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Department of Materials and Life Sciences, SeiKei University, Kichijoji, Musashino, Tokyo 180-8633, Japan
Photocatalysis International Research Center, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
c
JFE Engineering Corporation, Research Centre, 2-1 Suehiro, Tsurumi-ku, Yokohama 230-8611, Japan
b
h i g h l i g h t s
The NO reduction is predominant in the absence of O2 under EB processing.
The O2 presence in the gas stream increases the NO2 formation during EB operation.
The moisture content in the stimulated gas found to inhibit the NO2 formation.
The Na2SO3 scrubbing of the gas during EB operation increases the NOx removal.
The NO and NOx concentration is reduced to the extent of 95% using reactor type II.
a r t i c l e
i n f o
Article history:
Received 31 January 2013
Received in revised form 7 June 2013
Accepted 10 June 2013
Available online 19 June 2013
Keywords:
Electron beam
NO
NOx
Reduction
Pollution control
a b s t r a c t
The NOx removal from gas stream by electron beam (EB) technique under ow through condition was
investigated using two different reactors. Initially reactor type I was fabricated to investigate the NOx
removal performance, based on its performance, the reactor type II was designed for further investigation
on NOx removal efciency. The inuence of the applied current, O2, water vapour and gas ow rate on the
removal of NO and NOx was studied. The FTIR spectrum of the NO gas samples acquired after EB irradiation indicated the formation of NO2 and N2O. It was observed that the NOx concentration could be
reduced to 95% from the initial NO concentration of 1000 ppm using reactor type II. The possible removal
mechanism of NOx under EB irradiation is discussed. It is inferred that the EB irradiation accelerate the
reduction of NO to N2 and O2 in the absence of O2. Addition of O2 and water vapour in the NO/N2 gas
stream was found to inuence the oxidation and reduction reaction, respectively under EB irradiation.
The Na2SO3 scrubbing of the gas increased the NOx removal performance during EB processing. The
N2O was observed to form mainly by the reduction of NO2 during EB irradiation.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Nitrogen oxides (NOx), are considered as one of the primary pollutants in the atmosphere. Their emissions into atmosphere not
only cause the formation of acid rain and ozone depletion, but also
adverse effect to human health [1]. The term NOx used to denote
both nitrogen monoxide (NO) and nitrogen dioxide (NO2). In the
recent decades, abatement of NOx from the combustion processes
has become one of national priorities and greatest challenges in
environmental protection. Though the efforts have been made to
control the NOx emission from the combustion process, post com-
Corresponding authors. Tel.: +81 422 37 3750; fax: +81 422 37 3871 (T. Kojima),
tel./fax: +81 422 37 3887 (A. Yamasaki).
E-mail addresses: akihiro@st.seikei.ac.jp (A. Yamasaki), kojima@st.seikei.ac.jp,
kojimaseikei@gmail.com (T. Kojima).
1385-8947/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.06.019
bustion NOx control techniques are mandatory to meet the stringent emission standards.
The most widely studied NOx control technique is selective catalytic reduction (SCR) with ammonia in the presence of oxygen, in
which the NOx could be reduced to 85% [25]. The SCR reaction is
promoted by the catalyst which enables the reaction to proceed at
low temperature. Nevertheless, the catalyst life time, catalyst poisoning and corrosion are common problems encountered in the
SCR technique [2]. The other conventional NOx control method is
selective noncatalytic reduction (SNCR) performed with ammonia
or cyanuric acid [5,6,2]. The high temperature window (982
1149 C) is necessary to operate the SNCR process, which limits
its application for the treatment of the diesel engine exhaust at
atmospheric pressure conditions. Similarly, the methods include
catalytic decomposition [7], adsorption [8,9], ion-exchanged zeolites [10,11], etc., have suffered with their limitations and
disadvantages.
345
346
EB reactor
Anode: CNT
NO standard gas, (1000 ppm)
N2 as Base gas
Cathode: Ti foil
Reactor type
Gas exit
FTIR analyser
O2 gas (99.99%)
Water gas at 20 oC
Moisture trap
Na2SO3 solution (3% w/v)
Flow rate: 1 cc/min
Electron beam
Gas inlet
NO,N2,O2,H2O
Electron beam
Gas inlet
NO,N2,O2,H2O
Gas outlet
Na2SO3
Circulation
Gas outlet
Reactor type I
Reactor type II
Fig. 1. Schematic diagram of EB reactor set up and the reactor type I and reactor type II used for NOx removal performance.
N2 e ! 2N e
The N atom is the most important reducing species in the absence of additives thus, promote mainly the reduction of NO to
N2 and O2 in the EB and discharge processing [23]. It was observed
from the Fig. 3a that around 370 ppm of NO is unaccounted after
EB processing. This is around 74% of total NO removal of
500 ppm. The unaccounted NO attributed to convert as N2 by the
N atom reduction on NO molecule. It is expressed as
Fig. 2. FTIR spectra of NO, NO2 and N2O standard gases.
N NO ! N2 O
347
3.1.2. Effect of O2
To study the effect of O2 as in the real diesel combustion exhaust on NO removal during EB processing, the gas ow was stimulated by mixing dry O2 in the N2 gas stream. The stimulated gas
that contains the composition of 1000 ppm of NO in 90.9% N2
and 9.1% O2 with the ow rate of 6.6 L/h was subjected to investigate the removal performance of NO under EB irradiation using
reactor type I. The inuence of the O2 was investigated under different EB dose varied from 169 to 583 J/L. The experimental conditions and results are depicted in Fig. 4. It was observed that the
mixing of O2 in the NO gas stream increases the generation of
NO2 even before the EB process. The increase in the NO2 concentration was proportional to decrease in NO concentration (Fig. 4a).
The oxidation reaction of NO by O2 can be represented as follows.
2NO O2 ! 2NO2
Fig. 3. (a) Effect of EB dose on NO gas, and (b) FTIR spectra of the NO gas during EB
processing.
The formation of the NO2 and N2O was identied in the FTIR
spectra of the gas stream (Fig. 3b). The NO2 concentration was observed to increase from 40 to 60 ppm for the EB dose increased
from 186 to 400 J/L, respectively. It indicated that the EB would
also accelerate the oxidation of NO by the reaction with O atom.
The generation of the NO2 is represented in the following equation.
NO O N2 ! NO2 N2
It was also noticed that the presence of O2 increases the oxidation of NO to NO2 during EB irradiation. The NO2 generation was
increased from 295 to 389 ppm for the EB dose increased from
169 to 583 J/L, respectively (Fig. 4b).
The NO removal efciency was increased to 49%, 65% and 67% at
the applied dose of 169, 363 and 583 J/L, respectively in the presence of O2. Nevertheless, The NOx removal was achieved only to
the extent of 30% at the higher applied dose of 583 J/L (Fig. 4c). This
could be attributed to oxidation of NO by EB irradiation. Similarly,
the N2O concentration was found to form around 35 ppm at the
higher applied dose 583 J/L (Fig. 4d), which is lower compared to
EB experiment conducted in the absence of O2 gas (Fig. 3a). It
was observed that the 250 ppm of NO found to be unaccounted,
which could be attributed to convert as N2 as expressed in Eq.
(2). The NO reduction efciency was lowered 12% compared to
the EB experiment conducted in the absence of O2 (Fig. 3a).
To understand the removal mechanism of the NO and NOx under EB irradiation, it is necessary to nd the species involved in
the oxidation and reduction reaction. For the better understanding,
the behaviour of the dry gases such as N2, O2 and the mixture of
90.9% N2 and 9.1% O2 investigated separately under EB irradiation
with a dose of 583 J/L. The ow rate was xed at 6.6 L/h. The FTIR
spectra of the resultant gas obtained from the EB processing are given in the Fig. 5. The FTIR spectra recorded for N2 gas acquired after
EB processing (Fig. 5b) did not exhibit any signicant difference
compared to the spectra of the N2 and O2 mixture gas obtained
in the absence of EB irradiation (Fig. 5a). The bands assigned at
2145 and 1052 cm1 in the FTIR spectra (Fig. 5c) recorded for the
It was observed that the N2O is formed only after the NO2 generation (Fig. 3a). Also, it was noticed that the N2O concentration is
increased than the NO2 concentration while increasing the dose
from 186 to 400 J/L. It indicated that the generation of N2O is ascribed to occur from NO2 concentration. The NO2 would undergo
reduction reaction with N atom to form N2O as EB processing
accelerates the reduction reaction. The vibration bands assigned
at 2234 and 1299 cm1 in the FTIR spectra conrmed the N2O formation (Fig. 3b). Thus, the N2O concentration was found to increase from 40 to 70 ppm for the dose increased from 186 to
400 J/L, respectively. The formation of N2O is represented in the
following equation.
N NO2 ! N2 O O
348
Fig. 5. FTIR spectra of the different gases during the EB processing (a) mixture of N2
(90.9%) and O2 (9.1%) gas (absence of EB processing), (b) N2 gas (Dose: 583 J/L), (c)
O2 gas (Dose: 583 J/L), (d) mixture of N2 (90.9%) and O2 (9.1%) gas (Dose: 583 J/L).
to the moisture content of 5%. The dry O2 gas was used as a carrier
gas for the water vapour generated from the water at 20 C (Fig. 1).
The stimulated gas mixture was subjected to the EB processing at a
dose of 169 J/L with the ow rate of 6.6 L/h. The reduction in the
concentration of NO and NOx is given in Fig. 6. It was observed that
the removal of NO and NOx is found to be 65% and 38%, respectively. The NO2 generation was found to form 250 ppm. This is
50 ppm less compared to NO2 generation in the experiment conducted with the dry mixture gas (Fig. 4b). The N2O generation is
reached to the extent of 10 ppm.
The EB processing is a promising technique to produce more
numbers of excited nitrogen atoms, N(2D) and N(2P) for the reduction of NO. Nevertheless, it is reported that the electronically excited metastable N atoms (N(2D)) react rapidly with O2 to
produce NO, and counter act the NO reduction process by the
ground state N radicals [27]. The presence of H2O found to inhibit
the reactivity of the N(2D) towards NO2 generation. It is reported
that the rate constant for the interaction of the N(2D) with H2O
(2.5 1010 cm3 molecule1 s1) is very high compared to rate
constant for the interaction of the N(2D) with O2 (6 1012 cm3 molecule1 s1) [28]. The reaction of H2O with N(2D) can be shown
as follows.
N2 D H2 O ! NH OH
12
O2 e ! O O e
NH NO ! N2 OH
O2 O ! O3
NO O3 ! NO2 O2
The spectra of mixture gas (N2 and O2) after the EB processing
shown in Fig. 5d. The bands at 2234 and 1052 cm1 could be attributed to vibration bands of N2O and O3, respectively. The N2O concentration was found to reach 28 ppm. The excitation and
dissociation of N2 leads to a number of additional reaction paths
involving nitrogen atom and excited molecular state N2 (N2(A)).
The generation of O3 and N2O can be expressed as follows.
N O2 ! NO O
10
N2 A O ! N2 O
11
O2 O ! O3
NH O2 ! NO OH
14
NO OH ! HNO2
15
2HNO2 ! NO NO2 H2 O
16
e N2 O ! N2 A O
13
349
II (Fig. 1). The selective reductant such as Na2SO3 (3% W/V) was
employed to scrub the NO2 formed during the EB processing. The
effect of the EB dose at 363 and 811 J/L on NO and NOx removal
was investigated with the gas ow rate of 6.6 L/h. The Na2SO3 solution ow to reactor was xed at 1 cc/min. The reduction in the concentration of NO and NOx and the experimental conditions are
depicted in Fig. 7. It was observed that the NO and NOx removal
could be achieved to 87.5% and 85%, respectively, with the retention time of 1.7 s. The high NOx removal could be attributed to conversion of NO2 to NO
2 by the Na2SO3 reduction. The overall
reaction of NO2 with SO2
3 can be expressed as follows [30,31].
2
2NO2 SO2
3 H2 O ! 2NO2 2H SO4
17
[1] A. Chaloulakou, I. Mavroidis, I. Gavriil, Compliance with the annual NO2 air
quality standard in Athens. Required NOx levels an expected health
implications, Atoms. Environ. 42 (2008) 454465.
[2] K. Skalska, J.S. Miller, S. Ledakowicz, Trends in NOx abatement: a review, Sci.
Total Environ. 408 (2010) 39763989.
[3] F. Luck, J. Roiron, Selective catalytic reduction of NOx emitted by nitric acid
plants, Catal. Today 4 (1989) 205218.
[4] T.C. Bruggemann, F.J. Keil, Theoretical investigation of the mechanism of the
selective catalytic reduction of nitric oxide with ammonia on H-form zeolites,
J. Phys. Chem. C 112 (2008) 1737817387.
[5] M.A. Gomez-Garcia, V. Pitchon, A. Kiennemann, Pollution by nitrogen oxides:
an approach to NOx abatement by using sorbing catalytic materials, Environ.
Int. 31 (2005) 445467.
350
[6] L.J. Muzio, G.C. Quartucy, Implementing NOx control: research to application,
Prog. Energy Combust. 23 (1997) 233266.
[7] L.Z. Gao, H.T. Chua, S. Kawi, The direct decomposition of NO over the la2CuO4
nanober catalyst, J. Solid State Chem. 181 (2008) 28042807.
[8] X. Chang, G. Lu, Y. Guo, Y. Wang, Y. Guo, A high effective adsorbent of NOx:
preparation, characterization and performance of Ca-beta Zeolites, Micropore
Mesopore Mater. 165 (2013) 113120.
[9] Z. Zheng, P. Lu, C. Li, L. Mai, Z. Li, Y. Zhang, Removal of NO by carbonaceous
materials at room temperature: a review, Catal. Sci. Technol. 2 (2012) 21882199.
[10] L. Olsson, H. Sjovall, R.J. Blint, Detailed kinetic modeling of NOx adsorption and
NO oxidation over CuZSM-5, Appl. Catal. B 87 (2009) 200210.
[11] A. Heyden, N. Hansen, A.T. Bell, F.J.J. Keil, Nitrous oxide decomposition over
FeZSM-5 in the presence of nitric oxide: a comprehensive DFT study, Phys.
Chem. B 110 (2006) 1709617114.
[12] W. Wang, Z. Zhao, F. Liu, S. Wang, Study of NO/NOx removal from ue gas
contained y ash and water vapour by pulsed corona discharge, J. Electrostat.
63 (2005) 155164.
[13] R. McAdams, Prospects for non-thermal atmospheric plasmas for pollution
abatement, J. Phys. D: Appl. Phys. 34 (2001) 28102821.
[14] G. Sathiamoorthy, S. Kalyana, W.C. Finney, R.J. Clark, B.R. Locke, Chemical
reaction kinetics and reactor modelling of NOx removal in a pulsed streamer
corona discharge reactor, Ind. Eng. Chem. Res. 38 (1999) 18441855.
[15] B.M. Penetrante, M.C. Hsiao, B.T. Merritt, G.E. Vogtlin, P.H. Wallman, Pulsed
corona and dielectric-barrier discharge processing of NO in N2, Appl. Phys. Lett.
68 (1996) 37193721.
[16] A.M. Vandenbroucke, R. Morent, N. De Geyter, C. Leys, Non-thermal plasmas for
non-catalytic and catalytic VOC abatement, J. Hazard. Mater. 195 (2011) 3054.
[17] H. Potts, J. Hugill, Studies of high-pressure, partially ionized plasma generated
by 2.45 GHz microwaves, Plasma Sources Sci. Technol. 9 (2000) 1824.
[18] Y.S. Mok, V. Ravi, H.-C. Kang, B.S. Rajanikanth, Abatement of nitrogen oxides in
a Catalytic reactor enhanced by nonthermal plasma discharge, IEEE Trans.
Plasma Sci. 31 (2003) 157165.
[19] C.W. Park, J.H. Byeon, K.Y. Yoon, J.H. Park, J. Hwang, Simultaneous removal of
odors, airborne particles, and bioaerosols in a municipal composting facility by
dielectric barrier discharge, Sep. Purif. Technol. 77 (2011) 8793.