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A: GENERAL
ELSEVIER Applied Catalysis A: General 147 (1996) 1-21
Review
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
3. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4. C o n c l u s i o n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1. Introduction
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.
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.
3. Applications
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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.
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10 M. Boutonnet Kizling, S.G. Jiir&s /Applied Catalysis A: General 147 (1996) 1-21
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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.
process. In addition, they have disclosed that nickel and iron, which enter into
the composition of steel, are responsible for this catalytic effect.
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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.
main control
~] on/off
power control
i
- ' - ' t\\Rt )i
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].
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.
--'0 Pt
/
//
10
,' • Pt
t
• //Jr
o
zx Ag
£
z
5
"" ..........X Fe
ou
Cu
~- ~100 torr
I I
50 1O0
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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].
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.
4. Conclusion
Acknowledgements
The authors thank Prof. P. Govind Menon for his critical and fruitful
comments during the revision of this manuscript.
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