Applied Thermal Engineering 70 (2014) 1253e1261

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Applied Thermal Engineering

journal homepage: www.elsevier.com/locate/apthermeng

Flue gas cleaning by high energy electron beam e Modeling and

sensitivity analysis
Valentina Gogulancea*, Vasile Lavric
Chemical and Biochemical Engineering Department, University POLITEHNICA of Bucharest, RO-011061, Polizu 1-7, Bucharest, Romania

h i g h l i g h t s

A mathematical model for the electron beam flue gas treatment was developed.

The main chemical processes in both gas and liquid phases are accounted for.

The droplet generation and adsorption of gas components are taken in consideration.

The model is in good agreement with the experimental data in bibliographical sources.

The sensitivity of the process was tested using a fractional factorial white experiment.

a r t i c l e i n f o a b s t r a c t

Article history: The removal of sulfur and nitrogen oxides from flue gases using high energy electron beams is based on
Received 4 January 2014 the generation of excited molecules when the flue gas is bombarded by accelerated electrons. The excited
Accepted 14 May 2014 molecules undergo ionization, dissociation and electron attachment to yield reactive species (ions,
Available online 22 May 2014
metastables, free radicals and electrons) which interact with the flue gas components. A complex
mathematical model was built-up, which includes the main chemical processes in both gas and liquid
Keywords:
phases together with the droplets generation and thermodynamic equilibrium between the two phases.
Electron beam
The simulation results are in good agreement with the experimental data gathered from literature.
Flue gas treatment
Sensitivity analysis
Modeling the formation of liquid droplets and the adjacent physico-chemical phenomena provide a
High energy better understanding of the process and a more accurate interpretation of the experimental results. The
Droplet generation model enables the investigation of the treatment efficiency's sensitivity upon the main operating pa-
SO2 and NOx abatement rameters. A fractional three level factorial white experiment was designed using as parameters the
irradiation dose, the water vapor content and the nitrogen oxide initial concentration of the flue gases.
The removal yield of SO2 is rather insensitive to the said parameters, while, on the contrary, the removal
yield of NO is very sensitive.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction
Growing population and the rise of industrial activities have
taken their toll on the quality of the environment. The pollutants
emitted from industrial facilities, power stations, residential heat-
ing systems and engine vehicles have adverse effects on human
health, cause stratospheric ozone depletion, which in turn leads to
climate change, and contaminate soil and water, leading to acidi-
fication and eutrophication [12].
Conventional methods for the removal of sulfur and nitrogen
oxides such as flue gas desulfurization and selective catalytic
* Corresponding author. Tel.: þ40 724065881.
E-mail address: v.gogulancea@gmail.com (V. Gogulancea).
reduction [14] have long proved their high removal efficiencies
[29]. However, this achievement is accompanied by large energy
consumption and space requirements resulting in soaring invest-
ment and operating costs [28].
Thus, new methods have been devised for the abatement of
sulfur and nitrogen oxides from flue gases. The electron beam flue
gas treatment (EBFGT) is a relatively new procedure, developed in
the late 1970s by the Ebara Corporation, in which the pollutants are
subjected to ionizing radiation leading to the formation of a high-
quality fertilizer mixture [8]. While achieving high removal effi-
ciencies for both sulfur and nitrogen oxides, the process can be
extended to the treatment of other gaseous pollutants and liquid
effluents [16,21].
Compared with more traditional methods, EBFGT has the
advantage of scalability and simplicity in addition to being an easily

http://dx.doi.org/10.1016/j.applthermaleng.2014.05.046
1359-4311/© 2014 Elsevier Ltd. All rights reserved.
1254 V. Gogulancea, V. Lavric / Applied Thermal Engineering 70 (2014) 1253e1261

controllable process [5]. The technology has gradually achieved Despite being slighted in the mathematical modeling of the
some level of market penetration, at first with the construction of a electron beam treatment of exhausts for the last decade, the
series of pilot plant installations in Japan, USA, Germany and modeling of liquid phase phenomena proved to be relevant in the
Poland, among others, and, more recently, with the development of economy of the process [5]. Our paper proposes new approaches to
two industrial facilities in Poland and China [7]. the liquid phase modeling as well as a more extended kinetics: 19
However, the technology suffers, just like the conventional chemical species and 32 chemical reactions, listed in the
treatment methods, from large energy requirements [2] and from Supplementary material.
reliability issues associated with the continuous operation of high
energy electron accelerators [20]. Consequently, numerous in- 2.1. Generation of reactive species
vestigations have been made into the possibility of reducing the
energy consumption for the process: employing hybrid irradiation Radiation energy is absorbed by the gas components which
methods such as combined microwave and electron beam treat- undergo ionization, excitation, dissociation and charge transfer
ment [18], turning to alternative non thermal plasma generation reactions. These processes are referred to as primary radiolysis
methods [10], fitting the plasma reactor with a catalytic layer [15], phenomena and have a time scale in the range of 1014e107 s. As it
using a variety of additives such as ammonia, hydrogen peroxide has proven quite difficult to accurately determine the rates of these
[1], natural gas and hydrated lime [25]. The potential use of me- reactions, the notion of electrochemical yield (G e value) has been
dium energy accelerators has also been investigated [5], with the introduced to account for the number of molecules or ions pro-
provision that a dispersed liquid phase should be introduced in the duced or destroyed per 100 eV of absorbed ionizing energy. The
reactor before the beginning of the irradiation treatment. interactions between fast electrons and the gas components are
Another method to reduce the energy consumption and the described by Eqs. (1)e(4) [27], which are the most cited in
operating costs is the investigation of more appropriate reactor literature.
configurations [23], either experimentally or through the use of
mathematical modeling [8]. The first mathematical models devel- 4:14N2 /0:885N2 D þ 0:295N2 P þ 1:87N4 P þ 2:27Nþ
2
oped started from the simplest reaction systems, formed only of N2, (1)
þ 0:69Nþ þ 2:96e
O2 and NO, considering as little as 29 chemical reactions [22] and
have been gradually improved to include over 850 chemical re-
5:3O2 /2:98O þ 2:25O1 D þ 2:07Oþ þ



actions in the gas phase [26]. However, the size of the kinetic sys- 2 þ 1:23O þ 3:3e (2)
tem greatly impacts the computational capacity so, more recent
modeling studies have only taken into consideration a fraction of

6:7H2 O/0:51H2 þ 4:25OH þ 4:15H þ 0:46O3 P
these chemical reactions [6,11] or have resorted to empirical or (3)
semi-empirical approaches [9]. Despite early interest in modeling þ 1:99H2 Oþ þ 1:99e
the liquid phase phenomena taking place during irradiation [19],
7:54CO2 /4:72CO þ 5:16O þ 2:24COþ þ

2 þ 0:51CO
the low liquid to gas ratio experimentally observed [32] has lead
researchers to neglect the formation and behavior of this liquid (4)
þ 0:07Oþ þ 2:82e
phase in their modeling efforts. However, experimental evidence
shows that the introduction of fine water droplets, even in small
2.2. Chemical reactions in gas phase
amounts, in the irradiation chamber can lead to serious energy
savings and lowers the operating costs [5].
The species produced by the abovementioned primary radiol-
The aim of the current paper is to advocate a complex mathe-
ysis phenomena react further with each other giving rise to a
matical model, considering 90 gas phase and 32 liquid phase
complicated reaction system. During these secondary radiolysis
chemical reactions that can accurately describe the behavior of the
phenomena, the reactants undergo ioneion recombination, radi-
sulfur and nitrogen oxides subjected to electron beam irradiation.
caleneutral and radicaleradical reactions as well as molecular re-
The model is, then, used to investigate the treatment efficiency's
actions. The most complex models consulted accounted for the
sensitivity upon the main operating parameters.
occurrence of over 850 chemical reactions in the gas phase
involving more than 100 neutral and charged species [27].
2. Theoretical aspects
We started to model the gas phase processes considering the
stoichiometry proposed by Ref. [31]. Afterward, we improved our
The treatment of flue gases with electron beams is based on the
model using the stoichiometry presented in Ref. [27] and
generation of high energy electrons that ionize the components of
completed with that of [22]. This way, we assembled a model
the gas carrying the pollutants and give rise to a series of reactive
consisting of 370 chemical reactions and 70 chemical species.
species: ions, radicals, metastables, etc. These in turn react with the
main components of the flue gas (N2, O2, CO2, H2O) and promote
the transformation of sulfur and nitrogen oxides into their corre-
sponding acids. Ammonia is added to the gas stream with the aim
of neutralizing the acids to ammonia sulfate and nitrate e which
are collected in an electrostatic precipitator [6,7].
The mathematical model proposed in this work follows the
main physico-chemical phenomena occurring in both gas and
liquid phases during the irradiation treatment. The inclusion of the
liquid phase phenomena together with the thermodynamic equi-
librium between the liquid and the gas phases represents an
original approach in modeling the electron beam treatment, one
that proves relevant in the light of more recent energy-reducing
developments, i.e. introducing fine water droplets in the irradia-
tion chamber [5]. Fig. 1. Mechanism of NO removal during EBFGT treatment.
 V. Gogulancea, V. Lavric / Applied Thermal Engineering 70 (2014) 1253e1261 1255

Due to the size and stiffness of the ordinary differential
equations system describing the gaseliquid processes and the
complexity of the gaseliquid equilibrium calculations, the
resulting model required a large computational time (days, up
to one week), with the benefit of its high accuracy. In order to
reduce the computational time still keeping a good accuracy,
we performed a critical kinetic analysis of the gas-phase
system.
This way, we excluded the chemical reactions with low reaction
rates or the species with very small number concentrations. In the
process, we gradually tested the results of the trimmed system,
comparing its performance against some published experimental
results; we ended up with the present model that takes into ac-
count only 90 gas phase reactions and 40 species (see the
Supplementary material) that is able to satisfactorily predict the
aforementioned experimental results, while being computationally
affordable (tens of minutes).
Sulfur dioxide is removed in the gas phase through two main
mechanisms: radio-chemical and thermal pathways. In the radio-
chemical reaction series (Eqs. (5)e(12)), SO2 is oxidized by the
hydroxyl and peroxyl radicals to yield the HS
O3 radical. The radical
is stabilized by reaction with molecular oxygen and forms sulfur
trioxide and sulfuric acid, the latter further reacting with the added
ammonia [13,31].

Fig. 2. The solving algorithm for liquid phase phenomena.

1256 V. Gogulancea, V. Lavric / Applied Thermal Engineering 70 (2014) 1253e1261

Table 1
Experimental conditions detailed in Ref. [9].

Experimental conditions

Experiment# Temperature ( C) Humidity (%) Dose (kGy) Residence time (s) [NO]initial (ppm) [SO2]initial (ppm) NH3 ratio

1 58.6 12.0 10.0 14.43 127 383 0.92

2 59.2 10.7 10.0 14.36 171 364 0.89
3 60.4 8.6 10.2 4.11 161 673 0.89
4 54.9 8.2 10.0 13.4 129 359 0.88
5 60.3 7.7 10.1 4.05 196 467 0.88
6 59.8 7.8 2.8 4.22 182 510 0.87
7 59.1 9.0 8.0 4.03 146 462 0.93
8 59.3 8.0 10.4 4.13 158 624 0.91
9 59.0 12.4 11.4 13.78 181 358 0.9
10 60.6 10.7 12.1 14.36 168 377 0.87

SO2 þ OH þ N2 /HS O3 þ N2 (5) NH3 SO2 þ NH3 /ðNH3 Þ2 SO2 (14)

HS O3 þ OH /H2 SO4



(6) ðNH3 Þ2 SO2 þ 0:5O2 /NH4 SO3 NH2 (15)

HS O3 þ OH /SO3 þ H2 O



(7) ðNH3 Þ2 SO2 þ H2 O/ðNH4 Þ2 SO3 (16)

HS O3 þ O2 /SO3 þ HO2



(8) ðNH3 Þ2 SO2 þ H2 O/ðNH4 Þ2 SO4 (17)
The removal of nitrogen oxides has a slightly more complex



HS O3 þ HO2 /SO3 þ H2 SO5 (9) mechanism, as the pollutants simultaneously undergo oxidation
reactions e the favored removal mechanism, which ultimately
SO3 þ H2 O/H2 SO4 (10) leads to the formation of nitric acid e and reducing reactions,
promoted by the presence of atomic nitrogen and amidogen radi-

cals [22]. The schematics of the removal process are presented in
HS O3 þ O2 /HOSO2 O2 (11) Fig. 1.

H2 SO4 þ NH3 /ðNH4 Þ2 SO4 (12)

The thermo-chemical pathway is described by the set of Eqs.
(13)e(17): the reaction mechanism was initially proposed by Ref.
[13] and refined by Ref. [4]. In the absence of irradiation, the
thermo-chemical pathway is solely responsible for the removal of
sulfur dioxide, which can be as high as 40% [3].
SO2 þ NH3 /NH3 SO2
2.3. Droplet formation
To model the gaseliquid thermodynamic equilibrium and the
liquid radio-chemical reactions system, we started from the refer-
ence works of [17,24,30]. The mathematical relationships devel-
oped in these works for the sulfuric acid nucleation and gaseliquid
absorption, were tested and integrated in our mathematical model.
(13) The use of the parameterizations proposed in the referenced paper
is novel; the method of [13] was computationally exhausting.

90 100

80
NO removal efficiency (%)

SO2 removal efficiency (%)

90
70

60
80

50
Experimental Experimental
Model Model
40 70
0 1 2 3 4 5 6 7 8 9 10 11 0 1 2 3 4 5 6 7 8 9 10 11
Experiment # Experiment #

Fig. 3. Experimental vs model removal efficiencies for NO. Fig. 4. Experimental vs model removal efficiencies for SO2.
 V. Gogulancea, V. Lavric / Applied Thermal Engineering 70 (2014) 1253e1261 1257

Table 2
Model and experimental, as detailed in Ref. [9], results comparison.

Experiment# NO removal efficiency (%) Relative deviation (%) SO2 removal efficiency (%) Relative deviation (%)

Experimental Model Experimental Model

1 77.9 81.4 4.5 93.2 96.1 3.1

2 72.5 67.8 6.5 99.2 96.5 2.7
3 82.1 84.7 3.2 81 83.4 3.0
4 81 77.2 4.7 98.6 94.6 4.1
5 74 65.6 11.4 74.1 75.5 1.9
6 47.3 43 9.1 89 80.8 9.2
7 63.7 70.3 10.4 77.9 75.8 2.7
8 75.1 86.7 15.4 84.6 82.3 2.7
9 74.6 70.2 5.9 97.4 95.23 2.2
10 76.7 74.6 2.7 99.3 95.1 4.2

The H2SO4 molecules produced in gas phase rapidly gain water These species undergo dissociation phenomena Eqs. (20)e(27),
vapor and nucleate to form small H2SO4/H2O droplets, condense on modeled through the mass and charge balances for the corre-
existing particles or on the walls of the reactor and coagulate to sponding molecular and ionic species.
form larger clusters [17].
In the present mathematical model, the assumption was that H2 SO4 þ H2 O/HSO4  þ H3 Oþ (20)
the condensation and coagulation processes have much lower rates
than both the nucleation and the chemical processes, and thus, they
have been neglected. HSO4  þ H2 O/SO4 2 þ H3 Oþ (21)
For the description of the nucleation phenomena and the
composition of critical clusters, an empirical model was employed, SO2 $H2 O/HSO3  þ Hþ (22)
valid between 300 and 400 K, with sulfuric acid concentrations
ranging between 104 and 1016 molecules/cm3 and the relative hu-
midity larger than 35%. The empirical Eq. (18) was used to compute HSO3  þ H2 O/SO3 2 þ H3 Oþ (23)
the rate for nucleation, according to Ref. [24]

log Jnucl ¼ 7  64:24  4:7$RH þ ð6:13 þ 1:95$RHÞlog½H2 SO4 G HNO3 þ H2 O/NO3  þ H3 Oþ (24)
(18)
HNO2 þ H2 O/NO2  þ H3 Oþ (25)
where Jnucl is the nucleation rate for sulfuric acid, RH represents the
relative humidity and [H2SO4]G is the sulfuric acid concentration in
gas phase. NH3 $H2 O/NH4 þ þ OH (26)
The composition of the clusters was determined using the set of
parameterized equations presented in Ref. [30]. H2 O þ H2 O/OH þ H3 Oþ (27)

2.4. Liquid phase phenomena
The formation of a liquid phase leads to the absorption of several
components from the flue gas into the liquid, mainly SO2, HNO2,
HNO3, NH3, O2, (NH4)2SO4, NH4NO3, (NH4)2SO3 and NH4NO2.
Considering the relatively small concentration of these species,
Henry's Law e Eq. (19) e was applied for the modeling of the
gaseliquid phase equilibrium
ci ¼ pi $KH
where ci ethe concentration of species i in liquid (mol/L); pi e the
partial pressure of component i in gas phase (atm); and KH e
Henry's constant for species i (mol/L atm).
The accelerated electrons also interact with the liquid droplets
leading to a series of chemical reactions promoting the trans-
formation of S(IV) to S(VI) compounds, encompassing the third
mechanism for the removal of sulfur dioxide.
Even though the ratio of liquid to gas in the irradiation chamber
is relatively low (~106), the liquid processes show a significant
impact on the overall removal efficiency for sulfur dioxide and
provide a better understanding of the process.
Unlike the approach of [19], who also considered both
(19) gaseliquid phenomena, but assumed that the liquid phase is in
steady state, in our model both phases are in a dynamic regime.
This assumption leads to a system of ordinary differential equations
for the liquid phase mass balance too, as opposed to a system of
algebraic equations [19].

Table 3
Fractional simulation design.

Simulation 1 2 3 4 5 6 7 8

Case (þ,þ,þ) (þ,þ,) (þ,,þ) (þ,,) (,þ,þ) (,þ,) (,,þ) (,,)

Dose, kGy 12.2 12.2 12.2 12.2 8.2 8.2 8.2 8.2
Humidity, % 10.3 10.3 6.8 6.8 10.3 10.3 6.8 6.8
NO, ppm 193 129 193 129 193 129 193 129
SO2 efficiency, % 84.2 83.6 84 83.7 83.1 82.3 83.8 83.2
NO efficiency, % 87 98.7 85.3 97.9 65 85.1 63.3 83
1258 V. Gogulancea, V. Lavric / Applied Thermal Engineering 70 (2014) 1253e1261

Table 4
Fractional simulation results.

Simulation qDose qHumidity qNO initial Sensitivity

number (%) (%) concentration
NO removal SO2 removal
(%)
relative yield (%) yield relative (%)

1 19.6 19.8 19.9 2.7 1.0

2 19.9 16.5 0.2
3 19.8 19.9 0.7 0.7
4 19.9 15.6 0.4
5 19.6 19.8 19.9 23.3 0.4
6 19.9 0.5 1.3
7 19.8 19.9 25.3 0.5
8 19.9 2.0 0.2

3. Solving algorithm

The majority of the mathematical models to date has either an

empirical approach or only takes into consideration the gas phase
chemistry of the process. The mathematical model developed in
this work was solved using Matlab™ (MathWorks®, Natik, MA)
programming environment and was structured to describe in detail
the main phenomena involved in the treatment of flue gases with
high energy electron beams. Fig. 6. NO removal efficiency function of humidity and initial NO concentration at
different irradiation dose.

3.1. Gas & liquid phase transformations

The mass balance for each of the components (free radicals, The mass balance equations for both liquid and gas were solved
ionic species and molecular compounds in both gas and liquid together using an in-house written routine specifically designed for
phases) was written using Eq. (28), according to [31], systems of stiff ordinary differential equations.

dci 3.2. Condensation process

¼ Gi $D* $Xi þ rate of formation  rate of decomposition
dt
(28)
where ci represents the concentration of the reactive species i; D* is
the irradiation rate; Xi denotes the molar fraction of the species i
and Gi is the corresponding radio-chemical yield. The first term
accounts for the generation of reactive species via irradiation while
the rates of formation and disappearance are associated to the
chemical reactions involved in the treatment process.
After each integration step, the integrator halts and the number
and composition of sulfuric acidewater clusters freshly generated
is computed using the parameterizations presented in the previous
chapter. Subsequently, the concentrations of sulfuric acid and water
in the gas phase are adjusted to account for the nucleation phe-
nomenon and the liquid to gas volume fraction of is recalculated, as
presented in Fig. 2.

Fig. 5. SO2 removal efficiency function of humidity and initial NO concentration at Fig. 7. NO removal efficiency function of dose and initial NO concentration at different
different irradiation dose. humidity content.
 V. Gogulancea, V. Lavric / Applied Thermal Engineering 70 (2014) 1253e1261
Fig. 8. SO2 removal efficiency function of dose and initial NO concentration at different
humidity content.
3.3. Absorption phenomena
Following the nucleation calculation, the solving strategy goes
on to determine the rate at which the gas phase components are
absorbed in the liquid. To compute the number of molecules
absorbed in the liquid at the current integration time t, the Henry's
law (Eq. (19)) is the starting point. The molar concentration gets
substituted with the number concentration for the species n, (Eq.
(29)), and the value of Henry's constant is adjusted by dividing it to
Avogadro's number in an effort to reduce the computational time
(Fig. 2).
In Eq. (29), VL represents the volume of the liquid phase (cm3)
and NnLt is the number of molecules present in the liquid after the
current integration step. This number can be expressed as the sum
Fig. 9. SO2 removal efficiency function of dose and humidity at different initial NO
concentration.
1259
Fig. 10. NO removal efficiency function of dose and humidity at different initial NO
concentration.
between the already existing number of molecules absorbed in the
liquid phase ðNnL t1 Þ and the freshly absorbed molecules ðDL Þ;
n
computed according to Eq. (30) (Fig. 2).
Thus the concentration of the species in the liquid phase should
be computed using Eq. (31). For the right part of Henry's law, the
partial pressure of the gas molecules can be expressed using Eq.
t is the number of molecules of species n in the gas
(32), where NnG
phase at time t, Kgas stands for the total number of molecules in the
gas phase and psystem is pressure of the system, set at 1 atm.
Going back to Henry's law, substituting and rearranging, the
number of molecules freshly absorbed in the liquid is computed
using Eq. (33) (Fig. 2).
3.4. Dissociation phenomena
With the number concentrations of the main components
determined from the previous step, a mass and charge balance is
written in the form of a system of 15 non-linear equations, solved
using Matlab's built e in routine fsolve. The concentrations of the
species are adjusted one final time both in gas and liquid and the
stiff differential equation solver passes to the next integration step
(Fig. 2).
4. Results and discussion
The simulations of the proposed mathematical model were
compared against the experiments detailed in Ref. [9], who per-
formed a series of pilot scale tests in order to develop an empirical
model for the EBFGT. The selected experimental conditions are
presented in Table 1, keeping in mind that the experiments were
performed using double stage irradiation e thus doubling the re-
action time.
The model shows a good prediction capability, see Figs. 3 and 4,
with a mean error of 8.3% in the case of NO and 4.1% for SO2. The
comparison between the model predictions and the experimental
results obtained by Ref. [9] shows that the mathematical model is
able to predict in a consistent and accurate manner the behavior of
sulfur and nitrogen oxides when subjected to electron beam irra-
diation (Table 2).
1260 V. Gogulancea, V. Lavric / Applied Thermal Engineering 70 (2014) 1253e1261
Both modeling and experimental results show that in the case of
nitrogen oxide a steep decrease in irradiation dose is mirrored by a
similar drop in the removal efficiency (especially in the case of
simulation 6). Moreover, the increase of the irradiation dose above
the level of 10.2 kGy has only a marginal effect on the removal
efficiency for both pollutants, as seen for the tenth experiment. The
initial concentration of nitrogen oxide and the humidity percent
show marked effects on the overall efficiency of the process; the
model being in good agreement with the experimental findings e
displaying improved removal at higher humidity values (experi-
ment 1 vs experiment 4) and lower performances for high NO
concentrations.
The best agreement between the simulation results and the
experimental data are registered for the third simulation, showing
83.4% removal efficiency for sulfur dioxide, against 81% reported for
the experiment, and 84.7% for nitrogen oxide, against 82.1% ob-
tained in the experiment; the results obtained using the empirical
model proposed in the original work were 81.1% and 76.5%
respectively.
The nitrogen oxide and sulfur dioxide are removed with com-
parable efficiencies from the flue gas, mainly due to the high irra-
diation rate and suitable water vapor content of the gases. The
relatively small removal efficiency for SO2 (efficiencies as high as
95% have been reportedly obtained in industrial installations) is
explained by the reduced residence time in the irradiation cham-
ber, which diminishes the contribution of the thermo-chemical
reaction pathway.
4.1. Sensitivity analysis
In order to thoroughly investigate the sensitivity of the mathe-
matical model, a fractional factorial white experiment was pro-
posed, using the experimental conditions for which our model best
matched the experimental data (see Table 2, experiment 3). The
selected parameters are the absorbed dose, the humidity and the
initial NO concentration and their combination for the additional
simulations are presented in Table 3. Due to the lack of reliable
temperature e absorbed dose dependencies in the open literature,
the temperature was disregarded as parameter in the white
experiment we envisaged to study the sensitivity of our model to
the main operating parameters.
The sensitivity analysis results are presented in Table 4 in terms
of relative deviations q, which are computed using the relation
(34):
pm  pref
q¼ (34)
pref
where pm represents the modified value of the parameters or
yields, while pref stands for the reference values.
The results of this white experiment show that at higher levels
of irradiation, higher removal efficiencies of NOx and SO2 are ob-
tained. In accordance with literature data, our model predicts that
the sulfur dioxide is affected to a lower degree (see Fig. 5) than the
nitrogen oxide. For sulfur dioxide high removal efficiencies are
obtained using doses as low as 4e6 kGy; the removal efficiency
reaching a plateau for doses increased above this level. Overall, the
behavior of sulfur dioxide is only slightly affected by the changes in
the operating conditions, see Table 4: the highest sulfur dioxide
removal efficiency was registered for high humidity, irradiation
dose and initial NO concentration (84.2%) while the minimum
removal efficiency was 82.3%.
In contrast, the removal efficiency for NO has a significant
sensitivity to these operating parameters, as depicted in Table 4. It
significantly improved by the increase in the absorbed irradiation
dose, as seen in Fig. 6. For the irradiation dose of 12.2 kGy, the
removal efficiency has values above 85% in all cases while for the
lower doses, efficiencies as low as 63e65% are obtained. The higher
irradiation dosage promotes the formation of free radicals with
great oxidizing capacity which in turn favor a higher NO removal
efficiency.
Similarly, the increase in the humidity content of the flue gas
aids the formation of hydroxyl free radicals during the primary and
secondary radiolysis phenomena, accounting for the increase in the
removal rate of nitrogen oxide, depicted in Fig. 7. In addition to this,
the increase of humidity promotes the nucleation associated phe-
nomena and enhances the rate of the physico-chemical processes
in the liquid phase, slightly improving the sulfur dioxide removal
process as shown in Fig. 8.
The NO initial concentration is also a significant factor affecting
the removal efficiencies of the gaseous pollutants, presented in
Figs. 9 and 10. It has been proved that lower initial concentrations
of nitrogen oxide have a positive impact on the removal of nitrogen
oxide: a lower initial number of NO molecules leads to a higher
efficiency for the interactions between them and the oxidizing
radicals responsible for their removal, resulting in a better perfor-
mance for the NO abatement. However, the sulfur dioxide's removal
is negatively impacted as the pollutants interact with each other
during the irradiation treatment and the decrease in the initial NO
concentration is followed by a decrease in the rate of these mo-
lecular interactions.
5. Conclusions
The results obtained from the proposed new mathematical
model are in good agreement with published experimental data
from literature. The model predicts with good accuracy the per-
formances obtained experimentally for a relatively large array of
operating conditions: in the majority of cases the departure model
e experiment is within the experimental error range. Moreover, the
model is more accurate in predicting the sulfur dioxide behavior, as
its removal pathway, despite being more complex, involves fewer
radio-chemical reactions.
In the best case scenario, the predicted nitrogen and sulfur ox-
ides' removal efficiencies are very similar to those obtained
experimentally for a residence time of 4.11 s and an irradiation dose
of 10.2 kGy being closer than those predicted by the empirical
model in the case of nitrogen oxide. Nitrogen oxide's slightly better
removal can be explained by the low initial concentration of this
pollutant and the high irradiation rate.
The factorial white experiment has proved the capacity of this
new mathematical model to capture the sensitivity of the process,
showing that both these parameters have a marked effect on the
removal efficiency of the nitrogen oxides: even small positive var-
iations in initial pollutant concentration (in the range of tens of
ppm) lead to significantly poorer performance for the process, in
good agreement with the experiments.
The increase in irradiation dose and humidity content have a
notable beneficial effect on the abatement of nitrogen oxide from
flue gases, the former being almost entirely removed from the gas
in the most favorable scenario (high humidity and irradiation dose
and low initial concentration).
However, increasing the irradiation dose has a negative effect on
the energy consumption of the process and may lead to mainte-
nance problems for the accelerators in the long-run. In addition to
this, the water vapor content reduces the temperature of the flue
gases and poses problems for the equipment, both factors leading
to greater operating and investment costs.
The sulfur dioxide's removal efficiency shows small improve-
ments with the increase of irradiation dose and humidity content of
 V. Gogulancea, V. Lavric / Applied Thermal Engineering 70 (2014) 1253e1261
the flue gases. The removal of sulfur dioxide is negatively impacted
by the addition of a less than stoichiometrical quantity of ammonia,
the small nitrogen oxide initial concentration and the relatively
short residence time.
The new mathematical model proposed for characterizing the
abatement of sulfur and nitrogen oxides can predict in a consistent
manner the overall process efficiency of the irradiation beam
treatment for flue gases while showing appropriate sensitivity
against the main operating parameters.
Appendix A. Supplementary material
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.applthermaleng.2014.05.046.
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