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University POLITEHNICA of Bucharest, ]149 Calea Victoriei St., 010072 Bucharest, Romania
National Institute for Lasers, Plasma and Radiation Physics, Electron Accelerators Laboratory, P.O.Box: MG-36, ]409 Atomistilor St., 077125 Magurele, Ilfov, Romania
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Institute of Nuclear Chemistry and Technology, ]16 Dorodna St., 03-195 Warsaw, Poland
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H I G H L I G H T S
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a r t i c l e i n f o
a b s t r a c t
Article history:
Received 30 May 2012
Accepted 11 October 2012
Available online 20 November 2012
The Electron Beam Flue Gas Treatment (EBFGT) has been proposed as an efcient method for removal of
SO2 and NOx many years ago. However, the industrial application of this procedure is limited to just a
few installations. This article analyses the possibility of using medium-power EB accelerators for offgases purication. By increasing electron energy from 0.7 MeV to 12 MeV it is possible to reduce the
energy losses in the windows and in the air gap between them (transformer accelerators can be applied
as well in the process). In order to use these mid-energy accelerators it is necessary to reduce their
penetration depth through gas and this can be achieved by increasing the density of the reaction
medium by means of dispersing a sufcient amount of ne water droplets (FWD). The presence of FWD
has a favorable effect on the overall process by increasing the level of liquid phase reactions. A special
reactor was designed and built to test the effect of FWD on the treatment of ue gases with a high
concentration of SO2 and NOx using high-energy EBs (9 MeV). By determining the energy efciency of
the process the favorable effect of using FWD and high-energy EB was demonstrated.
& 2012 Elsevier Ltd. All rights reserved.
Keywords:
Flue gases
NOx and SO2 removal
Electron beam
Fine water droplets
1. Introduction
New technologies and processes have promoted our economic
growth and have been remarkably changing our lifestyles. However, technological innovation is not always welcome. It has
impact on the environment and may have effects related to the
peoples health. The emission of inorganic pollutants such as
nitrogen oxides (NOx) and sulfur dioxide (SO2) has been remarkably reduced by application of state-of-the-art technologies
during the past 60 years. However, industrialized countries have
been using the big amounts of oil and coal for energy production
n
131
have been applied to treat SO2 and NOx. However, the wet lime
scrubber method requires wastewater treatment, and the catalysts have to be replaced periodically. New technology is expected
for simple and simultaneous treatment processing of the both
pollutants. The electron-beam irradiation process for ue gas
purication (EBFGT) has been proposed as an efcient method
because it has the following advantages (Hatano et al., 2011):
(Matzing
and Paur, 1992; Tokunaga and Suzuki, 1988). In the case
of high water concentration, oxidizing radicals HO and HO2 and
excited species such as O(3P) are the most important product
formed (Person and Ham, 1988). In the presence of water
droplets, the radiolytically produced hydrated electron reacts
very fast with the dissolved oxygen to produce the superoxide
(O2 ) radical. Since the O2 has a pKa value of 4.7, it will be
converted to HO2 in acidic medium. HO2 is also produced by the
reaction of H-atom with oxygen. However the yield from this
reaction is only about 0.06 mmol per joule.
N2 ,O2 ,H2 Ovapors_at_high_concn e -HO ,HO2 ,On ,ions,excited-species
1
In the presence of these reactive species, NOx and SO2 from
ue gases are oxidized and produce nitric acid and sulfuric acid,
respectively, as intermediate products. These acids are neutralized with ammonia, giving powders of ammonium nitrate and
ammonium sulfate, respectively (Namba et al., 1998) (Fig. 1).
The total yield of SO2 removal consists of the yield of thermal
and radiation induced reactions that can be written (Chmielewski
(3)
Fig. 1. The main reactions used in EBFGT to convert SO2 and NOX (Namba et al., 1998).
(4)
(5)
(6)
SO3 H2O-H2SO4
(7)
(8)
132
10
Electron ranges in other materials can be estimated by multiplying the polyethylene range with the ratio of their CSDA ranges.
Rmaterial Rpolyethylene CSDAm=CSDApe
Fig. 3. Electron energy losses function of incident electron energy for ue gases
treatment by EB (Cleland, 2007).
11
Fig. 4. Electron energy deposition vs. thickness density in water at 1.0, 1.5, 2.0,
2.5, 3.0, 3.5 4.0, 4.5 and 5.0 MeV incident electron energy (IAEA, 2010).
Fig. 6. The inuence of liquid water fraction (L) in ue gases on the density of ue
gases with FWD and penetration depth for EB of 2.5 MeV.
High driving force for the most oxidation process due to low
Gibbs free energy of the products obtained in liquid phase;
133
the phases densities, rgas and raq. Since the ratio raq/rgas is typically
Z103, then DRaq/DRgas raq/rgas Z103, assuming that the stopping
powers of the gas and liquid phase are quite the same. Thus the dose
rate in the droplet is higher than that of the gas by a factor of at least
three orders of magnitude. This means that the ratio of the chemical
reactions rates of the pollutants oxidation in the two phase system
is controlled by the phases densities.
With regard to the portioning of absorbed doses between the two
phases, which determines the extent of pollutant removal during
irradiation, one gets (Cooper et al., 1998): Daq/Dgas Z raq*L/rgas.
When L is quite low (in a typical EBFGT process Lr10 6), it is
unlikely that the radiation-induced reactions in the liquid phase
can a play a signicant role in the removal of pollutants from the
irradiated gas, but if L 10 3 the reactions in liquid phase become
important. For such conditions, the chain oxidation takes place in
liquid phase, but the chain is initiated by active particles formed
in the gas and liquid phase (Potapkin et al., 1995).
It was found (Yermakov et al., 1995) that the extents of NOx and
SO2 depletion on simultaneous irradiation and spraying of water
(or water solution) are sensitive not only to absorbed dose but also
to the amount of water existing in the gas as liquid droplets.
The conversion of SO2 can be obtained by reactions in gas
phase (thermal and radio-induced) and by reactions in liquid
phase. Because of high value of solubility of SO2 in water (Henrys
constant1.23 Mnatm 1) SO2 is easily absorbed in water and
here the SO2 is oxidized by a chain reaction in the presence of
dissolved oxygen (Potapkin et al., 1995). The conversion of NO
takes place only by radio-induced reactions. In gas phase NO is
oxidized to NO2 by reactions of NO with O and O3. In the absence
of water droplets the removal efciency of NO dropped sharply
after NO conversion to NO2 (Potapkin et al., 1995). This is because
12
NO2 N-N2 O O
13
14
15
No2 HSO
3 -NO2 HSO3
16
H2 O
2
No
2 HSO3 H - SO4 NH4
17
NO
2 HSO3 --HSO4 N2
18
134
2. Experimental
The experimental part took place in the irradiation laboratories of the National Institute for Lasers, Plasma and Radiation
Physics Bucharest using an ALIN-10 EB accelerator.
The ALIN-10 accelerator is a laboratory installation designed
for fundamental research. It is located in a horizontal position
inside the irradiation room and is equipped with a postacceleration beam focusing and bending to project accelerated
EB loading characteristic
EB power characteristic (100 Hz)
182
12.46 MeV
12
156
10
130
PEB max
104
9.17 MeV
78
6.23MeV
13 A
52
26.25 A
26
0
0
10
15
20
25
EB average current, IEB (A)
30
35
14
Fig. 8. EB average energy (EEB) and electron average beam power (PEB) versus EB
average current (IEB).
Fig. 9. The schematic drawing of EB reactor for treatment of ue gases by EB in the presence of FWD.
135
Table 1
Treatment conditions and results obtained for ue gas treatment by EB, in the presence of ammonia and of FWD.
No.
Treatment conditions
Flow rate (l/h)
1
2
3
4
5
6
7
8
9
a
Gases
Liq. water
1000
5200
5200
14,000
14,000
14,000
14,000
14,000
14,000
0
0
50
0
50
0
50
0
50
Results
NH3 stoecha
0.8
0.9
0.9
0.6
0.6
0.95
0.95
0.95
0.95
NO
2000
812
812
1116
1116
423
423
520
520
400
44
44
102
102
135
135
292
292
Treatment type
RE SO2
RE NOx
EB
EB
EB FWD
EB
EB FWD
EB
EB FWD
EB
EB FWD
0.98
0.85
0.94
0.70
0.88
0.97
0.98
0.97
0.98
0.62
0.78
0.98
0.36
0.88
0.32
0.84
0.20
0.8
that are mechanically tted with screw clamps and helically and
equidistant distributed to 1201. The high pressure causes water to be
sprayed through nozzles as small droplets of the diameter close to
10 mm.
The electrons are introduced in the EB reactor through two exit
windows, one of each in the form of cylinder, made of 100 mmthick aluminum foils. The EB current is collected on the electrical
insulated inner vessel of the EB reactor, integrated and displayed
on the control desk.
The characteristics of ALIN-10 EB accelerator used in our
experiments (Ibeam current, Eelectrons energy and PEB
power) highlight on Fig. 8, are
Iexit accelerator 13 71 mA
Eexit accelerator 9.17 0.23/ 0.1 MeV
ireactor as Faraday cup (without FWD): 1011 mA
Ireactor as Faraday cup (with FWD): 0.51 mA
Pexit accelerator 13 mA 9.17 MeV119.21 W
Preactor inside power (without FWD) 10 (11) mA 9.17 MeV 91.7
(100.87) W (about 27.317.34 W are losses in the two
windows of the reactor, the two air gaps, and other uncontrolled losses).
Obs.
Pinlet Poutlet
100%
Pinlet
19
EB_input_power W
60 103
RIED kJ=L
gas_f low_rate L=min
20
Pinlet RE
103
EE g=kWh
RIED
21
136
Table 2
RIED and EE values for different treatment conditions.
No
Treatment conditions
Liquid water
fraction, L
1
2
3
4
5
6
7
8
9
0
0
0.0096
0
0.0036
0
0.0036
0
0.0036
Density (g/L)
1.06
1.06
10.64
1.06
4.6
1.06
4.6
1.06
4.6
Penetration
depth, (cm)
4530
4530
426
4530
1260
4530
1260
4530
1260
Absorbed EB
power (W)
9
9
82.6
9
25
9
25
9
25
RIED (kJ/L)
RIED (kJ/L)
0.032
0.006
0.057
0.002
0.006
0.002
0.006
0.002
0.006
EE (g/kWh)
SO2
NOx
172.8
316.5
38.1
964.4
436.5
506.6
184.2
622.7
226.5
10.3
7.4
1.0
21.3
18.7
25.0
23.6
33.8
48.7
0.347
0.067
0.067
0.025
0.025
0.025
0.025
0.025
0.025
EE (g/kWh)
SO2
NOx
16.2
29.6
32.7
90.1
113.3
47.3
47.8
58.2
58.8
1.0
0.7
0.9
2.0
4.9
2.3
6.1
3.2
12.6
Table 3
Values for industrial EBFGT plant of Pomorzany (Chmielewski et al., 2004).
Results for total EB power
SO2
NOx
SO2
NOx
1,125,000
259,700
0.9
1500
0.014
97.47
1,125,000
259,700
0.7
391
0.014
19.76
1,125,000
203,085
0.9
1500
0.011
123.31
1,125,000
203,085
0.7
391
0.011
25.00
Table 4
Values of beam power losses function of EB energy obtained at pilot plant operated at EPS Kaweczyn (for 0.5, 0.6 and 0.7 MeV) and calculated for different energies of
electron beam in the presence of FWD (for 12 MeV).
EB energy
(MeV)
0.5
0.6
0.7
0.7
47.4
29.2
21.8
21.8
0.4
2.9
14.8
14.8
14.3
46
1.5
8.4
74
6.2
82
5.2
39
19
4
56
39
25
10
1
74
65
53
39
19
Energy economy
(kW or %)
EnEc1
0.0001
0.0001
0.0005
0.001
0.0005
0.001
0.0015
0.002
0.003
0.0005
0.001
0.0015
0.002
0.003
3.9
3.89
19.45
38.90
19.45
38.90
58.35
77.80
116.70
19.45
38.90
58.35
77.80
116.70
With out
FWD
With FWD
2.1
3.81
3.81
3.81
6.71
6.71
6.71
6.71
6.71
9.56
9.56
9.56
9.56
9.56
1.8
3.47
2.54
1.91
4.47
3.35
2.68
2.24
1.68
6.37
4.97
3.98
3.32
2.49
5.70
3.00
8.04
3.08
1.83
4.21
9.09
13.71
43.56
11.52
21.83
29.90
35.21
53.77
EnEc2
10.5
15.54
10.58
11.57
9.19
4.31
0.31
30.16
4.08
6.23
14.3
19.61
38.17
22
4. Conclusions
Electron beam accelerators most often applied for ue gas
treatment are those with medium electrons energy ( o1 MeV) in
order to obtain low penetration depths ( 3 m). At this energy
level of electrons a signicant level of electron beam power is lost
in the metallic foil windows and in the air gap between them. If
higher electron beam accelerators can be used (minimum
1.5 MeV), these losses would be signicantly reduced. At this
level of energy, however, the penetration depth increases signicantly (approx. up to 7.5 m), which means that the treatment
of gases becomes due to the process vessel design difculties.
However if FWD are added to the reaction mixture, the density of
this mixture increases largely, which determines the reduction of
the penetration depth to reasonable values (23 m).
The overall efciency of the process can be measured using the
energy efciency (g pollutant/kWh of effectively used EB). The use
of this parameter allows us to compare the classical experiments
(in which only EB treatment was used) with the experiment in
which EB treatment in the presence of FWD was used at volumetric ratios liquid/gas between 0.0035 and 0.0096.
The presence of FWD determines the increase of the EB power
used, and the energy efciency values obtained are higher than
the ones obtained in an industrial plant in which only EB
treatment is used.
When the power necessary to pump water in order to obtain
FWD is included in the total energy balance it can be noticed that
there is a limit value of the volumetric ratio liquid:gas (L). For a
137
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