Research Article

Catalytic Flue Gas Treatment from Nitriding

Processes
Efficient control and minimization of emissions from technical processes is of
major concern in industrial development and process operation. The technical
process in the focus of the present contribution is the nitriding process of metallic
specimen. The ammonia content in nitriding process flue gases reaches up to
618 gm
3
(80 vol.-%) and needs to be reduced to less than 30 mgm
3
(40 ppm)
to fulfill present regulations. Exhaust gases from nitriding processes today are
burnt in flares without emission control where fuels need to be added that pro-
duce additional exhaust gas components. The objective of this investigation is to
develop an alternative gas cleaning route for nitriding processes based on catalytic
dissociation of ammonia. The decomposition was studied for different catalysts
at varying process conditions. With these results a dissociation pilot plant was
successfully tested in a technical-scale nitriding process.
Keywords: Catalytic gas cleaning, Flue gas cleaning, Gas nitriding, Process emissions
Received: June 6, 2009; accepted: October 12, 2009
DOI: 10.1002/ceat.200900291
1 Introduction and Statement of the
Problem
In 2005, Germanys ammonia emissions attained approx.
61910
3
tons [1] that need to be reduced to 55010
3
tons by
2010 [2]. The official standards for the German national lim-
itation of emissions from industrial processes are based on the
requirements of the Federal Immission Control Act (Bundes-
Immissionsschutzgesetz) [3] and the Clean Air Guidelines
(TA-Luft) [4]. The limit established here for ammonia in waste
gases is 30 mg/m
3
(40 ppm). In addition, the mass flow rate of
0.15 kg/h must not be exceeded within an hour during normal
operation. Waste gases from nitriding processes contain 3080
% ammonia depending on the process conditions and must be
subjected to a post process flue gas treatment to reduce the
ammonia content. This generally occurs in gas burners with
addition of fuels (e.g., propane). As this burning process is not
regulated, unburnt ammonia is also released together with
CO
2
and NO
X
. Typical ammonia emission levels exceeding the
established limit often occur, e.g., in the start-up process.
This contribution investigates an alternative system for the
controlled reduction of the ammonia content in waste gases
from nitriding processes with the target of reducing NH
3
emis-
sions to comply with the limit established in the TA-Luft. The
aimed waste gas purification process should require small
technical and financial expenses, produce no other pollutants,
and needs to be tailored to the process and material character-
istics of the nitriding process. Possible purification processes
have been evaluated with respect to the practicability of their
application in nitriding systems where catalytic ammonia dis-
sociation was selected for use in further investigations.
1.1 Process Conditions in Nitriding Systems
The furnace atmosphere in nitriding processes can differ sig-
nificantly depending on the composition of the sub-assemblies
and the desired nitriding result. Besides high concentrations of
ammonia it may also contain nitrogen, hydrogen, and in the
related nitrocarbonizing process carbon carriers. It has to be
assumed that the vaporizing residues of cleaning agents, anti-
corrosion agents, and cooling lubricants used in the pretreat-
ment of the sub-assemblies also enrich the atmosphere with
further unknown carbon compounds. Depending on the ac-
tual size of the furnace, the ammonia volumetric flow rates in
pure gas nitriding processes may be in the range from
1 to 12 m
3
N
/h. In the nitriding furnace the partial dissociation
of ammonia at 820 K obtains hydrogen and nitrogen. The dis-
sociation grade in the nitriding furnace is generally between 20
and 80 % [5] depending on the process conditions and con-
trol. Therefore, the residual NH
3
content can be as high as
80 vol.-%.
Chem. Eng. Technol. 2010, 33, No. 1, 145154 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
Heidi Ludewig
1
Brigitte Haase
2
Udo Fritsching
3
1
Bremer Energie Institut,
Research V, Bremen, Germany.
2
Hochschule Bremerhaven,
Process Engineering and
Technology, Bremerhaven,
Germany.
3
Universitt Bremen,
Fachbereich 4
Produktionstechnik, Bremen,
Germany.

Correspondence: Heidi Ludewig (ludewig@bremer-energie-institut.de),

Bremer Energie Institut, College Ring 2, Research V, D-28759 Bremen,
Germany.
Flue Gas Treatment 145
2 State of the Art
Catalytic dissociation of ammonia is selected as a suitable pro-
cess for the system concept as it produces no air pollutants
and may achieve an NH
3
conversion of 99 % [6]. The basic re-
action mechanism has been described in the relevant literature
[712]. Above 750 K ammonia is thermodynamically instable
and dissociates on catalytic surfaces according to:
2 NH
3
N
2
+ 3 H
2
(1)
The reaction is associated with doubling the gas volume at
constant pressure. The temperature which is thermodynami-
cally required to reach the equilibrium at which materials dis-
sociation meets the required limit can be calculated using the
equilibrium constant K:
K
x
N
2
x
H
2

3
p
2
x
NH
3

2
(2)
lnK
D
R
G
RT
(3)
where x
i
=p
i
/p are the amount fractions of the substances am-
monia, hydrogen, and nitrogen in the equilibrium, D
R
G is the
free reaction enthalpy, R is the general gas constant, and T is
the temperature. Tab. 1 shows the calculated free reaction en-
thalpies, the equilibrium constants, and the partial pressures of
ammonia reached at equilibrium for different process temper-
atures.
The aimed equilibrium partial pressure of 4 Pa (40 ppm) is
not reached below 1200 K. Prerequisite for the scale-up process
is knowledge of the dependency of the reaction rate r
Diss
on
the process parameters of temperature, ammonia concentra-
tion, and catalyst material. A first-order reaction rate equation
was determined empirically for the dissociation of ammonia at
high temperatures [11], thus:
r
Diss

1
V
N
t
c
NH
3
t k (4)
The derivative
N
t
describes the change in the amount of the
substance in relation to time. The phrase -c
NH3
(t) in molL
1
is
the ammonia concentration decreasing in the direction of flow,
k is the rate constant of the reaction in s
1
, and V is the reac-
tion volume. For a plug-flow reactor the integral for irrevers-
ible reactions of first order with increasing volume can be cal-
culated [13] as:
1 a ln
1
1 X
a X k s
M
(5)
The rate of the ammonia dissociation is definitively fixed by
the most inhibiting, i.e., the slowest elementary step in the re-
action. Ganley et al. [14] and other authors subdivided the
gross reaction into six elementary reactions:
NH
3,g
NH
3,ad
(a)
NH
3,ad
NH
2,ad
+ H
ad
(b)
NH
2,ad
NH
ad
+ H
ad
(c)
NH
ad
N
ad
+ H
ad
(d)
2 H
ad
H
2,g
(e)
2 N
ad
N
2,g
(f)
As the recombination of the atomic nitrogen in combination
with desorption of the N
2
molecule (step f) requires the high-
est activation energy, this sub-step is regarded as being the
slowest [6]. Other authors suspect that the temporally defined
sub-step is dependent on the temperature. At temperatures be-
low 650 K, the recombination and desorption of nitrogen are
limiting the rate, and beyond 750 K the breaking of the N-H
bonds [10]. McCabe [15] investigated the dissociation of am-
monia on nickel wires and determined that above 1000 K the
reaction order increased from zero to first order, combined
with a change of the rate-depending step. He proved that the
rate is limited by the rate of nitrogen desorption at low tem-
peratures and by the ammonia adsorption on the substrate at
high temperatures. The influence of the catalyst material on
the ammonia dissociation process not yet agreed. Among
other factors, the activity of the catalyst is strongly influenced
by the size of the surface, integrated promoters, and the
grid structure of the metal [10]. Choi [16] observed an in-
crease in activity when the size of the catalyst particles was in-
creased and the total surface area decreased, respectively,
while Jedynak et al. [17] observed a much higher turnover fre-
quency when smaller iron particles were employed. Li et al. [7]
determined that beside the catalyst material influencing the
activation energy of the reaction also the manufacturing
process (e.g., particle size distribution on the support) is
relevant. In a plug-flow reactor, the residence time s of
the gas in the reaction zone also decides the ammonia
conversion; a short residence time reduces the conversion
[12, 19].
2.1 Calculating the Required Conversion in the
Waste Gas Purification
The maximum ammonia volume fraction in the nitriding
waste gases is approx. 80 vol.-% and must be reduced to
30 mg/m
3
N
to meet the TA-Luft threshold. The required
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Table 1. Equilibrium partial pressure of ammonia at different tempera-
tures.
Temperature (K) D
R
G
(kJmol
1
)
Equilibrium constant
of ammonia K
Equilibrium partial
pressure p
NH3
(Pa)
298 33 1.610
6
9410
3
500 9.7 1.010
1
810
3
800 79.9 1.710
5
80
1200 181.3 7.810
7
4
1300 207.7 2.210
8
2
146 H. Ludewig et al.
ammonia conversion X
NH3
in the waste gas purifi-
cation for this can be calculated as [13]:
X
NH
3

1
c
NH
3
c
0;NH
3
1 a
c
NH
3
c
0;NH
3
6
where c
0;NH
3
(molL
1
) is the ammonia concentra-
tion before dissociation, c
NH
3
(molL
1
) is the con-
centration after dissociation, and a is the coeffi-
cient of volume expansion. The required ammonia
conversion is X
NH3
= 0.9999 (99.99 %).
3 Experimental Section
3.1 Laboratory System
Fig. 1 shows the setup of the laboratory-scale experimental
setup for ammonia dissociation, comprising a gas mixing
station, the plug-flow reactor, and the gas analysis.
The catalytically active materials and parameters of plug
flow reactor can be seen in Tab. 2.
3.2 Measuring Program
3.2.1 Influence of Temperature
The gas mixtures and temperatures used are listed in
Tab. 3.
3.2.2 Influence of the Catalyst Material
The influence of different catalyst materials on the ammo-
nia conversion was compared at the reaction temperature
T
R
=1273 K and different ammonia volume fractions at
the reactor entrance, see Tab. 4.
For X4CrNi18-10, the volume flow rate at the entrance was
3.6 L
N
min
1
, for nickel oxide it was 2.6 L
N
min
1
, and for pure
nickel it was 3 L
N
min
1
. It should be noted, however, that with
the different volume flows, the same volume fractions give dif-
ferent ammonia substance flows. To ensure the comparability
of the results, the measured results are represented subject to
the ammonia flow rate at the reactor entrance.
3.2.3 Influence of the Volumetric Flow Rate
(Residence Time in Reactor)
The influence of the residence time s on the disso-
ciation process was investigated at a reaction tem-
perature T
R
=1273 K and 80 vol.-% ammonia. The
volume flow rates employed were 1.0; 1.5; 2.0; 3.0;
3.5 L
N
min
1
.
4 Results and Discussion of the Laboratory
Tests
4.1 Influence of NH
3
Volume Fraction and
Temperature
The influence of the temperature on the dissociation process is
shown in Fig. 2 for the pure nickel catalyst as an example.
At reaction temperatures of T
R
=973 K, the NH
3
volume
fractions U
NH3
increase much more steeply at the reactor exit
Chem. Eng. Technol. 2010, 33, No. 1, 145154 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
Figure 1. Setup of the laboratory-experimental station.
Table 2. Parameters of catalysts and plug flow reactor.
Catalysts
X4CrNi18-10
(chips)
Nickel oxide
(balls)
Nickel
(wire)
Volume of catalysts V
Cat
(cm
3
) 7 30 22
Surface of catalysts A
Cat
(cm
2
) 1061 129 284
Mass of catalysts m (g) 38 41 180
Reactor
Length L (cm) 22
Inside diameter D (cm) 2.2
Total volume V
reactor
(cm
3
) 83
Free volume V
f
(cm
3
) 76 53 61
Table 3. Experimental parameters using nickel wire as catalyst.
Nickel (wire)
Temperature T
R
(K) 973 1173 1273
Ammonia volume
fraction
U
0,NH3
(vol.- %)
0.1 / 0.5 / 1 / 5 /
10 / 20 / 30
0.5 / 1 / 5 / 10 /
20 / 30 / 40
10 / 20 / 30 / 40
Flue Gas Treatment 147
than at 1173 K and 1273 K. The ammonia volume fraction of
U
0,NH3
=30 vol.-% fed into the reactor is reduced to
U
NH3
=8910
3
ppm (8.9 vol.-%) at T
R
=973 K, to 1144 ppm
(0.11 vol.-%) at T
R
=1173 K, and to 158 ppm (0.01 vol.-
%) at T
R
=1273 K. At U
0,NH3
=40 vol.-% NH
3
at the reactor
entrance and a reaction temperature of 973 K in the reactor,
the NH
3
volume fraction at the reaction exit exceed the upper
measuring limit, so there no valid result could be achieved. At
a reaction temperature of 1173 K and a maximum ammonia
volume fraction, the mean value at the reactor exit is
U
NH3
=1643 ppm, and U
NH3
=423 ppm at 1273 K. The am-
monia conversion subject to the ammonia volume fraction at
the reactor entrance U
0,NH3
is shown in Fig. 3.
At 973 K and smaller ammonia fractions in the
gas mixture the conversion increases to almost
90 %, reaches a maximum at 1 vol.-%, and falls to
<70 % as the ammonia fraction is increased
further. The conversion is thus dependent on the
ammonia volume fraction in the gas mixture up to
the maximum conversion. Thereafter, the conver-
sion becomes limited, particularly because of the
low temperature. The calculated ammonia conver-
sion for 900 and 1273 K only decreases slightly in
the regions investigated and is always beyond 99 %.
At the maximum ammonia volume fraction
U
0.NH3
=40 vol.-% the calculated conversion is
X
NH3
=99.4 % at 1173 K and X
NH3
=99.8 % at
1273 K. In addition, the constant conversion shows
that the NH
3
volume fraction fed in at this temper-
ature has a negligible impact on the dissociation
process. The ammonia conversion increases when
the reaction temperature is increased. Li et al.
showed that the rate of ammonia dissociation with
ruthenium and nickel catalysts almost tripled when
the reaction temperature was increased by 200 K [7]. More-
over, it can be established that the difference between the con-
version at 973 K and 1173 K is considerably larger than the dif-
ference between those at 1173 K and 1273 K. This means that
the influence of the temperature reduces, the higher the reac-
tion temperature is. Yin et al. [8] calculated an equilibrium
conversion for reaction temperatures between 523 and 773 K
and concluded that the influence of the temperature on the
conversion becomes less as the temperature increases. If one
takes into account that the required conversion of 99.99 % de-
mands almost complete dissociation, the reaction temperature
to form the basis for the scale-up process must be high.
4.2 Influence of the Catalyst
Material
Fig. 4 shows the ammonia volume
fractions U
NH3
at the reactor exit de-
pending on the NH
3
flow rate q
n0,NH3
at the reactor entrance at a reaction
temperature of 1273 K. The threshold
for ammonia is also shown.
At a reaction temperature of 1273 K
the trend lines of the measured NH
3
volume fractions U
NH3
for the catalysts
X4CrNi18-10 and nickel oxide overlap,
though the NH
3
values measured when
using X4CrNi18-10 are slightly lower
than with nickel oxide. The gradient of
the trend lines is slight across the
whole substance flow region; at
q
n0,NH3
=8 molh
1
the highest NH
3
value measured was 71 ppm. The trend
line for pure nickel is, as shown in Fig.
4, much steeper than those of the other
two catalysts and the NH
3
value mea-
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Table 4. Experimental parameters to investigate the influence of the different cat-
alyst materials.
Catalyst Volume flow rate NH
3
volume fraction Ammonia flow rate
q
V,0
(L
N
min
1
) U
0,NH3
(vol.- %) q
n0,NH3
(molh
1
)
Nickel oxide 2.6 10
40
60
80
0.71
2.83
4.24
5.65
Nickel wire 3 10
20
30
40
0.82
1.63
2.45
3.26
X4CrNi18-10 3.6 10
20
40
60
80
0.99
1.99
3.98
5.95
7.95
Figure 2. Ammonia volume fraction in the effluent gas as a result of different reaction tem-
peratures.
148 H. Ludewig et al.
sured of U
NH3
=400 ppm at q
n0,NH3
=3 molh
1
is approxi-
mately tenfold those of the other two catalyst materials.
The conversion calculated for the three catalysts versus the
ammonia flow rate at the reactor entrance at 1273 K is illus-
trated in Fig. 5.
All conversions are beyond those at 1173 K (not shown
here), but the difference is small in comparison to the differ-
ences between 973 K and 1173 K. The conversions there in-
creased at up to 40 % via the temperature increase, while the
temperature increase from 1173 K to
1273 K merely resulted in an increase
in conversion, e.g., of 0.06 % at the
maximum ammonia substance flow
for X4CrNi18-10. In conclusion, the
temperature only has a small influence
on the catalysts conversion at high re-
action temperatures, and the true lim-
iting component is clearly the specific
activity of the catalyst material. When
nickel is used, the conversion is not
approximately constant, but rather de-
creases significantly as the ammonia
substance flow increases. Nickel is thus
not suitable as a catalyst material in
this application. The conversion trends
for nickel oxide and X4CrNi18-10 are
almost identical. The required conver-
sion of 99 % is achieved with both cat-
alysts, although for the residence time
selected for the laboratory unit this
was only sufficient up to an ammonia
flow rate of q
n0,NH3
=4 molh
1
. To in-
crease the conversion at higher ammo-
nia flow rates, the reaction temperature
could be raised, yet the influence re-
mains small and this would also re-
quire the use of highly thermoresistant
materials. For the dimensioning of the
prototype in the scale-up process, an
alternative would be to analyze the
reactor size extensively and thereby ex-
tend the residence time of the gases in
the reactor, which would in turn in-
crease the conversion.
4.3 Influence of Gas Volume
Flow and Residence Time
The influence of the residence time on
the ammonia dissociation process was
investigated by varying the volume
flow rate at a constant NH
3
volume
fraction in the gas mixture. The aim of
this was to determine the minimum
required residence time for sufficient
ammonia conversion to satisfy the TA-
Luft limit. The mean residence time s
M
of the gas in the reaction zone V
reactor
is determined by the vol-
ume flow rate q
V
where:
s
M

V
reactor
q
V
(7)
As the dissociation of ammonia is associated with the in-
crease in gas volume this must be taken into account when cal-
culating the residence time of the gas in the reactor. The in-
Chem. Eng. Technol. 2010, 33, No. 1, 145154 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
Figure 3. Ammonia conversion due to different reaction temperatures.
Figure 4. Ammonia volume fraction at the outlet of the reactor using different catalysts.
Flue Gas Treatment 149
crease in the volume flow rate subject to the ammonia conver-
sion X results from:
q
V
t q
V;0
1 X (8)
with the volume flow q
V,0
at the reactor entrance. The mean
residence time of the gas in the reactor is thus calculated with
the mean volume flow rate q
V,M
:
q
V;M

1
t

Z
t
0
q
V
tdt 9
At almost complete conversion, the
mean volume flow is approximately 1.9
times that of the volume flow at the
entrance q
V,0
. The following figures
show the influence of the gas volume
flow rate on the ammonia conversion
in the reactor for the catalysts
X4CrNi18-10 and nickel oxide. The
achieved conversions with nickel were
not sufficient for being taken into ac-
count in the scale-up process.
Fig. 6 shows the NH
3
volume frac-
tion U
NH3
at the reactor exit subject to
the gas volume flow rate q
V,0
at a reac-
tion temperature of T
R
=1273 K.
When X4CrNi18-10 is used as the
catalyst, the NH
3
volume fractions
measured U
NH3
are below the limit es-
tablished in the TA-Luft of 40 ppm up
to a volume flow rate of approximately
2.5 L
N
min
1
. Increasing the flow rate
further results in values of up to four
times higher (approx. 160 ppm). With
the nickel oxide catalyst the limit is
met up to 2 L
N
min
1
. Below a flow rate
of 1.5 L
N
min
1
with nickel oxide the
NH
3
volume fractions U
NH3
with
20 ppm are just half as large as for
X4CrNi18-10. For volume flow rates
exceeding 1.5 L
N
min
1
, however, the
NH
3
volume fractions U
NH3
increase
more strongly with nickel oxide than
with X4CrNi18-10 and at 100 ppm at a
volume flow rate of 3 L
N
min
1
they are
already double.
The calculated ammonia conversions
at a reaction temperature of 1273 K for
X4CrNi18-10 and the nickel oxide cat-
alyst are given in Fig. 7. The required
ammonia conversion is represented by
the dashed line in the figure.
The required conversion is achieved
at approximately 2.8 L
N
min
1
with
X4CrNi18-10. With nickel oxide, the
NH
3
conversion at 1.5 L
N
min
1
of
99.996 % is higher than with
X4CrNi18-10, but the required conversion of 99.99 % is al-
ready met at 2 L
N
min
1
.
The trends for each conversion are always similar in shape:
the conversion remains relatively constant up to a certain flow
rate and then falls off steeply. Arabzcyk and Zamlynny [12] in-
vestigated the conversion trends at increasing space velocity
and also recorded a tendency to decrease. However, this did
not include the time in which the conversion remains constant,
which may be down to the much lower reaction temperature
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Figure 5. Ammonia conversion using different catalysts.
Figure 6. Ammonia volume fraction at the outlet of the reactor depending on the volume
flow rate.
150 H. Ludewig et al.
(500 C). Liang et al. [18] also recorded a decrease in the con-
version at increasing space velocity. The dropping conversion
shows that the reaction rate does not increase proportionally
to the substance quantities introduced, but rather is limited by
mass transfer limitation. The ratio from empty reactor volume
to total volume is defined as porosity and is significantly lower
with nickel oxide than with X4CrNi18-10 so that the mean
residence time at the same volume flow is significantly shorter.
For this reason, the following shows the NH
3
conversion de-
pending to the mean residence time of the gases in the reactor.
Fig. 8 shows that the required con-
version of 99.99 % at NH
3
volume
fraction U
0,NH3
=80 vol.-% can be
achieved by correctly rating the resi-
dence time.
When X4CrNi18-10 is used as the
catalyst, the required conversion is
achieved at a mean residence time of
approx. 0.2 s. Extension of the resi-
dence time can only result in a slight
increase in conversion up to approxi-
mately 99.992 %. Shortening of the
residence time to less than 0.17 s re-
sults in a considerable decrease of con-
version. The nickel oxide catalyst
achieves the required conversion at a
shorter residence time of 0.18 s. The
conversion increases as the residence
time is extended up to as high as
99.996 %. Decreasing the residence
time results in a steep conversion de-
crease just as for X4CrNi18-10.
5 Scale-up Process
A prototype for waste gas purification
in nitriding processes has been devel-
oped based on the kinetic data from
the laboratory investigations and with
respect to the following boundary con-
ditions:
The pressure loss caused by the
waste gas purification must be small
enough that it does not exceed the
difference between the triggering
pressure of the safety valves in the
nitriding furnace (usually 15 mbar)
and the furnaces operating pressure
(35 mbar).
The catalyst material should be cost-
effective and easily procurable, i.e.,
expensive precious metals should be
avoided wherever possible.
The optimal process conditions were
determined in the laboratory tests.
The following applies:
The reaction temperature is 1273 K
at the highest ammonia volume fraction of 80 % and the
maximum volume flow rate.
The minimum residence time of the gas in the reactor is
s
M
=0.2 s for X4CrNi18-10 and s
M
=0.18 s for nickel oxide.
The design of the prototype is based in combination with an
industrial-scale nitriding furnace. The maximum ammonia
volume flow rate which can be fed into the nitriding furnace
is:
q
V,nit
=1.5 m
3
N
h
1
.
Chem. Eng. Technol. 2010, 33, No. 1, 145154 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
Figure 7. Ammonia conversion depending on the volume flow rate.
Figure 8. Ammonia conversion depending on the mean residence time.
Flue Gas Treatment 151
The ammonia dissociation grade in the nitriding furnace
and the related volume increase must be taken into account
when calculating the volume flow q
V,pilot
which leaves the ni-
triding furnace and is fed into the prototype. With a maximum
residual NH
3
fraction of 80 vol.-% in waste gases from nitrid-
ing processes (in general) the NH
3
conversion in the nitriding
furnace can be calculated as follows [19]:
X
NH
3

100 NH
3
i:A:
100 NH
3
i:A:
= 0.11 (10)
Assuming that the gas is already at the reaction temperature
when it enters the prototype, the volume flow at the entrance
is:
q
V,pilot
=7.8 m
3
h
1
As in the test unit, a mean volume flow q
V,M
is calculated
taking into account the increase in gas volume at a conversion
of X
NH3
=99.99 % in the waste gas purification. The mean vol-
ume flow q
V,M
is:
q
V;M
=15 m
3
h
1
.
The following applies to the prototypes required reactor
volume according to [20]:
V
reactor

q
V;M
s
M
e
(11)
where s
M
is the experimentally determined minimally required
residence time and e is the porosity of the catalyst bed.
X4CrNi18-10 chips have a higher porosity than the nickel ox-
ide catalyst (also see Tab. 5) and cause less flow resistance.
(also see Tab. 6). The pressure loss caused by the catalyst filling
thus can be kept low.
In addition, the higher porosity of the X4CrNi18-10 at an
approximately identical residence time s
M
of the gas in the re-
actor can also indicate smaller dimensions for the system. The
calculated reactor volumes are 1.5 dm
3
for nickel oxide as the
filling and 1 dm
3
for X4CrNi18-10. The 50 % larger reactor
volume when nickel oxide is used invokes considerably higher
investment costs, with the result that, in line with the project
specification, X4CrNi18-10 is chosen as the catalyst filling for
the reactor. The diameter of the flow reactor is selected as low
as possible to minimize radial concentration gradients and
avoid dead spaces in the reactor. The maximum possible
length of the reactor is given by the tube furnace intended for
the heating and stands at 48 cm. Thus, a total volume of 1 dm
3
results in an internal diameter of the flow tube of 6 cm. To pro-
tect against high-temperature corrosion the reactor is made
from the nickel-based alloy NiCr23Fe (alloy 601, material
no. 2.4851). The alloy is suitable for continuous operation up
to 1420 K.
5.1 Test Program
The varied process parameters for the prototype testing are
given in Tab. 6.
5.2 Results and Discussion
During test runs 14 the nitriding furnace was initially fed
with a small NH
3
volume flow rate of q
V,nit
=1 m
3
N
h
1
and the
NH
3
volume fraction at the entrance to the furnace gradually
increased up to 80 vol.-%. The reaction temperature was
1173 K. The ammonia measured values recorded at the exit of
the prototype are shown in Fig. 9.
In test 5, the nitriding furnace was fed with the maximum
ammonia volume flow rate. The residual NH
3
content after
the nitriding furnace was 80 vol.-% and the reaction tempera-
ture in the waste gas purification was T
R
=1273 K. The ammo-
nia measured value at the exit of the waste gas purification
was 38 ppm, which means that the objective of meeting
the threshold established in the TA-Luft of 40 ppm has
been achieved. The NH
3
conversions in the prototype were
also calculated and can be found in Fig. 10 versus the ammo-
nia volume fraction at the entrance to the waste gas purifica-
tion.
All conversions are above the required value of 99.99 %. The
conversion achieved at maximum volume flow rate with an
NH
3
fraction of 80 vol.-% totals 99.991 % and thus correlates
the conversion determined in the experiments on the laborato-
ry system (see also Fig. 8). Tests 1-4 showed a higher conver-
sion than the respective laboratory tests. The conversion
achieved in the laboratory tests at a reaction temperature of
1173 K and 40 vol.-% ammonia at the reactor entrance was
99.91 % and was thus 0.085 % under the conversion achieved
www.cet-journal.com 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2010, 33, No. 1, 145154
Table 5. Design data of the prototype.
X4CrNi18-10 Nickel oxide
Mean volume flow rate q
V,0
(m
3
h
1
) 15 15
Minimal residence time s
M
(s) 0.2 0.18
Porosity e 0.9 0.5
Volume of reactor V
reactor
(L) 1 1.5
Internal diameter D (cm) 6 7
Length L (cm) 48 48
Table 6. Process variables of the nitriding furnace and pilot
plant.
Nr. Volume flow rate
at the inlet of
nitriding furnace
Ammonia volume fraction
in the waste gas of
nitriding furnace
Reaction
temperature
_
V (m
3
N
h
1
) U
0,NH3
(vol.- %) T
R
(K)
1 1 30 1173
2 1 40 1173
3 1 60 1173
4 1 80 1173
5 1.5 80 1273
152 H. Ludewig et al.
on the prototype under the same process parameters. In con-
trast to the laboratory reactor, which was made from X6CrNi-
MoTi17-12-2 (1.4571), the prototype reactor is made of the
nickel-based alloy NiCr23Fe (2.4851). There is considerable
difference between the nickel fractions of the two alloys. While
1.4571 has approximately 12 % nickel by weight, the nickel-
based alloy has up to 63 % by weight. It can be assumed that
the high nickel content of the internal walls of the test reactor
caused the higher conversion. This conclusion is confirmed by
the results of Choudhary et al. [6] with
two different nickel contents. They de-
termined a conversion of 70 % with
Ni-SiO
2
containing 10 % nickel and
97 % with Ni-SiO
2
-Al
2
O
3
containing
65 % nickel. As the tests were con-
ducted under otherwise identical pro-
cess conditions, it can be assumed that
the higher nickel content of the catalyst
caused the higher conversion.
6 Conclusions
The reduction of the ammonia content
in waste gases from nitriding processes
by means of catalytic dissociation re-
quires a conversion of 99.99 % to meet
the threshold set out in the German
regulations. A laboratory unit was used
to determine the design data and pro-
cess conditions for a prototype. The
prototype attained the required con-
version of 99.99 % and thus the objec-
tive of falling below the Clean Air
Guideline limit of 40 ppm was
achieved. It was shown that the deter-
mination of a minimum residence time
in heterogeneous catalyzed gas reac-
tions with an increase in volume is a
suitable means of achieving a required
conversion. The transferability to in-
dustrial systems was proven by the ef-
fective application on the prototype.
Acknowledgements
This study was done within the Project
FH
3
No. 1723X06 sponsored by the
German Federal Ministry of Education
and Research. H. Ludewig acknowl-
edges support from HWP II by the
Senate of Bremen, Germany, and the
industrial partners.
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