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ELSEVIER Applied Catalysis A: General 147 (1996) 1-21

Review

A review of the use of plasma techniques in catalyst


preparation and catalytic reactions
Magali Boutonnet Kizling *, Sven G. J~ir~s
Department of Chemical Engineering and Technology. Chemical Technology, The Royal Institute of
Technology, S-10044 Stockholm, Sweden
Received 19 January 1996; revised 7 June 1996; accepted 10 June 1996

Abstract

The application of plasma techniques in the preparation of catalysts and in catalytic reactions
published during the last fifteen years is briefly reviewed. Two different types of plasma are used
in this field: low temperature plasma (low pressure plasma) and high temperature plasma. The first
type of plasma technique is widely used for the modification of surface oxides, and for the
preparation and regeneration of catalysts as well as for catalytic synthesis and decomposition. The
second type is applied for the preparation of ceramic-based supports, recovery of precious metals
from used catalysts, and catalytic reactions. Both oxides and supported metal catalysts have been
prepared by this method. The catalytic reactions involving the plasma technique essentially
involve NO, methane or ammonia as reactants. An interesting potential for this technique is its
application in the recovery of the precious metals from car exhaust catalysts.

Keywords: Ammonia; Automotive catalysts; Preparation; Hydrocarbons; Nitrogen oxide; Metal; Oxides:
Plasma; Vacuum resids

Contents

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2. The different plasma techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3


2.1. The gaseous plasma techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. The electrical condensation method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

* Corresponding author. Fax: (+46-8) 10 85 79; e-mail: magali@ket.kth.se.

0926-860X/96/$15.00 Copyright © 1996 Elsevier Science B.V. All rights reserved.


PII S 0 9 2 6 - 8 6 0 X ( 9 6 ) 0 0 2 1 5 - 3
2 M. Boutonnet Kizling, S.G. JiirZts/Applied Catalysis A: General 147 (1996) 1-21

3.1. Preparation and regeneration of catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4


3.1.1. Electrical c o n d e n s a t i o n m e t h o d . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1.2. G a s e o u s p l a s m a techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2. H e t e r o g e n e o u s catalytic reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2.1. Nitric oxide synthesis; Nitrogen fixation . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2.2. Synthesis and d e c o m p o s i t i o n o f a m m o n i a . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2.3. Synthesis a n d c r a c k i n g o f h y d r o c a r b o n s . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2.4. H y d r o c o n v e r s i o n of deasphalted v a c u u m resids . . . . . . . . . . . . . . . . . . . . . . . 19
3.2.5. R e c o v e r y o f precious metals f r o m car exhaust catalysts . . . . . . . . . . . . . . . . . . 19

4. C o n c l u s i o n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

1. Introduction

A plasma is composed of highly excited atomic, molecular, ionic and radical


species. It might be regarded as a fourth state of matter. The plasma state is
generated by the ionization process that takes place when a sufficient amount of
energy is supplied to a gas. The process of gas ionization occurs due to collision
of ingoing molecules with electrons and by absorption of electromagnetic
radiation. The reactivity of the obtained species will depend on the type of
plasma source and the gas used. Two principal ways of plasma generation can
be distinguished. A cold gas plasma, known as a glow discharge plasma, is
obtained at low pressure and low temperature. This type of plasma is widely
used in surface modification. A thermal plasma, or an arc jet plasma, is
produced under atmospheric pressure at high temperature. Choice of plasma
process for a given application is dictated by the desired final result.
In many technological applications the state of the surface of the materials
used in the process determines the outcome. Plasma is a very helpful technique
where surface chemical modification is required. Plasma treatment is surface
specific, hence it can be employed to modify surfaces without affecting the
characteristics of the bulk. Consequently, plasma processes have found a wide
range of very important technological applications for modifications of surface
energetics to improve adhesion strength, cleaning, coating, biocompatibility to
mention a few.
The surface of a catalyst takes a particular place among the surfaces with
specific requirements. For reasons of economy and environmental concern,
catalytic processes require continuous improvements. Such improvements may
be achieved in different ways. One way is to find out new modes for the
preparation of catalytic materials that promote the desired reactions. Another
M. Boutonnet Kizling, S.G. Jiir&s/Applied Catalysis A: General 147 (1996) 1-21 3

one is improvement of the output of the reactions by modifying other factors


than the catalyst. The plasma technique may be beneficial in both cases.
The plasma processes have successfully been applied to two different areas in
the field of catalysis; firstly in the preparation and regeneration of catalysts.
Secondly, the plasma process was used to directly excite the reactants.
It is also interesting to consider industrial problems that are closely related to
those encountered in catalysis and in which plasma processes may simplify the
procedure for overcoming them.
Plasma techniques are finding increasing and varying applications in cataly-
sis. In Table 3, 29 patents on this subject are compiled; these testify to the
interest in the commercial application of plasma within the field of catalysis.
The purpose of this short review is to draw attention to these developments
during the last 15 years. We further discuss the use of plasma techniques in the
preparation of catalysts and catalytic reactions.

2. The different plasma techniques

There are in principle two kinds of plasmas [ 1]. The low temperature plasma
that is known as a cold gas or glow discharge plasma. The other one is a high
temperature plasma. They are both mainly used as gaseous plasmas. It should be
mentioned that corona and ozone generator dischargers are hybrid plasmas, thus
lying between cold and thermal plasmas. However, it is possible to sustain the
plasma state in liquids as well.

2.1. The gaseous plasma techniques

In the plasma state, a gas is constantly ionized providing neutral atoms,


positive and negative ions, and free electrons. It includes reactive neutral species
as well. As the components formed during the ionization recombine, photons of
ultra-violet and visible radiation are released emitting a faint blue glow. The
cold gas plasma is created when a gas at low pressure is exposed to an
electromagnetic field within radio or microwave frequencies [2]. There is direct
correlation between excitation frequency and plasma reactivity. Nevertheless, it
seems that a 13.56 MHz radio frequency source is preferentially used. In a cold
gas plasma neutral molecules and gaseous ions have temperature ranges between
ambient and a few hundred degrees. The electrons, on the other hand, have
energies corresponding to high temperature values. Thus, the system is not
under thermal equilibrium conditions. As a cold gas plasma is a vacuum process
it has to be created in an isolated space. The main components of the
experimental equipment used for cold gas plasma are the following: a vacuum
chamber, a system to evacuate the chamber, a gas introduction device, and an
excitation source producing electromagnetic radiation within radio frequencies
4 M. Boutonnet Kizling, S.G. Jiir~ts/Applied Catalysis A: General 147 (1996) 1-21

for initiating and sustaining plasma. The construction materials are glass, quartz
or aluminum. The process variables are the radio frequency power, gas, process
pressure and process time. Commercial plasma processing equipments consist of
similar components but there are variations in operating parameters depending
on the design.
The low temperature plasma is specially suitable for surface modification, the
most common application being sputtering of surfaces. This plasma has also
found a direct application in the catalytic reactions and the catalyst preparation.
Thermal plasmas are produced by gas arcs under atmospheric pressure in the
1 - 4 . 1 0 4 K region. The energy distribution of the gas molecules, ions and
electrons in the thermal plasma indicates that the system is in thermal equilib-
rium. The high temperature plasma can be used for the synthesis of materials
such as ceramics.
Process parameters of the low pressure and the atmospheric plasmas are listed
in Table 1.

2.2. The electrical condensation method

The plasma state can be also created in liquids. A pulsed high-frequency ac


spark-discharge can be used to obtain reactive species in inert liquids such as
hydrocarbons. Svedberg described the formation of metal particle dispersions by
the condensation method as early as in 1922 [3]. The electrical condensation
method uses an oscillatory circuit according to the Svedberg design, that is, a
pulsed high frequency ac spark-discharge. The electrodes are made of the metal
to be dispersed. The high frequency current causes the formation of atomic
metal vapor that condenses giving highly dispersed metal particles in organic
media [4].

3. Applications

3.1. Preparation and regeneration of catalysts

3.1.1. Electrical condensation method

3.1.1.1. Metal sols. Tiny narrowly size-distributed particles are of interest in


many fields of technology such as ceramics, catalysis, and polymers. Suspen-
sions of catalytically active metal particles with a narrow size distribution are
attractive specially when they are used as a catalyst for structure-sensitive
reactions. Of special interest in this context is the possibility for preparing metal
particles in the absence of a support, thus avoiding the influence of the support
on the formation of the particles.
M. Boutonnet Kizling, S.G. Jiirhs /Applied Catalysis A: General 147 (1996) 1-21 5

= e.
.~ o

i
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.=_

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6 M. Boutonnet Kizling, S.G. J~irhs//Applied Catalysis A: General 147 (1996) 1-21

1
2
Reactor
Insulated electrode
t
3 Movable electrode F

4 Hydrocarbon
5 Nitrogen
6 Magnetic stirrer
7 HV-DC generator

2
3 6
Fig. 1. Apparatus for the preparation of plasma catalysts. After Rouleau et al. [6].

Lunina and Novozhilov [4] have prepared sols of different metals in organic
media using the electrical condensation method described previously. Reaction
conditions were: current strength less than 1 A, effective voltage 600 V and a
frequency of 800-900 kHz. Thus, suspensions of particles of Ag, A1, Bi, Cd,
Cu, Mo, Fe, Ni, Zr, Pt, Sb, Sn and Co were prepared in alcohols, acetone, ethyl
acetate and in hydrocarbons. Korenev and Lunina [5] also prepared a highly
dispersed Fe sol with a metal concentration as high as 2 wt.-% in organic media
containing some stabilizers such as aluminum stearate.

3.1.1.2. Metal particles on support. The electric condensation method appears to


be suitable for preparing supported catalysts. Rouleau et al. [6] have recently
used a method similar to the one of Lunina and Novozhilov (see Section 3.1.1.1)
to prepare Ni based catalyst for hydrotreating vacuum resids. The formation of
Ni particles by evaporation of Ni metal takes place simultaneously with the
formation of the carbon support that is formed by pyrolysis of a hydrocarbon in
order to trap Ni particles. The apparatus used for the preparation of these
catalysts is shown in Fig. 1. The conditions for the preparation were: a voltage
of 20 kV and a current lower than 3 mA. The electrodes were made of nickel
and immersed in a light hydrocarbon. The resulting catalyst consisted of Ni
particles deposited on a carbonaceous substance that resulted from the pyrolysis
of the hydrocarbon. The mean size of the obtained Ni metal particles was 35 nm
with a wide size distribution. Metal content was 19.5 wt.-%. It was shown that
sulfidation does not influence the dispersion of Ni metal on the carbon support.
This result is an important one in connection with the application of these
catalysts to the hydroconversion of deasphalted vacuum residue where hydrogen
sulfide is always present in the feed. The Ni catalysts prepared by the electric
M. Boutonnet Kizling, S.G. Jiirgts/ Applied Catalysis A: General 147 (1996) 1-21 7

condensation method have shown a notable activity at low catalyst to charge


ratio. This mode of preparation was original in that the metal particles as well as
the support material were obtained simultaneously, the latter having as precursor
the solvent used in the process.

3.1.2. Gaseous plasma techniques

3.1.2.1. Catalyst preparation. As mentioned previously, the plasma technique


provides the possibility for forming catalysts in the gas phase. Several authors
have used this method of preparation to obtain supported catalysts for various
applications. Vissokov and co-workers [7-9] used an electric arc low-tempera-
ture plasma in the preparation of catalysts for ammonia synthesis. These
catalysts consisted of a mixture of several oxides such as Fe304, Fe203, FeO,
AI203, K20, CaO, SiO2, MgO at various concentrations. The precursors of the
catalysts were metal oxides, hydroxides, carbonates or nitrates. The electric
power used during the reaction was 15 kW and the carrier gas was argon,
nitrogen, oxygen or air depending on the type of catalyst to be prepared. The
particles prepared under such conditions had an average size of 50 nm, and
X-ray analysis showed a more compact crystal lattice than that of particles
prepared using a conventional method. The value of the crystal lattice parameter
had decreased by 0.9%. Thus, as Vissokov has shown several types of oxides,
nitrides and metal particles can be synthesized in large amounts using a
low-temperature plasma process instead of the classical condenser methods.
A more basic study of the preparation of a supported Ru catalyst using the
cold gas plasma has been carried out by Halverson and Cocke [10]. Using a
mixture of oxygen and water as plasma gas they prepared an aluminum oxide
support from a pure metal substrate. The conditions of the reaction were the
following: radio frequency 13.56 MHz and a power of 100 W; the temperature
was varied between 125 and 575°C. By impregnation of the obtained alumina
with an aqueous solution of ruthenium chloride followed by an oxidation-reduc-
tion treatment the Ru/AI203 catalysts were prepared. Highly dispersed metallic
particles as well as large metal aggregates are produced under such conditions.
They were used as models for bulk ruthenium catalysts.
Khan and Frey [11] prepared perovskite oxides as LaMO x films (where M is
Co, Mn or Ni) deposited on alumina by a plasma spray deposition technique.
They compared the structural and catalytic properties of the LaNiO x and
LaCoO, perovskite oxides obtained by plasma. They related the differences in
their catalytic activities to the different electronic structures of the surfaces of
these two perovskites.
The plasma spray technique has been used by Subramanian et al. [ 12] in order
to prepare Raney nickel electrodes. The preparation included plasma spraying of
Ni and A1 alloys on a stainless steel sheet and elimination of the aluminum
metal. Raney nickel electrodes were thus obtained. Comparison of the properties
8 M. Boutonnet Kizling, S.G. Jiir&s/Applied Catalysis A: General 147 (1996) 1-21

in the hydrogen evolution reaction on the Ni electrodes prepared by plasma with


those of electrodes prepared by electroplating, for example, showed that the first
one exhibited a lower overvoltage and better stability.
The influence of a low temperature plasma treatment on the surface properties
of a W O 3 / S i O 2 catalyst has been studied by Blecha et al. [13]. The activation of
the catalyst by a nitrogen plasma changes its catalytic properties in the reaction
of propene disproportionation (metathesis) compared with those of a catalyst
activated by heat treatment in a nitrogen atmosphere. Comparison of the
properties of these different catalysts shows that the plasma-activated catalyst is
more active and more selective towards ethylene formation.
The arc plasma method has been used to prepare ultrafine SiC powder with
13-structure. These particles showed good efficiency as photocatalysts in water
decomposition [14]. The preparation of bifunctional zeolite catalysts can be
carried out using a low temperature plasma to decompose Pt(NH 3) 42 + in
mordenite [15]. The low temperature plasma calcination of NH4, Na-Y zeolites
permits the removal of NH 3 in order to give Brfinsted acid sites but causes at
the same time a severe loss of crystallinity [16]; this is not surprising in view of
the residual Na content still present in them.
The modes of preparation of supported catalysts using plasma and described
in Section 3.1.2 are presented in Table 2. References to the patents given in this
field have been assembled in Table 3.
The works described previously show that plasma techniques can be success-
fully applied to the preparation of metal particles on support and also of various
oxides such as silica, alumina and perovskites to be used as supports. For these
purposes, either high temperature or cold plasmas were employed depending on
the nature of the material to be prepared.

3.1.2.2. Regeneration and sputtering of catalyst. The argon low temperature


plasma is usually employed to clean up, that is to sputter, solid surfaces before
analysis by X-ray photoelectron spectroscopy. By applying this procedure
repeatedly, it is possible to remove the uppermost surface region layer by layer.
Thus, the argon low temperature plasma can also be used for regeneration of
catalysts when the deactivation is due to formation of carbonaceous deposits,
that is coke, on the active part of a metallic catalyst. It is commonly known that
coke is the main cause of catalyst deactivation.
These carbonaceous deposits in the case of metal-supported catalysts, for
example, are usually removed from the surface of the catalysts by heat treatment
following by an oxidation-reduction treatment. Maeson et al. [17] investigated
the oxidative removal of tetrapropylammonium and diethylamine species from
zeolites using low-temperature oxygen plasma. The effect depends upon the
chemistry and dimensions of the zeolite framework as well as on the removed
molecule. Thus, the N-containing molecules could be removed from channels at
the depth of 5 to 70 ram, respectively. On the other hand, Bibby et al. [18]
M. Boutonnet Kizling, S.G. Jiir~ts/ Applied Catalysis A: General 147 (1996) 1-21 9

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M. Boutonnet Kizling, S.G. Jiirgts / Applied Catalysis A." General 147 (1996) 1-21 11

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12 M. Boutonnet Kizling, S.G. Jiirhs /Applied Catalysis A: General 147 (1996) 1-21

Table 4
Regeneration of Catalyst by Plasma
Catalyst Nature of plasma Applications/Remarks References
Iron oxide/alumina argon nitrogen plasma reduction rate is 2.5 times [19,20]
catalyst higher than for
untreated catalysts
Stainless steel fuel radio frequency plasma study of carbon deposition [21,22]
pins in an AGR, discharge, 2 kV, 2.5 MHz onto metallic surfaces
20% Cr/25% Ni/Nb CO 2 / C H 4 mixture

reported that they were unable to completely remove coke from zeolite channels
despite an extended exposure to radio-frequency oxygen plasma.
Vissokov and co-workers [19,20] have studied the influence of an argon or
nitrogen plasma on the regeneration of an iron oxide/alumina catalyst, a
commercial ammonia synthesis catalyst, after deactivation and passivation. They
observed that the rate of reduction was 2-5 time higher for the plasma-treated
deactivated catalyst than for the untreated one. Furthermore, the activity of the
regenerated catalyst in ammonia synthesis was 10% higher than that of the fresh
catalyst.
In Table 4, all methods for catalyst regeneration by plasma are listed.

3.1.2.3. Study of carbonaceous deposition in advanced gas-cooled reactor. The


formation of carbonaceous deposits or coke is not only a troublesome occur-
rence for the processes which involve catalysts. It has also been found to occur
on the metallic surfaces in contact with hydrocarbon gases in heat exchanger
systems. A tangible example in this matter is the formation of carbonaceous
deposition that has been found to occur under certain conditions on the steel fuel
pins of the advanced gas-cooled reactor (AGR). Even if, in this case, the
formation of coke is not directly related to catalysis, the results obtained by
Cairns et al. [21] as well as Blaikley and Jorgensen [22] concerning occurrence
of carbonaceous deposition in non catalytic processes are of interest to get a
better insight into this problem. These groups were interested in protection
against carbonaceous deposits on the fuel pin and boiler in an advanced
gas-cooled reactor (AGR). To simulate the formation of the carbonaceous
deposit in an AGR, they both used a radio frequency plasma discharge in the
presence of a C O 2 / C H 4 gas mixture to produce carbon deposits on a steel
surface. Parallel experiments carried out under the same conditions on a
silica-coated steel gave no carbon-deposition. They explained this difference by
the fact that the surface of the steel itself acts as a catalyst in the modification of
the gas composition near the surface and consequently favors carbon formation
while deposited silica is inactive in this reaction. They have independently
shown [21,22] that the formation of carbonaceous deposition is a catalytic
M. Boutonnet Kizling, S.G. Jiir~ts /Applied Catalysis A: General 147 (1996) 1-21 13

process. In addition, they have disclosed that nickel and iron, which enter into
the composition of steel, are responsible for this catalytic effect.

3.1.2.4. Modification of oxide surfaces. Metal oxides are usually employed as a


support for metal catalysts. It is well known that the adhesion and interaction
between the metal particles and the support are important factors that influence
the stability, activity and selectivity of a catalyst. The techniques of surface
modification, for example plasma, can be useful in order to improve the
adhesion or to modify interaction between metal and support.
The glow discharge plasma is a suitable method for modification of oxide
surfaces. Considerable work has been carried out in order to study the influence
of plasmas of argon and hydrogen on the surface of oxides such as SiO 2, ZrO 2,
M o O 3 o r V205 o n S i O 2 and TiO 2. The treatment of SiO 2 by hydrogen plasma
causes changes in the 02 adsorption on SiO 2 resulting in the formation of
paramagnetic centra on the surface [23]. Che et al. [24] have shown that
hydrogen atoms created by microwave discharge are able to produce isolated,
reduced transition metal ions at low temperature in MoO 3 or V205 on SiO 2 and
T i O 2. Argon sputtering of ZrO 2 leads to a gradual build up of an oxygen-de-
pleted layer with a thickness of 1.2 nm and composed of ZrO; a distribution in
depth of different oxide phases is created during the process [25]. The different
techniques of oxide modification by plasma described in this section are listed in
Table 5.

3.1.2.5. Plasma catalytic reactor. Plasma techniques can be used to prepare


in-situ catalysts deposited onto the inside walls of a reactor. Dalai et al. [26]
have used the plasma technique for such a catalytic reactor. The inside wall of a
tube reactor was covered with a plasma sprayed catalyst. The catalyst consisted
of a mixture of metallic Fe and Co at different concentration ratios. The reactor
was then used for Fischer-Tropsch synthesis. BET analysis of the catalyst
revealed a low surface area but despite that the uptakes of CO and O~ were
found to be quite high.

3.2. Heterogeneous catalytic reactions

In many heterogeneously catalyzed reactions, the reacting molecules have to


be transformed into activated species. The role of a catalyst is often to promote
the formation of such species. A low pressure plasma can be used to modify the
chemical reactivity. Most of the reactions where the plasma technique has been
involved are model reactions. However, some recent results show that the
plasma technique is being employed in industrial applications as well.

3.2.1. Nitric oxide synthesis; nitrogen fixation


The function of low pressure plasma in the catalytic synthesis of nitrogen
oxides has been studied to quite a large extent by different research groups.
14 M. Boutonnet Kizling, S.G. Jiirhs /Applied Catalysis A: General 147 (1996) 1-21

o
=

=~~:~ ~..~

o~
~ ~ ~o
o

e~
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.<

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.0

~Nz :~=:N
M. Boutonnet Kizling, S.G. Jiir&s/ Applied Catalysis A: General 147 (1996) 1-21 15

Pt

8
CuO

Cu
Fe
6
Ag

20 40 60 80
U~,Wh/dm 3

Fig. 2. Specific energy versus [NO] % ~ r a stoichiometric mixtu~ of N 2 and 02 at 50 to~. After
Venugopalan and Vep~k[29].

Among them, Amouroux and co-workers [27,28] have made very basic studies
of the interaction between the chemical species which constitute the plasma and
solid surfaces; they used transition metal oxides such as WO 3 and M o O 3. The
collision of the molecules in the plasma induces an increase in the vibration
energy of nitrogen molecules which then will be polarized in the neighborhood
of solid surfaces and may be chemisorbed. The last step of the reaction occurs
on the surface; its features depend on the nature of the metal (Fig. 2) [29]. In
case of a transition metal oxide, the adsorbed, vibrationally excited nitrogen
atom reacts with the free oxygen atoms from the oxides. A step similar to the
one previously described can explain the process of nitrogen fixation in the
system N 2 - C H 4 [31] when the reaction is carried out in a plasma reactor (Fig. 3)
[30] in the presence of a catalyst based on metals such as Fe, Cu, W, Ta or Mo
[32].
According to the work of Mutel et al. [33] the use of a low pressure plasma in
the synthesis of nitrogen oxides can lower the energy costs by 53% in compari-
son with the industrial process used at present. However, the experimental
conditions are still far from being of practical significance.

3.2.2. Synthesis and decomposition of ammonia


Bergougnan et al. [34] have studied NH 3 decomposition in a low pressure
plasma without and in the presence of a W or Mo based catalyst. The NH 3
plasma is created by a high frequency discharge (40 MHz) at low pressure
( 5 - 4 0 mbar).
16 M. Boutonnet Kizling, S.G. Jiir&s/Applied Catalysis A: General 147 (1996) 1-21

main control
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power control

temperature i generator <~. intensity


I vo!tsili l H.F. <'T'> voltage
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i ', water / ', manometer
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pre~re '--[gas---heai-treating ~ s?eciment
chamber '. dose
manometer ~ distance
~ , pressu re control
~ control

I
gas
sample as feed
Fig. 3. Experimental apparatus for plasma generation. After Gicquel et al. [30].

The activated state of the ammonia molecule is a crucial factor of the


decomposition process without catalyst. The mechanism of the NH 3 decomposi-
tion according to the authors is the following.
The ammonia molecule in low pressure plasma produces two different excited
species. The first one is an electronically excited dissociative species NH 3 * (the
upper pathway on Scheme 1). The second one, NH 3 , is a highly excited species
in the vibrational energy mode; these species relax to the ground state (the lower
pathway on Scheme 1).
The main step which controls the reaction of decomposition is a slow,
endothermic dissociation (NH3)**--+ (NH)* In the presence of a catalyst,
however, the vibrationally excited (NH3)* species are chemisorbed on the
surface and are involved in the catalytic reaction. The same authors [34] have
studied the influence of the nature of the catalyst on the rate of NH 3 decomposi-
tion. Comparison of W (transition metal) and Si (semiconductor) based catalysts
showed that the first one increased the rate of the reaction while the second one

kl
k2
/~ (NH3)** ~ (NH)* P N 2 + H2

Nil 3 +e
xil (Nit3), _- NH3
Scheme 1.
M. Boutonnet Kizling, S.G. Jiirfs / Applied Catalysis A: General 147 (1996) 1-21 17

catalyst
3800 ! Tvib

\
towards \ with W
3400 heat /
treatment
- chamber

2900 -
distance

Fig. 4. Variation of the vibrational temperature in the reactor in the presence of a metallic foil (W or Mo)
( P = 5 mbar, PI = 0.8 kW, DNH 3 = 0.5 1/min). After Rapakoulias et al. [36].

inhibited the reaction. The authors concluded that the catalytic activity of any
material depends on its ability to influence the vibrational energy of the plasma
at the interface plasma-solid. Furthermore, it seems that the real catalyst in the
reaction is not the metal itself but its nitride. The efficiency of a catalyst for
NH 3 decomposition will depend on its ability to form nitrides. Consequently, W
based catalysts will be better than Mo based catalysts while Si will act as an
inhibitor. The effect of titania [35] on the decomposition of ammonia in a
plasma reactor is identical to that observed in the case of W or Mo based
catalysts (Fig. 4) [36].
The chemisorption of N 2 on a ruthenium black catalyst is made possible
when nitrogen atoms are produced by a plasma discharge [37]. The reaction of
the chemisorbed nitrogen with hydrogen forms ammonia at room temperature.
Magnesium and calcium oxides show a catalytic effect in the ammonia synthesis
when the reaction is carried out in the presence of an H 2 - N 2 plasma [38]. The
influence of the nature of the metal on the produced amount of ammonia is
shown in Fig. 5 [29]. Similar studies carded out on iron wires [39] and platinum
catalyst [40] have also shown a catalytic effect of these metals in the plasma
synthesis of ammonia.

3.2.3. Synthesis and cracking of hydrocarbons


An argon/hydrogen plasma can be used in a novel cyclone reactor to carry
out high temperature and low pressure catalytic conversion of natural gas. The
role of the argon/hydrogen plasma is to create methyl and ethyl radicals from
methane, ethane and ethylene molecules. The mixture is heated before the
plasma treatment [41]. Motallebi et al. [42] have studied methane conversion in a
18 M. Boutonnet Kizling, S.G. Jiir&s /Applied Catalysis A: General 147 (1996) 1-21

--'0 Pt

/
//
10
,' • Pt
t

• //Jr
o
zx Ag
£
z
5
"" ..........X Fe

ou
Cu

~- ~100 torr
I I
50 1O0
U/v, Wh/dm 3

Fig. 5. Variation of the ammonia concentration with specific energy at a pressure of 50 torr (curves leading to
open points) and 100 torr (curves leading to solid points) for different catalysts. Dotted parts were not
determined experimentally. Points from circulation experiments; solid lines from flow experiments. After
Venugopalan and Veprek [29].

plasma spouted-bed device. The products consisted mainly of acetylene and


ethylene. A microwave plasma reactor has been used to carry out the conversion
of methane into higher hydrocarbons such as ethane, ethylene, and acetylene
[43]. Depending on the nature of the catalyst and on the plasma experimental
conditions, very high selectivities to the different products could be obtained.
For example, ethane gave only ethylene when the conversion was 7-10%. Here,
the role of the catalyst is to adsorb hydrogen and hydrocarbon radicals and to
desorb product molecules, while in the absence of plasma the function of the
catalyst is to adsorb the hydrocarbon reactants, to dissociate the C - H bonds and
finally to desorb the products of the reaction.
Vapors of aluminum or tungsten produced in a high-temperature plasma
reactor have been used as catalysts in the cracking reaction of propane. The
maximum yield of acetylene was 93% when the temperature reached 4000 K
[44].
Another interesting aspect of the application of a plasma to organic com-
pounds is the cleaning of exhaust systems. Nonequilibrium plasma processes are
beginning to find application in the removal, by destruction, of hazardous
volatile organic compounds from effluent and exhaust streams of industrial
plants. Electron-beam-generated nonequilibrium plasmas appear to efficiently
decompose halogenated volatile organic compounds at very low concentrations
in an air stream. This kind of plasma preferentially interacts with the compounds
to be decomposed, leaving the carrier gas unchanged [45].
M. Boutonnet Kizling, S.G. Jiirfis /Applied Catalysis A: General 147 (1996) 1-21 19

4\ 21
7

(-)

m
)
m
B
m
If I I I / [ I l I I I
m
in
If
I
i i
I III
i i
I I I I

Fig. 6. Experimental set-up showing the transferred plasma arc mode of autocatalyst smelting. After Mishra
and Reddy [47]. (1) Plasma gun (500 kW). (2) Autocatalyst feed. (3) Dust collector. (4) Argon gas. (5) dc
power supply. (6) Plasma arc. (7) Castable refractory cover. (8) Insulating refractory, (9) Slag, (10) Graphite
crucible, (11 ) Platinum group metals collector. (12) Graphite block.

3.2.4. Hydroconversion of deasphalted uacuum resids


Rouleau et al. [46] have studied the hydroconversion of a deasphalted vacuum
residue in the presence of a Ni-based catalyst prepared by the electrocondensa-
tion method [6]. They observed that a quite high catalytic activity could be
obtained at very low catalyst concentration. Some additional properties of these
catalysts, which are of importance, were that the formation of the coke deposits
was prevented and the aromatization of the feed avoided.

3.2.5. Recouery of precious metals from car exhaust catalysts


Nowadays, due to environmental regulations, most cars have to be equipped
with a car exhaust catalyst. Despite an intensive research in this field, the
efficient but expensive catalyst based on P t / R h metals as yet cannot be replaced
by an equally effective but cheap one. In order to keep the costs of the P t / R h
car exhaust catalyst low an efficient recycling of the catalyst has to be used. A
plasma arc furnace was used by Mishra and Reddy [47] (Fig. 6) to melt different
compounds of an autocatalyst in order to recover precious metals. The process is
carried out in the following way: first iron metal is melted using a 500 kW
plasma gun in order to be used as a collector for the precious metal. Then the
charge of the autocatalysts is introduced into the reactor and melted at 1600-
1700°C. The metals are then separated from the metal collector. The recovery of
the precious metals using this process was, in the case of honeycomb car
exhaust catalyst, 91.9% for Pt, 94.6% for Pd and 91.8% for Rh. Tajmouati et al.
[48] have replaced the metal collector by an oxygen gas flow produced by a
plasma source, the evaporation of the precious metals took place at 1620 K.
The analysis of the metal content of car exhaust catalysts can be simplified
20 M. Boutonnet Kizling, S.G. Jiir&s /Applied Catalysis A: General 147 (1996) 1-21

using a technique that combines the plasma process with a spectrometric


estimation. Brown et al. [49] have used a plasma coupled to mass spectrometry
and Rao et al. [50] applied a plasma coupled to emission spectrometry.

4. Conclusion

Plasma technology and especially cold gas plasma is finding continuously


increasing application in industrial processes requiring surface chemical modifi-
cation. The use of plasma techniques for catalyst preparation and catalytic
reactions has interested several researchers in the field of catalysis. It appears
from the reviewed studies that it is possible to prepare by these techniques
dispersions of metal particles and also supported catalysts. Furthermore, the
surface properties of different oxides can be modified at low temperature. Thus,
with these techniques it is possible to obtain catalytically active materials with
new surface properties that will in turn give modified activity and selectivity.
Besides, a direct application of plasma to the activation of catalytic reactions can
result in novel catalytic activities and selectivities for these reactions compared
with a conventional catalytic process. So far, catalytic reactions studied by
means of a plasma process, concern only nitrogen oxide synthesis and ammonia
decomposition. In addition, some interesting results were obtained when a
plasma process was involved in hydroconversion.
Another interesting application of this process could be the development of
highly effective recovery methods for precious metals from car exhaust cata-
lysts. Finally, this review shows that there is a potential for successful applica-
tions of the plasma techniques to the field of catalysis in order to improve
existing catalytic processes.

Acknowledgements

The authors thank Prof. P. Govind Menon for his critical and fruitful
comments during the revision of this manuscript.

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