Contrib. Plasma Phys. 54, No. 2, 187 201 (2014) / DOI 10.1002/ctpp.

201310063

Atmospheric Pressure Plasma Application for Pollution Control

in Industrial Processes
Th. Hammer
Siemens AG, CT RTC PET, Erlangen, Germany
Received 13 August 2013, revised 06 September 2013, accepted 25 September 2013
Published online 10 February 2014
Key words Non-thermal plasma, pollution control, nitric oxides; sulfur dioxide, electrostatic precipitatio,
corona discharge, dielectric barrier discharge, dielectric packed bed reactor, plasma-catalytic reactions,
electro-hydrodynamics.
Economic application of atmospheric pressure plasma technology for industrial pollution control requires fullling two propositions: First application of pollution control technologies needs to result in clear environmental, health, or safety benets motivating political measures. Second plasma technology needs to be competitive
as compared to other available pollution control technologies. Thus in this article methods for the evaluation of
atmospheric plasma application for industrial pollution control are reviewed: Examples of emission regulations
and emission control technologies are given. Requirements of industrial scale emission control and of thermal and non-thermal exhaust gas treatment technologies are described. The potential of various non-thermal
plasma reactor concepts for cost effective treatment of industrial scale gas ows is analyzed, and methods for
the evaluation of plasma energy balance and plasma chemical kinetics are given for them. How to deal with
shortcomings of atmospheric pressure plasmas such as lack of plasma-chemical selectivity is addressed in a
section about plasma-catalytic hybrid processes. Further the progress made recently in electrostatic precipitation is reviewed, and the importance of electro-hydrodynamic effects for the reactor design both for electrostatic
precipitation and for plasma chemical pollution control is considered.
c 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim


1 Introduction
Health- and environmental effects of industrial pollution of air and water had been recognized soon after beginning of industrialization. In several cases local, regional, or national regulations forced plant owners to take
responsibility for the damage caused by noxious plant emissions [1]. Since in the beginning of industrialization
coal was the dominating fuel, the most obvious emissions were those of particulate matter and sulfur dioxide.
Thus wet scrubbing for ue gas desulphurization (FGD) was one of the early pollution control technologies developed as early as 1850 [1]. However, rst large scale application did not happen before 1931, when Battersea
Power Station in Great Britain was equipped with an FGD. Widespread application of industrial pollution control
technologies was enforced by legislation in a lot of countries all around the globe starting in the 1970s. This
did not only promote FGD but also led to widespread introduction of electrostatic precipitation (ESP) for the
emission reduction of solid and liquid particulate matter from industrial processes and power generation [2-5]
and selective catalytic reduction (SCR) of nitric oxides emitted by combustion processes in thermal power plants,
stationary and mobile internal combustion engines and so on [6-9]. It is interesting to note that in a lot of industrial processes mechanical ltering using e.g. baghouse lters or candle lters turns out to be not economical for
gas cleaning because of the back pressure introduced by these mechanical means. The development of electrostatic precipitation (ESP) for industrial separation and gas cleaning by Cotrell in 1907 described in his US-patent
no. 895,729 [10] thus can be seen as important step for efcient, atmospheric pressure plasma based particulate
matter emission reduction from industrial sources. The efciency and reliability of ESP technology had been
increased over decades by improving ESP design, insulator materials, and power supply concepts.
In the recent decades various atmospheric pressure plasma applications were investigated going far beyond
electrostatic precipitation applied in energy generation and industry. These investigations were motivated by

Corresponding author. E-mail: thomas.hammer@siemens.com

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Th. Hammer: Atmospheric pressure plasma application for . . .

rapid propagation of Diesel engines in cars, especially in Europe, by emission regulations requiring emission
reduction of nitric oxides (NOx ), sulfur dioxide (SOx ), mercury (Hg), volatile organic compounds (VOC), and
particulate matter (PM), in particular Diesel soot, from mobile engines and stationary sources in industry and
energy generation, the propagation of decentralized renewable energy generation, sustainable energy & fuel
conversion processes, and ground water clean-up [11].
However, it needs to be pointed out that economic application of atmospheric pressure plasma technology
for industrial pollution control requires fullling two propositions: First of all there needs to be a clear environmental, health, or safety benet motivating legislation to set regulations into force promoting pollution control
technologies. Second plasma technology needs to be competitive as compared to other available pollution control technologies. A decision about competitiveness may be met based on criteria such as removal or conversion
efciency of the pollutant, selectivity of the removal of conversion process, side effects such as formation of unwanted by-products, energetic efciency, operation and maintenance costs, and nally the investment required.
In this article a short review of methods for the evaluation of atmospheric plasma application for industrial
pollution control is given. It is introduced by examples of emission regulations and emission control technologies.
This is followed by considerations of the requirements of industrial scale emission control and of thermal and
non-thermal exhaust gas treatment technologies. Then examples of non-thermal plasma reactor concepts and
methods for the evaluation of plasma energy balance and plasma chemical kinetics are given. How to deal with
shortcomings of atmospheric pressure plasmas such as lack of plasma-chemical selectivity is addressed in a
section about plasma-catalytic hybrid processes. Further the progress made recently in electrostatic precipitation
is reviewed, and the importance of electro-hydrodynamic effects for the reactor design both for electrostatic
precipitation and for plasma chemical pollution control is considered.

2 Emission Regulations and Control Technologies

Both in USA and in Europe Union pollutant emissions of industrial processes, in particular of combustion plants,
of fossil fuelled thermal power plants, and of gasoline or Diesel fuelled cars and trucks are limited by emission
regulations setting upper limits for the states of USA or countries of the European Union, respectively. These are
published e.g. on the web pages of the European Union [12] and of the US Environmental Protection Agency
[13]. On a global level the environmental, health, and safety guidelines of the International Finance Corporation
(World Bank Group) may be considered as a basis for setting emission limits [14].
It is a common procedure to relate emission limit values (ELV) to a certain O2 -concentration of the dried
exhaust gas depending on the source of emissions and type of fuel. Thus for comparison with ELVs care needs
to be taken for normalizing measured concentration values to the O2 -concentration corresponding to emission
source and fuel type using the following relation:
 


d,N
d,air
d,air
d
/ XO2
(1)
Xid,N = Xid XO2
XO2
XO2
d
are the
where indices d, N and i designate dry gas, normalized value, and compound, respectively. Xid and XO2
d,N
d,air
molar fractions of compound i and oxygen measured in dried exhaust gas. XO2 and XO2 = 0.2095 are the
molar fractions of O2 given as a reference value and in dry air, respectively.
Single states of the USA such as California are known to have much more stringent regulations than those set
by US EPA, and the same applies for some countries of the European Union. Stationary gas turbines for energy
generation, for example, need to comply with an NOx-emission limit of 50 mg/Nm3 (operation with natural gas,
emission normalized to 15 % O2 ) according to the regulations of the European Union, which can be achieved
without any exhaust gas after-treatment using dry, low NOx (DLN) combustion technology. The regulations set
by US EPA, however, require NOx-emissions being below 5 ppmvol (single cycle power plant, power > 10 MW,
permit condition for > 877 hrs/yr operation with natural gas; emission normalized to 15 % O2 ). Such low
emissions can only be achieved applying after-treatment technologies such as selective catalytic reduction of the
nitric oxides using V2 O5 /WO3 /TiO2 -catalysts and ammonia as a reducing agent. Since often most of the NOx is
emitted as NO, the SCR process can be described by the following reaction equation:

4 NO + 4 NH3 + O2 4 N2 + 6 H2 O
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(2)
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Depending on the V2 O5 content of the V2 O5 /WO3 /TiO2 -catalyst this reaction reduces NO efciently for temperatures between 250 C and 550 C. Too high temperature causes oxidation of the ammonia used as reducing
agent reducing the chemical efciency and in the worst case generating NO. If substantial fractions of the NOx
are emitted as NO2 , either because of special properties of the combustion process or because of conversion
processes induced by a catalyst or non-thermal plasma, additional reactions have to be taken into account [16],
[17]:
NO + NO2 + 2NH3 2N2 + 3H2 O

(3)

6NO2 + 8NH3 7N2 + 12H2 O

(4)

2NO2 + 2NH3 N2 + H2 O + NH4 NO3

(5)

Reaction (3) enables low temperature SCR down to temperatures as low as 140 C and is known as fast SCR reaction. Under typical SCR operation conditions, where the catalyst temperature exceeds 200 C and a substantial
fraction of the NOx is emitted as NO [18], reactions (4) and (5) are slow compared to (2) and (3). However, in
case of high NO2 concentrations and low temperatures these reactions increase ammonia consumption and cause
formation of the unwanted aerosol ammonium nitrate, respectively.
Similarly, emission limits apply for SO2 -emissions. Since the source of SO2 -emission is the fuel itself, the
most economic way reducing SO2 -emissions of gas turbines is desulfurizing the fuel. In cases where fuel desulfurization cannot be applied or is not economical, wet ue gas desulfurization (FGD) is utilized. An example of
wet FGD process is given by the following reactions:
CaCO3 (solid) + SO2 CaSO3 (solid) + CO2

(6)

1
(7)
CaSO3 (solid) + H2 O + O2 CaSO4 (solid) + H2 O
2
Here aqueous limestone slurry is utilized to bind the SO2 in a rst step forming calcium sulte, which then is
oxidized to calcium sulfate (gypsum).
High hydrocarbon- (UHC) and carbon monoxide (CO) emissions indicating incomplete combustion of the
fuel can occur in case of low part load operation of gas turbines. These emissions can be reduced by means of
catalytic oxidation using precious metal catalysts.
UHC + O2 CO2 , H2 O

(8)

1
CO + O2 CO2
(9)
2
Since, however, incomplete combustion results in reduced efciency of power generation, the preferred solution
is optimizing the gas turbine combustor such that very low unburned hydrocarbon (UHC) and CO base load
emissions < 3 ppmvol are achieved.
Emission regulations for cement kilns do not only cover NOx, SOx, and dust, but also heavy metals, and in
case of hazardous waste combustion plants emissions of HCl, HF, volatile organic compounds (VOC), polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD, PCDF) are also limited [15]. A lot of these
emissions can be reduced using wet scrubbing, electrostatic precipitation, and selective catalytic reduction. However, in some cases such as elemental mercury emission adsorption and ltering methods causing high operation
and maintenance costs have to be applied in addition to established technologies. These usually are the cases were
non-thermal plasma technology may offer promising solutions such as the multi-pollutant control technology for
utility boilers developed by Powerspan Corp. [19].

3 Non-Thermal Plasma Process Requirements

In order to get an idea of the basic requirements for the application of non-thermal plasma based emission control
technologies in industry, pollutant concentrations and ue gas ow rates need to be known. Pollutant concentrations depend very much on the industrial processes considered. The ow rates of combustion ue gases of
industrial processes, however, can very often be related to the thermal power of the combustion process utilized:
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This is shown for the combustion of natural gas (mainly consisting of CH4 ) and coal (here assumed to be pure
carbon) in 4: Fuel rich combustion characterized by fuel-to-air equivalence ratio > 1 is avoided because of
incomplete combustion caused by lack of oxygen. For equivalence ratios 0.65 < < 1 the high adiabatic ame
temperature results in high thermal NOx-formation rates such that NOx-emission limits are exceeded. A lower
limit for is given by the lower ammability limit of the fuel, which in case gas turbine combustion of natural
gas, depending on the temperature, is around 0.3. Thus as a rule of thumb a natural gas combustion process
providing a thermal power of 1 MW can be associated with a ue gas mass ow rate of 2500 kg/h or a volume
ow rate of 2000 Nm3 /h. For coal and oil slightly lower mass ow rates are to be expected.

Fig. 1 Flue gas mass ow rate Qm and adiabatic ame temperature T as a function of the fuel-to-air equivalence ratio
obtained from numerical simulation of equilibrium thermodynamics [20]. The fuel ow rates were kept constant at 72 kg/h
and 85 kg/h for CH4 and carbon, respectively, corresponding to a thermal power of 1 MW. Red shaded area partial oxidation,
blue shaded area high ame temperature causing high NOx-emissions.

From the mass ow rate and the required residence time of ue gas in a ue gas treatment reactor the reactor
volume can be estimated. Catalytic reactors e.g. are designed based on temperature and space velocity (being the
inverse of the residence time). SCR-reactors are typically operated at space velocities ranging from 20,000 h1 to
50,000 h1 . Thus the volume of an SCR-reactor needs to be 0.04 to 0.1 m3 /MW of thermal power. Non-thermal
plasma reactors applied for plasma enhanced SCR have successfully been operated at space velocities ranging
from 150,000 h1 to 1.43 Mio h1 [21-23]. Thus in case of plasma assisted catalytic processes the challenges
are not the size of the plasma reactor but, as will be seen below, more the electrical power supply and special
electrically insulating materials.
For the process economy of a non-thermal plasma induced process as compared e.g. to a thermal catalytic
one the energetic requirements need to be considered. Even in case of an exothermal reaction a certain activation
energy is required to overcome the reaction barrier. In case of a thermal process this is done by gas heating. The
thermal power required can be estimated by
Pth = Qm cp T ,

(10)

where Qm is the mass ow, cp the specic heat of the gas mixture, and T the temperature increase required.
Since the specic heat of combustion exhaust is typically in the range of 1 kJ/kg K, a temperature difference of
100 K corresponds roughly to specic energy requirement of 100 kJ/kg exhaust.
A non-thermal plasma induced chemical process typically is characterized by radical formation from one of
the major compounds contained in the gas passing the plasma reactor followed by chemical reactions of these
radicals with the pollutant to be removed and with scavengers [24]. In the case of 1st order reactions the specic
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energy being required for e-fold concentration reduction of the pollutant is

=

1
(kd np + ks ns ) ,
kd G

(11)

where kd is the rate coefcient for pollution destruction, np is the number density of the pollutant molecules, ks
is the scavenging rate coefcient, ns the scavenger number density, and G is the radical production efciency of
the non-thermal plasma. From this specic energy the plasma input power can be obtained using
PN T P Qm .

(12)

In case there are no scavengers in the gas mixture this simplies to

PN T P Yp

Qm
,
G

(13)

where Yp is the mass fraction of the pollutant. An upper limit for the radical production efciency is given
by the reaction enthalpy of the radical formation reaction, which e.g. in case of oxygen dissociation is 249.18
kJ/mole of oxygen radicals generated [25]. For a pollutant concentration of 100 ppmvol and 20 % efciency of
oxygen radical generation in lean combustion exhaust eq. (12) yields a specic energy requirement of 7.8 kJ/kg
of exhaust gas.
Thus non-thermal plasma treatment may be economically benecial as compared to thermal treatment as long
as the plasma power is small compared to the thermal power:
PN T P  Pth or Yp

Qm
 Qm cp T .
G

(14)

For the examples given above this relation obviously is fullled. In general this relation means that for low pollutant concentrations and sufciently high radical formation efciencies non-thermal plasma treatment is energetically more efcient than thermal treatment, whereas in case of high pollutant concentrations thermal treatment
may be preferred, especially when the temperature increase required is low or heat at the required temperature
level is available anyway.
However, the chemical kinetics of the non-thermal plasma process needs to be investigated carefully not only
for scavenging increasing the energy demand but also for chain reactions decreasing the energy demand: A
good example is given e.g. in non-thermal plasma treatment of Diesel exhaust, where the presence of unburned
hydrocarbons may decrease the energy demand by more than a factor of 10 [26].

4 Non-Thermal Plasma Reactor Concepts

Several non-thermal plasma reactor concepts had been proposed for the plasma-chemical treatment of industrial
exhaust gases (see e.g. [27, 11]):
The dielectric barrier discharge (DBD) reactor is widely used for generation of ozone [28] and recently has
been applied for exhaust gas treatment in mobile applications [22] as well as in some industrial applications
[29]. In dielectric barrier discharge reactors the direct current ow is impeded by at least one electrically insulating barrier between the electrodes providing the external electrical potential. Thus the electrical circuit of the
discharge reactor can be represented by the capacity of the dielectric barrier being in series with the discharge
gap represented by the variable ohmic impedance of the gas discharge plasma paralleled by the capacitance of
the discharge. Due to the capacitive coupling of the electrical current to the discharge gap DBD reactors have
to be operated with AC or pulse repetitive voltages. However, charging of the barrier capacity by the gas discharge current quenches the gas discharge plasma some 10 ns after initiation so that self pulsing occurs. Due to
this self-pulsing mechanism good plasma-chemical efciency can be obtained using relatively simple, low cost
power supplies. Atmospheric pressure DBDs usually are lamentary. However, in certain gas mixtures a quasihomogeneous glow mode can be observed [30, 31], and in some cases self organization causes regular patterns
being formed by the laments [32]. Since the plasma-chemical efciency of DBD reactors decrease with increasing discharge gap, typical discharge gap widths are in the range of a few mm, only. When pulsed excitation with
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sub-microsecond rise time is applied, the discharge gap of DBD-reactors can be increased from typically 1 mm
to about 1 cm without loss in plasma chemical efciency [33]. Nevertheless, the treatment of industrial scale gas
ows requires a lot of paralleled discharge gaps in order to keep the ow resistance low. Further reliable operation
requires high quality, low dielectric loss barrier materials having a dielectric strength > 10 kV/mm and high bulk
resistivity > 108 /cm. In the case of low temperatures polymeric barrier materials such as PTFE can be used.
For exhaust gases having temperatures > 100 C, however, rather expensive densely sintered ceramics or quartz
glass barriers are required. An advantage of DBD reactors is that barriers having certain catalytic properties can
be utilized for plasma catalytic hybrid treatment of gases [34].
The most widely investigated concept for plasma-catalytic reactions is the dielectric packed bed (DPB) reactor consisting of a discharge gap lled with pellets having a high dielectric permittivity and certain catalytic
properties [35]. Due to the enhancement of the electric eld in the vicinity of contact points of the randomly distributed pellets the non-thermal plasma is generated in contact with the pellet surfaces. Recently great progress
has been achieved both in understanding some basic mechanisms of plasma catalysis and in obtaining highly efcient plasma-catalytic oxidation of VOCs in laboratory scale experiments. Nevertheless, long term, large scale
application has not yet been demonstrated.
The pulsed corona discharge (PCD) reactor makes use of a corona discharge between a sharp edged and a
smooth electrode as in the ESP. However, in the ESP excited by DC voltage the active gas discharge volume
(characterized by net ionization) is very small compared to the reactor volume even when it is operated close to
the sparking limit. Using high voltage pulses having sub-microsecond duration spark over can be avoided, and
a non-thermal plasma lling the reactor volume to a high degree is obtained. Since discharge gaps of several 10
cm can be used, the PCD reactor is ideal for treatment of very large gas ow rates [36-38]. The costs of the PCD
reactor are low compared to a DBD reactor for the same gas ow rate, however, the development of cost effective
pulsed power supplies is challenging. Further for good efciency and long lifetime of the power supply care has
to be taken for good electrical matching between power supply and reactor [39].
Electron beam treatment is based on irradiation of the gas ow by high energy electrons being generated in
ultra high vacuum accelerators with voltages ranging from 60 kV to some MV and transmitted into the gas ow
e.g. through titanium foils [40]. Each of the primary beam electrons generates a large number of secondary
electrons in ionizing collisions, which have the right energy for efcient radical generation nally resulting in
pollutant destruction [41]. Here the challenge is the stability of the e-beam transmission window being typically
10 m thin under the harsh industrial operation conditions. Further the regulations for working with ionizing
radiation have to be obeyed.
Finally there had been attempts to increase the selectivity of non-thermal plasma processes by selectively
generating radicals in a single gas and injecting those radicals into the gas ow to be treated. In the corona
radical shower system an additive is fed into the corona reactor through sharp edged pipes acting as corona
electrodes such that radicals are selectively generated from the additive injected [42]. Plasma jets can also be
used for selective radical injection [43].

5 Evaluation of Plasma Chemical Efciencies

The efciency of non-thermal plasma induced chemical processes can be evaluated from the average plasma
input power and species conversion (formation or removal) efciencies. In case of the AC voltage excited DBD
or DPB reactor the average plasma input power can be obtained from reactor charge Qel and voltage U measured
over one full period 2/ of the applied voltage (Lissajous gure method):


PN T P =
Qel (U ) dU .
(15)
2
In case of pulsed repetitive excitation independent of the reactor concept (DBD, DPB, and PCD) the average
plasma input power can be obtained from time resolved measurement of reactor current I(t) and voltage U (t):
PN T P

pr
=
2


pulse

U (t) I (t) dt .

(16)

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The integral has to be performed over the complete pulse duration. Further care needs to be taken for the correction of phase shifts introduced by voltage and current transducers, especially when dealing with pulses having
ns rise time. The method for average plasma input power evaluation related to eq. (16) can also be applied in
case of AC excitation if current and voltage can be recorded with sufciently high time resolution. In this case
integration needs to be performed over one period of the applied voltage. With the exception of dielectric barrier
or pellet materials having substantial dielectric losses there is no need for calculation of the voltage drop at the
discharge gap prior to evaluation of eq. (15) or eq. (16) because integration of the reactive power over one period
(or the pulse duration) of the applied voltage yields 0. In case of dielectric losses, however, a barrier model needs
to be applied in order to separate the power dissipated in the barrier and the plasma input power [44].
Chemical conversion efciencies
i = 1 Yi /Yi0

(17)

are evaluated from species concentrations (mass fractions) before and after plasma treatment Yi0 and Yi measured
by means e.g. of Fourier transform infrared absorption spectroscopy, gas chromatography, mass spectroscopy,
or laser spectroscopy. Other than specic sensors all these methods allow measuring not only the conversion of
species being in the focus of investigation but also formation of unwanted by-products. This exibility is paid
with complexity requiring well trained staff operating these gas analyzers.
The energetic conversion efciency is given by


yi = Yi0 Yi Qm /PN T P .
(18)
The specic energy cost of plasma chemical conversion is the inverse of energetic conversion efciency. Finally
the selectivity of a plasma chemical conversion process forming a species j by conversion of a species i is given
by

 

sji = Xj Xj0 / Xi0 Xi
(19)
0
where Xi,j
and Xi,j are the initial and nal molar fractions of the species considered. It can easily be seen that
precision and repeatability of species concentration measurements are crucial for the determination of reliable
efciencies, especially in case of small chemical conversion efciencies.

6 Thermal Effects
In spite of the efcient coupling of electrical energy into electronic excitation, ionization, and dissociation of
molecules thermal effects of non-thermal plasma treatment should not be neglected: Even in the case of sufciently high reduced electric elds the fraction of energy supplied to vibrational excitation of molecules in a
non-thermal plasma may be substantial. 2 shows the results of numerical simulation of electron energy distribution function and electron collision reaction rate coefcients in synthetic air using the Boltzmann code contained
in the Chemical Workbench software suite [45] and the compilation of electron collision cross sections of A.V.
Phelps [46]: At the critical reduced electric eld strength of 100 Td (1 Td = 1021 Vm2 ) nearly 60 % of the
energy is transferred to vibrational excitation of N2 which is known to be converted to heat by means of V-Tcollisions. Both from numerical simulation [47] and from spectroscopic investigations [48] it is known that the
reduced electric eld in streamer heads can exceed 800 Td. However, in the streamer channel reduced electric
eld strengths being 10-20 times lower than in the streamer head were found in these investigations. Plasmachemical ozone generation efciencies in oxygen and air [28] and energetic efciencies of NO-reduction in N2
investigated both in DBDs and PCDs [49] could well be described by average reduced electric elds between 150
Td and 200 Td. Thus it is reasonable assuming that a substantial fraction of energy being supplied to the streamer
of a PCD or the discharge lament of a DBD results in vibrational excitation of N2 . Further the gas is heated
due to recombination reactions and quenching collisions [50, 51]. Thus typically 30 % of the plasma energy is
converted into heat. For DBD in air e.g. operated with a specic plasma input energy density of 100 J/liter a gas
heating of about 30 K would be expected. However, in laboratory scale non-thermal plasma experiments very
often gas heating is not observed because of heat transfer resulting in cooling. In a thermally insulated dielectric
packed bed reactor operated at high specic plasma input energy density gas heating was indeed observed [34].
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Fig. 2 Fraction of electron energy supplied to inelastic processes in synthetic air as a function of reduced electric eld
(1 Td = 1021 Vm2 )

7 Numerical Simulation of Non-Thermal Plasma Processes

Numerical simulation may be helpful for designing non-thermal plasma reactors, matching power supplies, and
understanding chemical kinetics induced by non-thermal plasma.
Electronic properties of gas mixtures can be simulated solving the Boltzmann equation [52, 53]. Coupling
this with the solution of the Poisson equation and a breakdown model [54], initiation voltages of electrical gas
discharges can be simulated [55-57].
Plasma chemistry can be simulated by adding electronic reactions and rate coefcients to the mechanism
treated by a chemical rate equation solver. Finally the electrical circuit differential equations may be treated in
the same way as the chemical reaction differential equations. For several of these tasks commercial computer
codes [20] or public domain codes [58], [59] are available. Getting the input data for electronic collisions may
be more challenging. For selected species data bases of electronic collision cross sections are available [60].
Before complex plasma-chemical conversion processes e.g. of Diesel- or gasoline exhaust [26] in DBD- or
PCD-reactors are simulated, characterization of the reactor using a simple conversion process with reasonably
well known chemical kinetics should be performed. Such a process can for example be the plasma-chemical
reduction of NO in N2 [49]. Peroxy radical reactions turned out to be important for understanding plasmachemical conversion of nitric oxides in exhaust gases containing hydrocarbons [61, 62]. Here publications and
databases of the combustion community can provide valuable information [63, 64].

8 Plasma-Catalytic Hybrid Processes

Plasma-catalytic hybrid processes had widely been investigated for the treatment of automotive lean burn combustion exhaust gases (see e.g. [65, 66], [16, 17, 21]). However, all these investigations had been performed in
the so called 2-stage reactor set-up, where non-thermal plasma pre-treatment of the exhaust gas, in some cases
being enriched with a hydrocarbon such as propene, results in formation of meta-stable intermediate compounds
promoting the catalytic reduction of nitric oxides in a catalytic reactor arranged ow-down of the non-thermal
plasma reactor over a wide range of temperatures.
Demonstrating the benet of the 1-stage reactor set-up targeting on plasma assisted catalysis (catalytic reactions promoted by plasma processes) turned out to be much more challenging [67-69]. However, H.-H. Kim
and A. Ogata [35] could show that ceramic pellets having a nano-dispersed metallic catalyst on the surface are
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not only superior with respect to catalytic activity but also enable formation of a non-thermal plasma covering
the pellet surfaces nearly homogeneously. This homogeneous distribution nally was the key to successful destruction of VOCs by means of plasma assisted catalysis. They further developed a 2-step process (Figure 3)
avoiding the formation of nitric oxides, which usually results from non-thermal plasma treatment of polluted
air when specic input energy densities of 50 J/liter are exceeded: In the 1st step VOCs are removed from the
exhaust gas fed e.g. through reactor DPB 1 by means of adsorption on bed 1 providing both sorbent and catalyst
properties. When the capacity of the sorbent is exhausted, the gas ow is switched over to reactor DPB 2 and
DPB 1 is regenerated. For this purpose oxygen is fed to DPB 1 and plasma power is supplied. This results in
very efcient plasma-catalytic oxidation of the VOCs without formation of unwanted by-products such as nitric
oxides or particulate matter. Numerous sorbent-catalyst combinations were investigated. For the adsorption and
decomposition of benzene Ag/HY-zeolite showed a very good performance.

Fig. 3 Schematic diagram of a cycled system for VOC removal from exhaust gas.

Pulsed corona discharges enable treatment of large gas ows without imposing a substantial pressure drop.
However, the availability of efcient, reliable, cost effective pulsed power supplies had been an issue for several
decades. Using high voltage pulsed power supplies switched by means of rotating spark gaps (typical scheme
shown in Figure 4) nanosecond rise time pulses were generated [70] allowing efcient destruction of VOCs in
PCD reactors. Other plasma-based switching elements such as triggered spark gaps, thyratrons, and pseudosparks also were successfully applied. Sophisticated methods for matching the pulsed power supply to the PCD
reactor had also been developed [39], but even in case of good matching the limited lifetime of the plasma based
switching element remained an issue.

Fig. 4 Scheme of a PCD reactor with rotating spark gap (RSG) switched power supply.

Recently semiconductor based circuit schemes supplying the corona discharge reactor either with superimposed DC- and AC-voltages [71] or with superimposed DC- and pulsed repetitive voltages [72] (see Figure 5)
were developed. These concepts are typically based on slowly charging a capacity (2x200 nF) on the primary side
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of a pulse transformer (ms timescale), discharging the capacity using a semiconductor switch (IGCT) on the s
timescale, transforming the pulse by means of the pulse transformer PT1 having parasitic inductivity Lp, capacity
Cp, and ohmic impedance Rp, sharpening the transformed pulse (secondary side of PT1) to sub-s duration using
a saturable inductor (MS 1), and impedance matched capacitive coupling (cable & load resistor, 10nF capacity)
of the sub-s pulse to the corona discharge reactor represented by the constant capacity of the discharge gap Cr
and variable (ohmic) discharge impedance Rrp and capacity of the space charge region Crs, respectively. The DC
bias voltage is coupled to the corona discharge reactor resistively (200k) in order to block voltage pulses from
the bias voltage power supply. Superimposed DC- / pulsed repetitive excitation obviously results in a glow-like
discharge having very high lament density (Figure 6).

Fig. 5 Circuit scheme of a corona discharge reactor excited by superimposed DC- / pulsed repetitive voltage (Siemens AG).

Fig. 6 Corona discharges generated in a wire-plate reactor

(slightly inclined end-on view) (a) with superimposed DC- /
pulsed repetitive excitation and (b) with DC-excitation, only.

Plasma-chemical characterization of the corona discharge reactor with superimposed excitation was performed
by means of ozone generation in synthetic air (80 % N2 , 20 % O2 ), where the chemical kinetics was reasonably
well known. For interpretation of the measurements numerical simulations were performed Chemical Workbench
2.5 [45]: In a rst step electron collision reaction rate coefcients were calculated as a function of reduced electric
eld using the integrated Selena module and the electron collision cross sections of Phelps compilation [46]. The
G-values (number of reactions per 100 eV of plasma input energy) were transferred into the Radiation Chemistry
Reaction (RCR) module containing an extended kinetic model of ozone formation (see e.g. Kogelschatz [28])
including side reactions forming e.g. nitric oxides. A typical result is shown in Figure 7.
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Fig. 7 Results of numerical simulation of ozone formation in synthetic air performed with Chemical Workbench 2.5 [45]:
Reduced electric eld 120 Td, pulse duration 1000 ns, rise/fall time 100 ns, dose rate 46.7 J/kg ns.

In a rst series of tests the pulses superimposed on the DC-voltage had a relatively low pulse energy of 15
mJ, only. This resulted in a disappointingly low ozone yield of about 20 g/kWh (Figure 8). Interpretation of
these results by means of numerical simulation indicated that the average reduced electric eld at which radicals
were generated was about 120 Td, which is roughly 15 % above the critical electric eld of 105 Td. Thus
it was concluded that in these experiments the corona discharge was dominated by DC-excitation and higher
pulse voltage amplitudes would be required in order to increase the energetic ozone yield. From experiments
performed with an improved power modulator indeed higher ozone yields of 42 g/kWh (superimposed DC /
pulse excitation) and 61 g/kWh (pulse excitation, only) were obtained (Figure 9). Thus pulsed excitation results
in highest energetic efciency. However, there is still potential for improvement of corona excitation by means of
superimposed DC- / AC-voltage and superimposed DC- / pulsed repetitive voltage. Further due to the high prices
of pulsed power supplies superimposed excitation is expected to have an economical advantage.

Fig. 8 Ozone concentration as a function of specic plasma input

energy density: Comparison of experiment (18 kV, 6 mA DC superimposed with 1 s long pulses having a pulse energy of 15 mJ and a
repetition frequency of 5 kHz, gas ow rate varied from 10 Nl/min to
180 Nl/min) and numerical simulation (reduced electric eld 120 Td).
www.cpp-journal.org

Fig. 9 Ozone concentrations achieved with an improved power modulator design as a function of
specic plasma input energy density: Filled symbols superimposed DC / pulse; open symbol
pure pulse excitation.
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Provided, that the development of power supplies makes further progress, there may be good opportunities
for corona plasma-chemical treatment of industrial exhaust gases. In a review presentation given in 2012 Keping
Yan showed that there is an unbroken trend of exponential increase of the mass ow rates of industrial exhaust
gas treated in corona plasma pilot plants from some 100 Nm3 /h in 1990 to > 100,000 Nm3 /h in 2010 [73].
It should be mentioned that application of superimposed DC / pulsed repetitive / high frequency AC voltages
results in improving the efciency of existing ESP installations. Since in a lot of countries around the world there
is a need for increasing dust removal efciencies in industry and power generation from coal [73] retrotting ESP
power supplies and control systems is a very attractive option.

9 Utilization of Electro-Hydrodynamic Effects

For a long time electro-hydrodynamic (EHD) effects had been assumed to inuence the efciency of electrostatic
precipitation. Indeed such effects on static or owing gases known as ionic wind, electric wind, or coronal wind
are known for centuries [74]. Flow velocities induced by EHD actuators in a resting gas can exceed 3 m/s [75].
Nevertheless, systematic utilization of EHD effects for industrial scale gas cleaning and separation processes can
be considered to be just at the beginning:
Recently ow elds in narrow ESP ducts were analyzed using particle image velocimetry (PIV) [76]. This
laser diagnostic tool combining double pulse illumination of small particles being carried by the gas ow with
two dimensional imaging and computer based image processing allows evaluating the gas ow vectors in the
complete cross section of the duct with 1 ms time resolution a feature being essential for analyzing turbulent
ow phenomena. The authors were able to show that in a duct having a central corona wire in a quadratic cross
section vortices developed in the corners of the quadratic cross section whereas in the remaining parts of the
cross section the radial transport of particles was very intensive. In case of a corona wire centered in a cylindrical
duct vortices didnt develop, and the radial particle transport had lower intensity. For the same electrical power
supplied the precipitation efciency in the quadratic duct cross section was substantially higher than in the circular
duct cross section.
Another example of EHD effects on gas treatment is given in the conference contribution of Jolibois, Takashima,
and Mizuno [77] reporting efcient NO conversion to NO2 in an asymmetric dielectric barrier surface discharge
reactor. An analysis of the experimental set-up (Figure 10) and of the experimental conditions revealed that the
high NO to NO2 conversion efciencies (nearly 100 %) observed in these experiments can only be explained
when intense transport processes take place inside of the reactor: Due to the low feed velocity of the gas mixture
laminar gas ow would be expected in the 10 mm wide gap between surface discharge plasma actuator and wall
(Reynolds number 22). The surface discharge plasma can be considered as a thin sheet covering the barrier
treating lling less than 10 % of the gap width. Treating 10 % of the gas ow would result in a NO conversion
efciency of less than 10 %. Thus there need to be processes causing transverse mixing. Diffusion processes
would be too slow for intense mixing. However, both the reactor design and the photographs of the surface discharge plasma published in the proceedings imply that strong EHD ows are generated causing intense mixing.

Fig. 10 Scheme of the dielectric barrier surface discharge reactor used in NO-conversion experiments [77].

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10 Summary and Conclusions

Insight has been given into selected non-thermal plasma concepts having the potential to fulll future requirements of industrial scale pollution control. Advantages and drawbacks of dielectric barrier discharge reactors,
pulsed corona discharge reactors, electron beam treatment, and dielectric packed bed reactors were given.
Plasma enhanced catalysis is a promising technology for pollutant control in mobility and industry. However,
it needs to compete with thermal catalytic processes.
Recently good progress has been made in understanding plasma assisted catalysis and drastically increasing
its efciency for destruction of VOCs. Now plasma assisted catalysis is much more efcient for VOC destruction
than plasma enhanced catalysis. Highly selective plasma induced reactions can be achieved in combinations
of non-thermal plasma with metallic catalysts nano-dispersed on the surfaces of sorbent pellets. More R&D
activities are required in order to establish plasma assisted catalysis in industrial applications.
The example of pulsed corona discharges shows the non-thermal plasma pollution control step by step develops towards industrial scale. The key for this progress is the development of semiconductor based power supplies
and innovative plasma excitation schemes such as superimposed DC / pulse or DC / high frequency AC. These
power supply concepts also offer the chance to improve the efciency of existing ESP installations by retrotting
the power supply.
Laser diagnostics and imaging are boosting the investigation of basic phenomena such as electro-hydrodynamics.
Ionic wind effects currently under investigation in several institutes around the world can be utilized for improving the efciencies both of electrostatic precipitation and of plasma chemical pollution control.

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