and compost can be used as active material (Barnes et injection followed by absorption process with Na2S as reducing agent
al., 1995). Here, the purification process relies on the activity of for simultaneous removal of NOx and SO2. NOx was first oxidized to
denitrifying organisms. Barnes et al. (1995) investigated feasibility of NO2, while SO2 was hardly affected by ozone injection. Then in an
biofiltration for NOx removal by bacteria indigenous to wood compost. absorber NO2 was reduced to N2 according to reaction (20):
They obtained up to 90% NO removal. In 1997 Nagase et al. studied
biological system exploiting unicellular microalga Dunaliella tertio- 2NO2 þ Na2 S→N2 þ Na2 SO4 ð20Þ
lecta for NOx removal. With NOx concentration from 25 to 500 ppm in
gas flow of 150 ml/min, about 65% of the NOx was removed. Moreover, Whereas SO2 can be removed by Na2S as follows:
in 1998 Nagase et al. obtained a removal of 96% of NOx with the use of
2SO2 þ Na2 S→2S þ Na2 SO4 ð21Þ
D. tertiolecta in a counter-flow type airlift reactor. Yang et al. (2007)
conducted research aimed at evaluation of the effect of various
Through this process 95% removal of NOx and 100% of SO2 was
parameters on NOx removal efficiency. A biofilter filled with medium
obtained.
containing wood chips and compost provided up to 99% NOx removal.
Wang et al. (2007) investigated also the process of simultaneous
Results of these studies indicate that denitrification process is oxygen-
NOx and SO2 removal improved by the ability to remove elementary
inhibited, high concentrations of NOx are better removed and that the
Hg. Mercury is one of the heavy metals emitted from coal-fired power
addition of glucose to the biofilter would significantly enhance
plants, and like with other air pollutants its level of emission is
removal effectiveness.
regulated by law. The studies were performed in temperature range
A biotrickling filter is the effective method for the treatment of gas
from 373 to 673 K, with the use of alkaline solution in a wet scrubber.
with relatively low concentration of pollutants at very large
The obtained removal efficiencies were similar to these achieved by
volumetric flux (Chen and Ma, 2006). A variety of microorganism
Mok and Lee (2006), 97% for NOx and 100% for SO2 while 360 ppm
and also higher plants are known to possess such ability (Barnes et al.,
ozone was added. More than 80% of atomic mercury can be oxidized
1995; Nagase et al., 1998). The abiotic and biological mechanism of
to Hg2+ with 80 ppm ozone added. It is well known that Hg2+ can be
NOx removal was studied by Chen and Ma (2006) in the biotrickling
easily trapped in the wet flue gas desulfurization (Wang et al., 2007).
filter. The results showed that both chemical oxidation and bioni-
Recently, Deshwal et al. (2008) proposed a method for nitric oxide
trification were involved in NOx removal. 64% NOx removal was
removal from fuel gas in a lab-scale bubbling reactor by aqueous
obtained but only 42 to 48% of NOx removal can be assigned to
chlorine dioxide ClO2 scrubbing solution. Here both oxidation and
biological processes. These results were obtained for empty bed
absorption processes are conducted in the wet bubbling reactor by
residence time (EBRT) equal to 6 min. Even though biofiltration is a
means of ClO2. Chlorine dioxide first oxidizes NO to NO2 (Eq. (22))
viable and cost-effective technology, it has two major drawbacks with
which can be then removed by absorption according to Eq. (23):
existing biofilters and biotrickling filters, i.e. uneven distribution of
ingredients and difficulty to control excess of biomass (Wang et al., 5NO þ 2ClO2 þ H2 O→5NO2 þ 2HCl ð22Þ
2006). Wang et al. (2006) applied a rotating drum filter to overcome
these problems. Satisfactory 98% NOx removal was obtained for empty 5NO2 þ ClO2 þ 3H2 O→5HNO3 þ HCl ð23Þ
bed residence time (EBRT) of 65 s, drum-rotating speed of 0.5 rpm
and NO inlet concentration of 529 ppm. ClO2 seems to be a promising additive for NOx removal since 100%
As mentioned already, NO2 can be effectively removed from the NO oxidation and 60% NOx removal efficiency were achieved. What is
exhaust gas by wet techniques. However NO2 constitutes only 5% of more, the products HNO3 and HCl can be easily handled by adjusting
NOx present in the exhaust gas this is why NO has to be first submitted pH. Other wet scrubbing methods for simultaneous removal of NOx
to an oxidation to increase the share of NO2 in the treated gas stream. and SO2 were presented by Long et al. (2008). The kinetics of the
This can be conducted in many different ways through non-thermal process with the use of a novel homogenous catalyst (cobalt
plasma, photocatalytic oxidation and ozone injection, etc. Non- ethylenediamine Co(en)3+ 3 ) was investigated.
thermal plasma has already been discussed in this paper. Photo- Following the need for an effective, environment-friendly and cost-
catalytic oxidation (PCO) employs semiconductors such as SrTiO3, effective NOx removal method, Barman and Philip (2006) proposed an
TiO2, ZnO, ZnS and CdS as photocatalysts, however, TiO2 is the most integrated system for flue gas treatment. The system consisted of
widely used (Devahasdin et al., 2003). PCO dealing with NOx removal photocatalytic and ozone oxidation of NO followed by scrubbing and
from ambient environment has been widely investigated (Devahasdin biological denitrification. The process making use of all of these methods
et al., 2003; Ichiura et al., 2003; Maggos et al., 2007; Wang et al., proved to be highly effective, as well as the one without photocatalytic
2008). Maggos et al. proposed the use of TiO2-containing paint for oxidation. Although ozone demand decreased with the use of photo-
photocatalytic degradation of NOx gases in indoor car parks. TiO2 is catalysis, application of this method requires two additional units thus
chemically activated by UV light (b387 nm) (Devahasdin et al., 2003). the capital and operational costs grow (Barman and Philip, 2006).
This can be considered as a limitation for its application. Introduction In this chapter, already applied and newly proposed solutions to
of TiO2 catalyst modified in such a way that its activation under visible NOx abatement in power plants are described. SCR is a well
established technology for this kind of NOx sources, however in 2004; Takahashi et al., 2007). During the former phase under an
general it is capable of providing 80–90% NOx removal. Even less oxidative or lean-burn atmosphere, NO is oxidized over precious
effective is SNCR which enables a 30–75% NOx reduction. Thus, studies metals to NO2, which combines as nitrates with NOx storage
are conducted around the world to redevelop these methods or find compounds. In this phase hydrocarbons, nitrogen and carbon
better solutions. In Table 4 we present a comparison of alternative monoxide are oxidized into water and carbon dioxide (Roy et al.,
methods. Several promising techniques have been proposed. Some, 2009). In the later stage under stoichiometric or reductive atmo-
like SCR hybrid systems with NTP or O3, turned out to be more sphere (fuel-rich) the stored nitrates ions are released and reduced
effective than the single SCR. However, there are other important to nitrogen through reactions with hydrocarbons, hydrogen and
aspects of NOx control techniques that have to be taken into carbon monoxide (Roy et al., 2009; Takahashi et al., 2007). Usually
consideration, mainly the investment and operational costs, genera- NOx storage materials consist of alkaline–earth metals and alkaline
tion of waste, etc. In the case of SCR, there are several problems with and noble metals such as platinum and rhodium dispersed on the
the application of catalysts and reducing agents. Therefore, the support, e.g. Pt–Ba/Al2O3 (Roy et al., 2009). This method is regarded
combination of NTP or O3 with absorption seems to be a more as one of the leading technologies for NOx control from lean-burn
interesting method. Especially, since it can additionally provide SO2 engines. It is worth noting that in this method no additional reducing
and Hg emission reduction. So far most of post-combustion agent is generally needed (Liu and Woo, 2006). Muncrief et al.
technologies have been performed individually. This approach (2004) studied NSR over Pt/BaO/alumina with the propylene
generates more costs than the application of simultaneous removal injection. They obtained high NOx conversions over wide tempera-
technologies, therefore multiple pollutants removal methods are ture window (473–673 K). Studies conducted by Takahashi et al.
becoming more popular. Especially interesting is the electron beam (1996) on the Pt/Ba/Al2O3 catalyst proved that it could provide 90%
flue gas treatment technology, which is very effective and, what is NOx conversion, whereas Castoldi et al. (2006) proved that the Pt–
more, already applied in a few locations around the world. Ba/Al2O3 NSR catalyst was able to simultaneously remove both soot
and NOx. The NSR system with the Pt catalyst and hydrocarbons
2.2. NOx abatement for car engines worked well for a long period in the absence of SOx, however it
deteriorated quickly in the presence of SOx (Nakatsuji et al., 1999).
In the case of mobile NOx sources EU imposed emission regulation Nakatsuji et al. (1999) managed to surmount this problem by
by the so-called Euro standards. Currently, NOx emissions are limited applying catalytic reduction over Rh/alumina catalyst with periodic
to 150 and 80 mg km− 1 for gasoline engines Euro-3- and Euro-4- two steps, named dual-phase NOx reduction. The operation in
passenger cars, respectively (Heeb et al., 2008). In the case of diesel oxidizing conditions and relatively short operation in reducing
vehicles this limits are about three times higher, 500 and 250 mg km− 1 conditions proved to be effective and resistant to SOx present in
for Euro-3- and Euro-4-diesel passenger cars, respectively (Heeb et al., the flue gas. This was proved by durability tests in the presence of
2008). As a result of the above and different types of pollutants 40 ppm SO2 performed for more than 20 h, in which no deactivation
produced by gasoline and diesel engines, various NOx control of the Rh/alumina catalyst was observed. This method can be
techniques are applied. practically used in vehicles with diesel engines, lean gasoline engines
It appears that for gasoline vehicles a three-way-catalyst (TWC) is and gasoline direct injection (GDI) engines (Nakatsuji et al., 1999). In
the state-of-the-art technology (Bröer and Hammer, 2000) as it is order to solve the sulfur problem, wide array of studies were
capable of simultaneous removal of NO x , CO and Cx Hy. The performed by Toyota researchers (Liu and Woo, 2006). According to
development of TWC began in the 1980s. It appeared as an extension Liu and Woo (2006) Toyota improved sulfur tolerance by adding TiO2
of “two-way catalysis”, capable of removal of incomplete combustion or LiO2 to the alumina support as well as by combining Rh and Pt. In
products, CO and residual hydrocarbons (HC) to simultaneously abate general, the NSR still fails when fuel contains high levels of sulfur
the NOx emission (Roy et al., 2009). The effectiveness of TWC can (Roy et al., 2009), thus other methods like selective catalytic
reach more than 95% (Heeb et al., 2008). The primary reaction in TWC reduction (SCR) gain interest. NSR faces also other problems like
is NO reduction by CO (Roy et al., 2009): thermal deterioration of catalysts. Recently Fanson et al. (2003) and
Yamazaki et al. (2004) proved that addition of iron to the NSR
NO þ CO→1=2N2 þ CO2 ð24Þ catalysts might improve thermal stability. According to Fanson et al.
(2003) addition of iron also improves the long-term stability against
However, it does not remove NOx in the case of diesel and lean- sulfur.
burn gasoline engines, because of high amounts of O2 present in flue Another, however not often applied method to reduce NOx
gases (Brandenberger et al., 2008; Bröer and Hammer, 2000; Liu and emission from fuel-lean or diesel engines is the selective NOx
Woo, 2006; Nakatsuji et al., 1999; Takahashi et al., 2007). Recently recirculation (SNR) which was developed by Daimler-Chrysler in
diesel and lean-burn gasoline engines became more popular around 1994 (Roy et al., 2009). The SNR involves concentration and
the world, as a result of lower fuel consumption than in conventional recirculation of NOx into combustion zone of the engine where they
gasoline engines. By applying excess air, the fuel consumption has are thermally decomposed (Roy et al., 2009).
been lowered up to 30% compared to the stoichiometric combustion In addition to these two methods, namely NSR and SNR, in the
with a simultaneous decrease of CO, HC and CO2 emission (Fanson 1990s also the use of selective catalytic reduction (SCR) for mobile
et al., 2003; Liu and Woo, 2006). In these types of vehicles traditional sources of NOx was proposed. However, as it was mentioned in
TWC is ineffective, since it requires fuel-rich conditions to effectively Section 2.1.2, the SCR faces some serious difficulties like poisoning of
remove NOx. In the last 20 years extensive researches were carried catalysts, distribution of ammonia, ammonia slip, etc. For mobile
out in order to find three-way catalysts that would be active under sources there are even more problems. As Roy et al. (2009) report, the
lean-burn conditions, however without positive results (Fanson et first generation of catalysts applied in vehicles were monoliths made
al., 2003, Yamazaki et al., 2004). The way out turned out to be two of anatase crystalline form of TiO2 supported on V2O5 or WO3. This
technologies proposed in the 1990s, namely the NOx storage type of catalyst was popularized as an industrial catalyst in SCR from
reduction (NSR) and selective NOx recirculation (SNR) (Roy et al., stationary sources. However, its application to mobile sources is
2009). Proposed first by Toyota in the mid 1990s NOx storage and connected with the problem of toxicity of vanadium (Roy et al., 2009).
reduction (NSR) is a promising technology for diesel vehicles Furthermore, at high temperatures (N673 K) this type of catalyst
(Fanson et al., 2003; Muncrief et al., 2004). This process consists of tends to form nitrous oxide (Koebel et al., 2000). For mobile diesel
two stages: oxidative adsorption and reduction (Muncrief et al., engines Fe-ZSM-5 is one of the most suitable catalysts because of its
Table 4
The comparison of alternative NOx control technologies.
Method Conditions Efficiencies (%) Advantages Disadvantages Reference Comments
O3 + SCR T = 443 K Benign products Relatively high energy consumption Mok and V2O5/TiO2
(selective T = 473 K 55 More effective in lower Nam
catalytic T = 503 K 64 temperatures than single (2004) NH3 as a reducing agent
reduction) CNOx = 300 ppm 68 SCR
Flow rate = 5 L/min
503 K 97/93 (without O3) Benign products Relatively high energy consumption Mok and
473 K 90/76 (without O3) Yoon
443 K 86/67 (without O3) Effective in lower (2006)
423 K 80/51 (without O3) temperatures than single
SCR
NTP (non- CO2 = 20% 80/50 (without NTP) Effective in lower Consumes more energy than O3 Mok et al. V2O5/TiO2
thermal T upto 473 K temperatures than single injection (2003)
plasma) + SCR CinNOx = 200– 40/10 (without NTP) SCR Risk of CO, O3 and formaldehyde Cr2O3/TiO2
400 ppm emission
Flow rate: 5 l/min
Cethylene = 750 ppm
HC-SCR + NTP T = 573 K More effective in lower Risk of CO and O3 emission Niu et al. Co-HZSM-5
(plasma over 500 ppm C2H2 95 temperatures than single (2006)
catalyst) 500 ppm C2H4 80 SCR
1000 ppm CH4 30
Electron beam Flow rate = 5 m3/h 85 NOx No wastes High energy consumption Basfar et By-product—(NH4)2SO4–
flue gas T = 673–813 K Useful by-products Exhaust gas should be cleaned off soot al. (2008) 2NH4NO3 can be used as a
treatment formation and other particulates fertilizer
CinNOx ≈ 160 ppm 95 SO2 Easy to control and to
operate
CinSO2 N 1200 ppm
Electron-beam T = 338–343 K 80 NOx No wastes Generation of High energy consumption Lazaroiu Authors used microwaves
NTP Flow rate = 1 m3/h useful by-products et al. to reduced the consumption
(2007) of energy
CinSO2 = 2000 ppm 98 SO2 By-product—(NH4)2SO4–
CinNOx = 750 ppm 2NH4NO3 can be used as a
NH3 in stoichiometric fertilizer
amounts
Biofiltration CinNOx = 100–500μL/L 90 Low operating cost Requires cooling system for exhaust Barnes et
gases al. (1995)
Flow rate = 1 L/min
CNOx = 25–500 ppm 65 Sensible to pollutants load and Nagase et Dunaliella tertiolecta
Flow rate=150 mL/ temperature variations al. (1997)
min
CinNOx = 100 ppm 96 Problem with excess biomass Nagase et Dunaliella tertiolecta
al. (1998) Counter-flow type air-lift
reactor
CinNOx = 200 ppm 99 Low operating cost Applicable for low concentrations of Yang et Medium containing wood
Flow rate = 30 L/min NOx and high volumetric flux al. (2007) chips and compost/
anaerobic conditions
Rotating drum CinNOx = 529 ppm 98 Solves the problem with Wang et
filter Flow rate = 0.8 m3/h excess biomass al. (2006)
Rotation
speed = 0.5 rpm
PCO CinNOx = 3 ppm 76 Pt-modified TiO2 PCO can Tested on very small NOx Ishibai et Standard TiO2 (UV)
(photocatalytic 82 work under visible light concentrations al. (2007) Pt-modified TiO2 (UV)
oxidation) Flow rate = 3 L/min 8 irradiation Standard TiO2 (VIS)
68 Pt-modified TiO2 (VIS)
PCO CinNOx = 90 ppm 70 Additional catalyst Wang et ZnTiO2
Flow rate = 2 L/min al. (2008)
O3 injection with CinNOx = 300 ppm 95 NOx NOx reducted to N2 H2S might be emitted Mok and Na2S as reducing agent
absorption– CinSO2 = 300 ppm Lee
reduction Flow rate: 5 L/min 100 SO2 SO2 is transformed to High energy consumption (2006)
CNa2S = 0.6%(w/w) Na2SO4 non toxic product
T = 298–503 K
O3 injection with 373–673 K Multi-pollutant High energy consumption Wang et Alkaline solution
absorption Flow rate: 1 L/min 97 NOx controlling system al. (2007)
CinNOx = 215 ppm 100 SO2
CinSO2 = 220 ppm N80 Hg
CHg = 50 μg/m3
Absorption CinNOx = 150– 60 Easily handled products Low effectiveness Deshwal Aqueous ClO2
1180 ppm et al.
CinSO2 = 0–1800 ppm (2008)
Flow rate = 45 L/min Multi-pollutant Application of chlorine compounds
T = 318 K controlling system
high activity and durability (Iwasaki et al., 2008). Another serious slip, manipulation, storage and NH3 corrosion (Liu and Woo, 2006).
contraindication for application of the standard SCR in vehicles is the Thus, instead of using NH3 in mobile SCR, the application of urea was
employment of ammonia as a reducing agent linked with NH3 proposed. This was published first by Held et al. in 1990 (Liu and Woo,
2006). The non-toxic urea can be used as a reducing agent, since it 2.3. NOx abatement in chemical industry
releases ammonia under thermal conditions according to:
Approximately 6% of global NOx emission comes from industrial
sources, mainly chemical industry where HNO3 is produced or used
COðNH2 Þ2 þ H2 O→CO2 þ 2NH3 ð25Þ
for nitrification or oxidation of organic compounds, e.g. monosacchar-
ides to oxalic acid (Jethani et al., 1992) and for the production of metal
Additionally, there are other reducing agents formed from urea nitrates (Dyer-Smith and Jenny, 2005). Opposite to exhaust gases
like ˙NH2 radicals or other intermediates (Liu and Woo, 2006). coming from combustion processes, the composition of NOx in
This method is preferred for heavy-duty vehicles, however its chemical flue gases is variable. The mixture of NO and NO2 depends
application in diesel engines results in a complex exhaust after- on acid concentration, the higher the concentration the higher the
treatment system consisting of a diesel oxidation catalyst, NH3 dosing percentage of NO2. Moreover, the volumes of these gases are relatively
unit, SCR catalyst, and NH3 oxidation catalyst (Roy and Baiker, 2009). low but concentration of NOx very high (Dyer-Smith and Jenny, 2005).
According to Brosius et al. (2005), in 2005 DaimlerChrysler commer- Usually absorption in alkali solutions or reduction with the use of
cialized the urea-SCR based post-treatment system for heavy duty hydrogen, methane or ammonia is applied for ‘end of the pipe’ NOx
trucks under the name of BlueTec technology. emission control (Chacuk et al., 2007; Miller et al., 2005). The process
For lean gasoline engines and gasoline direct injection (GDI) of NOx absorption is found to be extremely complex. It is mainly due
engines the method of choice would be probably the selective to numerous species of nitrogen compounds which are involved in
catalytic reduction with hydrocarbons, which are easily available in various reversible and irreversible reactions occurring in this process
fuel. An example of the reaction occurring in this process with (Chacuk et al. 2007; Miller et al., 2005; Thomas and Vanderschuren,
methane is presented below (Nakatsuji et al., 1999): 1997). Further to the above various scrubbing solutions can be used
thus different products are formed. The production of nitrites and
nitrates is the effect of application of alkaline scrubbing solution,
NO þ CH4 þ 3=2O2 →1=2N2 þ CO2 þ 2H2 O ð26Þ whereas in the case of water usage the mixture of nitric and nitrous
oxides is formed (Dyer-Smith and Jenny, 2005). Moreover, the
For HC-SCR NOx technology various hydrocarbons such as composition of products is also dependent on NOx composition in
methane, propane and ethane have been studied. Recently, studies flue gas (Dyer-Smith and Jenny, 2005). The main drawback of the
have been carried out on the use of ethanol as a reducing agent in HC- traditional absorption is disability to obtain flue gas without NOx. The
SCR, which show that it is superior to other hydrocarbons enabling reason for this is that HNO2 formed during absorption, decomposes in
over 90% reduction of NOx for temperature window 623–773 K (cited the presence of strong acids to form nitric acid and nitric oxide
after Tham et al., 2009). according to Eq. (27) (Chacuk et al., 2007; Miller et al., 2005; Thomas
Cu-ZSM-5 was the first catalyst for HC-SCR that showed high NOx and Vanderschuren, 1996, Thomas and Vanderschuren, 1997):
reduction in oxygen-rich conditions (Nakatsuji et al., 1999; Roy et al.,
2009). Since the development of HC-SCR various catalysts have been 3HNO3 →HNO3 þ 2NO þ H2 O ð27Þ
proposed. In general, for NOx reduction from mobile sources, zeolite-
It appears reasonable to introduce an oxidizing agent into the
based catalysts are more popular than the catalysts based on metal
absorption solution as nitrous and nitric acid can be transformed into
oxides. The activity of zeolite-based catalysts depends on the type of
compounds with higher level of nitrogen oxidation (Chacuk et al.,
zeolite, its structure and type of metal ion (Brandenberger et al., 2008;
2007; Miller et al., 2005). Potassium permanganate, sodium chlorite,
Liu and Woo, 2006). These catalysts are not demerit-free, they have
sodium hypochloride, hydrogen peroxide, chlorine dioxide and ozone
poor hydrothermal stability. Okada et al. (1997) compared Cu and Co
can be used for this purpose (Thomas and Vanderschuren, 1996,). At
exchanged zeolite ZSM-5 for propane-SCR. The Co-based catalyst
the threshold of the 21st century, Thomas and Vanderschuren (1996)
turned out to be better in the presence of water vapor.
performed NOx absorption in aqueous and nitric acid solutions
Next improvement to the SCR in mobile sources was introduced by
containing H2O2. In the presence of H2O2 nitrous acid gets oxidized
Toyota Company. They have developed the diesel particulate–NOx
to nitric acid (Eq. (28)), therefore NOx concentration in the outlet gas
reduction system (DPNR) which enables simultaneous removal of
decreases (Thomas and Vanderschuren, 1996, 1997).
soot particulate and NOx (Liu and Woo, 2006).
Certain number of researches in the field of NOx abatement from HNO2 þ H2 O2 →HNO3 þ H2 O ð28Þ
diesel engines was devoted to the application of plasma technologies:
plasma–catalyst with hydrocarbon injection method, plasma–SCR This method is valuable for nitric acid production plants, since the
with urea injection, oil droplet plasma injection system, silent addition of H2O2 to scrubbing solution generates additional amounts
discharge plasma system, corona radical shower system (Okubo et of nitric acid without forming other by-products. In more recent
al., 2008). Tonkyn et al. (2003) achieved a significant reduction of NOx works Miller et al. (2005) and Chacuk et al. (2007) investigated
over broad temperature window by combining atmospheric plasma ozonation of nitrous acid in the nitric acid solution. They concluded
with appropriate catalysts. Another approach with the same effect of that ozone usage made it possible to oxidize the whole amount of
NO oxidation to NO2, that is more energy-efficient than employment nitrous acid present in the solution. An oxidizing agent can also be
of plasma and electron beam, is the ozone injection to the exhaust gas applied directly to a manufacturing process as Dyer-Smith and Jenny
(Roy et al., 2009). In the case of plasma application, energy con- (2005) reported. They compared effectiveness of ozone and hydrogen
sumption is major demerit, since plasma must be always turned on peroxide application during industrial nitrification and oxidation with
during post-treatment (Okubo et al., 2008). Okubo et al. (2008) nitric acid. Both oxidizing agents were used in the copper nitrate
proposed a total diesel emission control system which can give production process. In both cases nitrogen oxides are oxidized to
plasma-assisted non-catalytic diesel particulate and NOx simulta- dinitrogen pentoxide which forms nitric acid through reaction with
neous reduction using ozone injection and plasma desorption. water. Although both O3 and H2O2 proved to be effective in NOx
Recently Song et al. (2009) proposed application of dielectric emission abatement without generating by-products, the application
barrier discharge (DBD) to simultaneously remove NOx, particulate of the former one appeared to be more cost-effective.
matter (PM) and hydrocarbons (HC). For the operating conditions The homogenous process of oxidizing NO to NO2 with ozone
they obtained the maximum PM, HC and NOx removal effectiveness of followed by SCR scrubbing etc. was widely studied (Jaroszyńska-
more than 80%, 75% and 65%, respectively. Wolińska, 2002; Mok and Lee, 2006; Mok and Yoon, 2006; Wang et al.,
2007). However, other researchers have proposed to extend the References

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Science of the Total Environment 408 (2010) 3976–3989

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Science of the Total Environment

Trends in NOx abatement: A review

Properties N2O NO N2O3 NO2 N2O4 N2O5

Color Colorlessa Colorlessa Blacka Red-browna Transparente Whitea

1.2. Sources of NOx

In 2007 total nitrogen oxides emission in Poland reached 890 Gg, in

Fig. 2. Schematics of atmospheric NOx reactions.

NO2 + O→NO + O2 ð5Þ NO3 þ hv→NO þ O2 ð15Þ

O þ O3 →2O2 ð6Þ or to NO2 and O

NO3 þ hv→NO2 þ O ð16Þ

Reactions ΔHreaction(kJ/mol) k298 (mol L s) Reactions ΔHreaction(kJ/mol) k298 (mol L s)

O3 + H = O2 + OH − 321.68 4.408 × 1011 NO + O(+ M) = NO2(+ M) − 306.37 1.363 × 1010

Technique Description Advantages Disadvantages General NOx

Fig. 3. Schematic presentation of described NOx abatement post-combustion methods.

Method Conditions Efﬁciencies (%) Advantages Disadvantages Reference Comments

2007). However, other researchers have proposed to extend the References

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