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ARTICLE IN PRESS

Radiation Physics and Chemistry 76 (2007) 14801484


www.elsevier.com/locate/radphyschem

Industrial applications of electron beam ue gas treatmentFrom


laboratory to the practice
Andrzej G. Chmielewskia,b,
a

Institute of Nuclear Chemistry and Technology, Warsaw, Poland


Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warsaw, Poland

Abstract
The electron beam technology for ue gas treatment (EBFGT) has been developed in Japan in the early 1980s. Later on, this process
was investigated in pilot scale in the USA, Germany, Japan, Poland, Bulgaria and China. The new engineering and process solutions
have been developed during the past two decades. Finally industrial plants have been constructed in Poland and China. The high
efciency of SOx and NOx removal was achieved (up to 95% for SOx and up to 70% for NOx) and by-product is a high quality fertilizer.
Since the power of accelerators applied in industrial installation is over 1 MW and requested operational availability of the plant is equal
to 8500 h in year, it is a new challenge for radiation processing applications.
r 2007 Elsevier Ltd. All rights reserved.
Keywords: Electron accelerator; Flue gas treatment; Sulfur dioxide; Nitrogen oxides; VOC

1. Introduction
The municipal and industrial activities of the man lead to
environment degradation. The pollutants are emitted to the
atmosphere with off-gases from industry, power stations,
residential heating systems and vehicles. Fossil fuels, which
include coal, natural gas, petroleum, shale oil and bitumen
are the main source of heat and electrical energy. All these
fuels contain beside major constituents (carbon, hydrogen,
oxygen) other materials as metal, sulfur and nitrogen
compounds. During the combustion process different
pollutants as y ash, sulfur oxides (SO2 and SO3), nitrogen
oxides (NOx NO2+NO) and volatile organic compounds are emitted. Fly ash contains different trace
elements (heavy metals). Gross emission of pollutants is
tremendous all over the world. These pollutants are present
in the atmosphere in such conditions that they can affect
man and his environment. Air pollution caused by
particulate matter and other pollutants not only acts
directly on environment but by contamination of water and
Fax: +48 22 8111532.

E-mail addresses: A.Chmielewski@ichtj.waw.pl,


A.Chmielewski@ichip.pw.edu.pl (A.G. Chmielewski).
0969-806X/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.radphyschem.2007.02.056

soil leads to their degradation. Wet and dry deposition of


inorganic pollutants leads to acidication of environment.
These phenomena affect health of the people, increase
corrosion of metal structures, historical buildings and
monuments. Widespread forest damage has been reported
in Europe and North America regions. Many cultivated
plants are not resistant to these pollutants either especially
in the early period of vegetation. The mechanisms of
pollutants transformation in atmosphere are described by
environmental chemistry. Photochemistry plays an important role in these transformations. SO2 and NOx are
oxidized and sulfuric and nitric acids are formed in
presence of water vapor, fog and droplets. Other discussed
problem connected with human activities is emission of
volatile organic compounds to the atmosphere. These
emissions cause stratospheric ozone layer depletion, ground
level photochemical ozone formation, toxic or carcinogenic
human health effects, enhancing the global greenhouse
effect, accumulation and persistence in environment
(Chmielewski, 2002). Waters in the open and underground
reservoirs are being polluted, as well as cultivated soil and
forests. Most of the plants, especially coniferous trees are
not resistant to sulfur oxides. In recent years, investigation
has shown that emission to the atmosphere of volatile

ARTICLE IN PRESS
A.G. Chmielewski / Radiation Physics and Chemistry 76 (2007) 14801484

organic compounds (VOC) can cause stratospheric


ozone layer depletion, ground level photochemical
ozone formation, and toxic or carcinogenic human health
effects.
They contribute to the global greenhouse effect adding a
new dimension to the environmental degradation as a
result of burning of fossil fuels. Chlorinated organic
pollutants which are emitted from fossil fuel power plants,
municipal waste incinerators, chemical industry are very
harmful to the environment and human being. Recent
studies reported that chlorinated benzenes or phenols are
suspected as precursors for dioxins emissions. Dioxins are
relatively chemical inert and demonstrate long lifetime in
environment, therefore they are called persistent organic
pollutants (POPs). They are transported by air and are
deposited on the surfaces of the soil, water and plants.
Then they may enter human food chain. Consequently, the
problems associated with air pollutants emission are no
longer just local or regional, but have become continental
in scope. The situation regarding environment contamination is becoming critical (EOLSS, 2001, 2002). Therefore
the economically and technically feasible technologies for
pollution control are searched for. The radiation offers
advanced solutions to the selected problems as well
(Chmielewski, 2005; Cooper et al., 1998; SNU, 2003;
IAEA, 2005).
2. Process theory
Wet ue gas desulfurization (FGD) and selective
catalytic reduction (SCR) can be applied for ue gas
treatment and SO2 and NOx emission control. VOCs are
usually adsorbed on carbon, but this process is rarely used
for lean hydrocarbon concentrations up to now. All these
technologies are complex chemical processes and waste,
like wastewater, gypsum and used catalyst are generated
(Srivastava et al., 2001).
Electron beam technology is among the most promising
advanced technologies of new generation. This is a dryscrubbing process of simultaneous SO2 and NOx removal,
where no waste except the by-products are generated.
Studies show that irradiation of ue gases with an electron
beam can bring about chemical changes that make removal
of sulfur and nitrogen oxides easier. The main components
of ue gases are N2, O2, H2O, and CO2, with much lower
concentration of SOx and NOx. NH3 may be present as an
additive to aid removal of the sulfur and nitrogen oxides.
Radiation energy is absorbed by gas components in
proportion to their mass fraction in the mixture. The fast
electrons slow down and secondary electrons are formed
which play important role in overall energy transfer. After
irradiation, fast electrons interact with gas creating various
ions and radicals, the primary species formed include e,
+
+
+
+
+
+
+
+
N+
2 , N , O2 , O , H2O , OH , H , CO2 , CO , N2*,
O2*, N, O, H, OH, and CO. In the case of high water vapor
concentration the oxidizing radicals OHd and HOd2 and
excited ions as O(3P) are the most important products.

1481

These species take part in a variety of ionmolecule


reactions, neutralization reactions, dimerization (Person
and Ham, 1988). The SO2, NO, NO2, and NH3 present
cannot compete with the reactions because of very low
concentrations, but react with N, O, OH, and HO2
radicals. After humidication and lowering its temperature, ue gases are guided to reaction chamber, where
irradiation by electron beam takes place. Ammonia is
injected upstream the irradiation chamber. There are
known several pathways of NO oxidation. In the case of
electron beam treatment the most important are as follows
(Matzing and Paur, 1992):
NO O3 P M ! NO2 M;
O3 P O2 M ! O3 M;
NO O3 M ! NO2 O2 M;
NO HO2 d M ! NO2 d OH M:
After the oxidation NO2 is converted to nitric acid in the
reaction with OHd according to the reaction:
NO2 d OH M ! HNO3 M:
HNO3 aerosol reacts with NH3 giving ammonium nitrate
that can be written
HNO3 NH3 ! NH4 NO3 :
Partly NO is reduced to atmospheric nitrogen.
There can be also several pathways of SO2 oxidation
depending on the conditions. In the electron beam
treatment the most important are radio-thermal and
thermal reactions (Tokunaga and Suzuki, 1984).
Radio-thermal reactions proceed through radical oxidation of SO2 in the reaction:
SO2 d OH M ! HSO3 M
then HSO3 creates ammonium sulfate in the following
steps:
HSO3 O2 ! SO3 HO2 ;
SO3 H2 O ! H2 SO4 ;
H2 SO4 2NH3 ! NH4 2 SO4 :
The thermal reaction is based on the following process:
SO2 2NH3 ! NH3 2 SO2 ;
O2 ;H2 O

NH3 2 SO2 ! NH4 2 SO4 .


The total yield of SO2 removal consists of the yield of
thermal and radio-thermal reactions that can be written
(Chmielewski, 1995; Matzing et al., 1993):
ZSO2 Z1 f; T Z2 D; aNH3 ; T.
The yield of the thermal reaction depends on the
temperature and humidity and decreases with the temperature

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A.G. Chmielewski / Radiation Physics and Chemistry 76 (2007) 14801484

increase. The yield of the radio-thermal reaction depends


on the dose, temperature and ammonia stoichiometry. The
main parameter in NOx removal is the dose. The rest of
parameters play minor role in the process. Nevertheless in
real, industrial process, dose distribution and gas ow
conditions are important from the technological point of
view (Chmielewski et al., 1998). The similar chemistry
of the process is observed in corona discharge process
(Shang et al., 2006), however energy consumption and
more complicated reactor design seems to be limitations of
the process.
3. Pilot plants
Japanese scientists demonstrated in 19701971 the
removal of SO2 using an electron beam from a linear
accelerator (212 MeV, 1.2 kW). A dose of 50 kGy at
100 1C led the conversion of SO2 to an aerosol of sulfuric
acid droplets, which were easily removed (Machi, 1983).
Ebara Co. used an electron accelerator (0.75 MeV,
45 kW) to convert SO2 and NOx into a dry product
containing (NH4)2SO4 and NH4NO3 which could be used
as a fertilizer.
Using the Ebara process, two larger scale plants were
constructed in Indianapolis, USA (Frank, 1995) and
Karlsruhe, Germany (Wittig et al., 1988). The Indianapolis
plant was equipped with two electron beam accelerators
(0.8 MeV, 160 kW) and had a capacity of 1.63.2 
10,000 m3/h with gas containing 1000 ppm SO2 and
400 ppm NOx. In Badenwerk, Karlsruhe, two electron
accelerators (0.3 MeV, total power 180 kW) were used to
treat 12  10,000 m3/h ue gas containing 50500 pm SO2
and 300500 ppm NOx. The rst pilot system in China,
using the same principle to remove SO2 and NOx in ue
gas, was built at the Thermal Power Plant of Science City
in Mianyang, Sichuan. Its designed ow volume is
300012,000 Nm3/h, SO2 removal rate is not o90% and
NOx, not o70% (Mao et al., 2000; Yonghua et al., 2002).
However the nal engineering design technology for
industrial applications was achieved at the pilot plants
being operated in Nagoya, Japan (Namba et al., 1995) and
Kaweczyn, Poland (Chmielewski et al., 1995). In the case
of the latter a new engineering solutions were applied;
doublelongitudinal gas irradiation, air curtain separating
secondary window from corrosive ue gases and modications of humidication/ammonia system (high enthalpy
water or steam injection, ammonia water injection) and
others. The obtained results have conrmed the earlier
discussed physico-chemistry of the process. The high dose
is required for NOx removal, while SOx is removed at
proper conditions, at low-energy consumption.
The new solutions are tested for low-grade fuels like
lignite. The pilot plant for treatment of ue gases from lowgrade lignite (high ash, high sulfur and high water content
has been constructed in Bulgaria (Doutzkinov, 2005). The
ow capacity is 10,000 Nm3/h and the accelerator from
Nagoya pilot plant was used.

4. Industrial plants
These new solutions led to the economical and technical
feasibility improvement and nal industrial-scale plant
construction.
Ebara Corporation constructed full-scale plant in
Chengdu, China mostly for SOx removal, therefore the
power of accelerators applied is 320 kW for treatment of
270,000 Nm3/h of the ue gas. Reported efciency is 80%
for SOx and 20% for NOx (Doi et al., 2000).
The ue gas treatment industrial installation is located in
EPS Pomorzany in Szczecin in the north of Poland
(Chmielewski et al., 2004). The installation puries ue
gases from two Benson boilers of 65 MWe and 100 MWth
each. The maximum ow rate of the gases is 270,000 Nm3/h
and the total beam power exceeds 1 MW. A ue gas
treatment plant was installed in EPS Pomorzany in
Szczecin, Poland. There are two reaction chambers with
nominal ow gas rate of 135,000 Nm3/h. Each chamber is
irradiated by two accelerators (260 kW, 700 keV) installed
in series. The applied dose is in the range of 712 kGy.
The removal of SO2 approaches 8090% in this dose
range, and that of NOx is 5060%. The by-product is
collected by the electrostatic precipitator and is shipped to
the fertilizer plant.
The installation consists of four main parts:






ue gas conditioning unit;


ammonia storage and dosage unit;
reaction chambers; and
by-product collecting and storage unit.

As it was previously mentioned the removal efciency


depends strongly on the process conditions. The highest
obtained efciency for SO2 reaches 95%, while for NOx it
reaches 70%. The data obtained during the operation of
the installation conrmed the previously considered
assumption on the impact of the process parameters on
the removal effectiveness. In the case of NOx removal the
most important parameter is the dose. The inlet concentration of NOx is the second parameter, that impact on this
pollutant removal was observed. The correlation is linear
and total removal (taken in mg/Nm3) increases with the
inlet concentration of NOx, while the relative removal
(in %) decreases with the parameter increase. The
ammonia stoichiometry factor has a very little impact on
the NOx removal.
In the case of SO2 removal there are more parameters
that affect this pollutant removal efciency. The most
important among them is temperature of the gas after
humidication due to the thermal reactions contribution.
Afterwards the dose should be mentioned. Although the
humidity seems to have the major impact on the process
efciency, it is hard to prove it with no doubt because
of the strong correlation between the humidity and
the temperature of the process (dew point temperature is
a factor of both parameters; humidity and temperature).

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A.G. Chmielewski / Radiation Physics and Chemistry 76 (2007) 14801484

The temperature decreases during the water evaporation


process and humidity increases. Unexpectedly high inuence of ammonia stoichiometry ratio on the SO2 removal
efciency has been observed. The other factors as ue gas
ow rate and inlet concentration have much less impact on
the removal efciency. During the experiments one more
parameter having impact on the whole process has been
detected: the ammonia injection mode. It was observed,
that the injection of part of ammonia water directly to
humidication tower increases the SO2 removal efciency.
The new industrial plant is under construction in China
in Beijing, Jingfeng Power Plant, the ow capacity will be
equal to 630,000 Nm3/h. Three accelerators will be
installed; 2  1000 kV/500 mA and 1  1000 kV/300 mA.
The plant will be operational in 2007 (Mao, 2005).
The critical point in the technology are accelerators. These
machines should be operated continuously 8500 h per year
and the period between maintenance services should be at
least 3000 h. The cable connections between high power
supply and accelerator should be avoided and good cooling
systems for the cathode and primary window provided. The
improved foil materials have to be applied. The results of the
work done by some centers demonstrated that such
improvements in the titanium foil can be achieved by Pd
surface alloying (Bonilla et al., 2006, 2006a).
5. New prospects of technologyradiation-induced VOC
removal from off gases

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and H atom abstraction (for the alkyl-substituted


aromatic compounds) or H atom elimination (for
benzene, naphthalene and the higher polycyclic aromatic hydrocarbons).
C6H5CH3+dOH Rd2 +H2O (H atom abstraction),
C6H6+dOH C6H5OH+H (H atom elimination).
Radicals (Rd1 , Rd2 ) formed above go though very complex
reactions: O2 addition, O atom release, aromatic CHO
(-dehydes), OH (-ol) compounds formed or ring cleavage
products:
Rd R1 d ; R2 d O2 RO2 d ;
2RO2 d 2ROd O2 ;
RO2 d NO ROd NO2 ;
ROd O2 HO2 d products aromatic 2CHO; 2O;
ROd ! aliphatic products:
The possibility of the process application for the dioxins
removal form ue gases has been studied (Hirota et al.,
1995; Paur et al., 1998) and recent pilot studies demonstrated that process is technically and economically feasible
(Hirota et al., 2003).
6. Conclusions

In the case of VOCs decomposition the process itself is


based on the similar principles as primary reactions
concerning SO2 and NOx removal i.e. free radicals attack
on organic compounds chains or rings causing VOCs
decomposition (Chmielewski et al., 2002).
For chlorinated aliphatic hydrocarbons decomposition (e.g.
chloroethylene), Cl dissociated secondary electron-attachment
and Cl, OH radicals reaction with VOCs play very important
roles for VOCs decomposition (Sun et al., 2006).
For aromatic hydrocarbons, VOCs decomposition will
mainly go through:
1. Positive ions charge transfer reactions
M RH RH VOC; e:g: Benzene or PAHs
M RH :
Because RH has lower ionization energy (IE)
(Benzene: IE 9.24 eV; PAHs: IEo10 eV) than most
primary positive ions (IE411 eV) formed above, part of
VOC will be decomposed by rapid charge transfer
reactions.
2. Radicalneutral particles reactions
d
OH radical plays very important role for VOC
decomposition, especially when water concentration is
10%. dOH radicals react with VOC in two ways:
d
OH radical addition to the aromatic ring (e.g. toluene)
d

OH C6 H5 CH3 R1 d

1. Electron beam ue gas treatment technology has been


applied in the full industrial scale.
2. The advantages of the technology i.e. high SO2 and NOx
removal efciencies were achieved.
3. No wastewater or solid wastes are generated and
byproduct is a high-grade fertilizer component.
4. The laboratory and pilot scale test have demonstrated
that the process can be applied for VOC removal as well.
Therefore three pollutants can be treated simultaneously. There is no other technology with such
capabilities.
5. The critical point in the technology implementation is
reliability of accelerators in continuous machine operation. The longer periods between servicing and good
corrosion/mechanical-stress resistance of the primary
and secondary window foils should be a target for future
developments. The results of the tests performed in the
industrial harsh conditions should be analyzed and
adopted by accelerator manufacturers, in both phases of
machine design and its manufacturing.
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